Updated on 2022/03/31

写真a

 
MATSUDA Ryotaro
 
Organization
Graduate School of Engineering Materials Chemistry 2 Professor
Graduate School
Graduate School of Engineering
Undergraduate School
School of Engineering Chemistry and Biotechnology
Title
Professor
External link

Degree 1

  1. 博士(工学) ( 2005.5   京都大学 ) 

Research Interests 9

  1. Nanospace

  2. Adsorption

  3. Solid State Chemistry

  4. Porous Compound

  5. Coordination Polymer

  6. Metal Complex

  7. MOF

  8. 金属有機構造体

  9. Nanospace

Research Areas 2

  1. Others / Others  / Functional Material Chemistry

  2. Nanotechnology/Materials / Inorganic/coordination chemistry

Current Research Project and SDGs 1

  1. 新規ナノ空間物質の創成

Research History 1

  1. Nagoya University   Graduate School of Engineering   Professor

    2015.11

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    Country:Japan

Education 3

  1. Kyoto University   Graduate School, Division of Engineering

    2002.4 - 2005.3

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    Country: Japan

  2. Kyoto University   Graduate School of Engineering   Department of Synthetic Chemistry and Biological Chemistry

    2002.4 - 2005.3

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    Country: Japan

    Notes: PhD. course

  3. Kyoto University   Faculty of Engineering

    1996.4 - 2000.3

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    Country: Japan

Professional Memberships 3

  1. 日本化学会

  2. 日本吸着学会

  3. JAPAN SOCIETY OF COORDINATION CHEMISTRY

Committee Memberships 5

  1. 錯体化学会   理事  

    2020.10 - 2022.9   

  2. 錯体化学会   BJSCC編集委員  

    2018.10 - 2020.9   

  3. 日本化学会東海支部   常任幹事  

    2017.4 - 2019.3   

  4. 日本吸着学会運営委員会   運営委員  

    2015.4 - 2023.3   

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    Committee type:Academic society

  5. 日本吸着学会評議会   評議員  

    2015.4 - 2023.3   

Awards 6

  1. 第16回日本学術振興会賞

    2020.2   日本学術振興会  

  2. 文部科学大臣表彰 若手科学者賞

    2015.4   文部科学省  

  3. 平成24年度日本吸着学会奨励賞

    2012.11   日本吸着学会  

  4. 第61回進歩賞

    2012.3   日本化学会  

  5. 平成22年度錯体化学研究奨励賞

    2010.9   錯体化学会  

  6. 第23回井上研究奨励賞

    2007.2   井上科学振興財団  

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Papers 142

  1. Topochemical [2+2] Cycloaddition in a Two-Dimensional Metal-Organic Framework via SCSC Transformation Impacts Halogen center dot center dot center dot Halogen Interactions

    Khan Samim, Frontera Antonio, Matsuda Ryotaro, Kitagawa Susumu, Mir Mohammad Hedayetullah

    INORGANIC CHEMISTRY   Vol. 61 ( 7 ) page: 3029 - 3032   2022.2

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    Language:Japanese   Publishing type:Research paper (scientific journal)  

    DOI: 10.1021/acs.inorgchem.2c00128

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  2. Design of a MOF based on octa-nuclear zinc clusters realizing both thermal stability and structural flexibility

    Ma Yunsheng, Tang Xiaoyan, Chen Ming, Mishima Akio, Li Liangchun, Hori Akihiro, Wu Xiaoyu, Ding Lifeng, Kusaka Shinpei, Matsuda Ryotaro

    CHEMICAL COMMUNICATIONS   Vol. 58 ( 8 ) page: 1139 - 1142   2022.1

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    Language:Japanese   Publishing type:Research paper (scientific journal)  

    DOI: 10.1039/d1cc05893b

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  3. Selective Photochemical Reaction by Fixing Reactant as a MOF Building Block

    Ono Katsuya, Kusaka Shinpei, Matsuda Ryotaro

    CHEMISTRY LETTERS   Vol. 50 ( 12 ) page: 1987 - 1989   2021.12

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    Language:Japanese   Publishing type:Research paper (scientific journal)  

    DOI: 10.1246/cl.210525

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  4. Synthetic Strategy for Incorporating Carboxylate Ligands into Coordination Polymers under a Solvent-Free Reaction

    Hinokimoto Akira, Izu Hitoshi, Wei Yong-Sheng, Nakajo Toshinobu, Matsuda Ryotaro, Horike Satoshi

    CRYSTAL GROWTH & DESIGN   Vol. 21 ( 11 ) page: 6031 - 6036   2021.11

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    Language:Japanese   Publishing type:Research paper (scientific journal)  

    DOI: 10.1021/acs.cgd.1c00587

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  5. Stabilization of radical active species in a MOF nanospace to exploit unique reaction pathways

    Harada Yuki, Kusaka Shinpei, Nakajo Toshinobu, Kumagai Jun, Kim Cho Rong, Shim Joo Young, Hori Akihiro, Ma Yunsheng, Matsuda Ryotaro

    CHEMICAL COMMUNICATIONS     2021.10

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    Language:Japanese   Publishing type:Research paper (scientific journal)  

    DOI: 10.1039/d1cc04267j

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  6. Water Confined in MIL-101(Cr): Unique Sorption-Desorption Behaviors Revealed by Diffuse Reflectance Infrared Spectroscopy and Molecular Dynamics Simulation

    Gao Jiao, Fei Shubo, Ho Ya-Lun, Matsuda Ryotaro, Daiguji Hirofumi, Delaunay Jean-Jacques

    JOURNAL OF PHYSICAL CHEMISTRY C   Vol. 125 ( 32 ) page: 17786 - 17795   2021.8

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    Language:Japanese   Publishing type:Research paper (scientific journal)  

    DOI: 10.1021/acs.jpcc.1c03351

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  7. Fabrication of a Kagome-type MOF Membrane by Seeded Growth on Amino-functionalized Porous Al2O3 Substrate

    Wang Xiaoguang, Kusaka Shinpei, Hori Akihiro, Matsuda Ryotaro

    CHEMISTRY-AN ASIAN JOURNAL   Vol. 16 ( 15 ) page: 2018 - 2021   2021.8

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    Language:Japanese   Publishing type:Research paper (scientific journal)  

    DOI: 10.1002/asia.202100507

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  8. Triplet Carbene with Highly Enhanced Thermal Stability in the Nanospace of a Metal-Organic Framework

    Nakajo Toshinobu, Kumagai Jun, Kusaka Shinpei, Hori Akihiro, Hijikata Yuh, Pirillo Jenny, Ma Yunsheng, Matsuda Ryotaro

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   Vol. 143 ( 21 ) page: 8129 - 8136   2021.6

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    Language:Japanese   Publishing type:Research paper (scientific journal)  

    DOI: 10.1021/jacs.1c02430

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  9. Enhanced CO2 Adsorption by Insertion Reaction in the Nanospace of a Porphyrin-based MOF

    Morita Masashi, Kusaka Shinpei, Yonezu Akira, Ohara Yuki, Sakamoto Hirotoshi, Matsuda Ryotaro

    CHEMISTRY LETTERS   Vol. 50 ( 4 ) page: 640 - 643   2021.4

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    Language:Japanese   Publishing type:Research paper (scientific journal)  

    DOI: 10.1246/cl.200785

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  10. An Open-shell, Luminescent, Two-Dimensional Coordination Polymer with a Honeycomb Lattice and Triangular Organic Radical

    Kimura Shun, Uejima Motoyuki, Ota Wataru, Sato Tohru, Kusaka Shinpei, Matsuda Ryotaro, Nishihara Hiroshi, Kusamoto Tetsuro

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   Vol. 143 ( 11 ) page: 4329 - 4338   2021.3

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    Publishing type:Research paper (scientific journal)  

    DOI: 10.1021/jacs.0c13310

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  11. Modulation of Self-Assembly Enhances the Catalytic Activity of Iron Porphyrin for CO2 Reduction

    Tasaki Masahiro, Okabe Yuki, Iwami Hikaru, Akatsuka Chiharu, Kosugi Kento, Negita Kohei, Kusaka Sinpei, Matsuda Ryotaro, Kondo Mio, Masaoka Shigeyuki

    SMALL     2021.3

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    Publishing type:Research paper (scientific journal)  

    DOI: 10.1002/smll.202006150

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  12. Molecular motion in the nanospace of MOFs upon gas adsorption investigated by in situ Raman spectroscopy Reviewed

    Shinpei Kusaka, Yasuaki Nakajima, Akihiro Hori, Akira Yonezu, Kenta Kikushima, Wataru Kosaka, Yunsheng Ma, Ryotaro Matsuda

    Faraday Discussions   Vol. 225 ( 0 ) page: 70 - 83   2021.2

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    Molecular motions taking place in the nanospace of metal-organic frameworks (MOFs) are an interesting research subject, although not yet fully investigated. In this work, we utilized in situ Raman spectroscopy in the ultralow-frequency region to investigate the libration motion (including the rotational motion of phenylene rings) of MOFs, in particular [Cu2(bdc)2(dabco)] (Cu-JAST-1), where bdc = 1,4-benzenedicarboxylate and dabco = 1,4-diazabicyclo[2.2.2]octane. The libration mode of Cu-JAST-1 was found to be significantly suppressed by the adsorption of various guest molecules, such as CO2, Ar, and N2. In addition, an appreciable correlation between the libration mode and adsorption equilibrium time was identified, which provides useful novel tools in the design of MOFs acting as molecular adsorption and separation materials.

    DOI: 10.1039/d0fd00002g

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  13. Tuning Gate-Opening of a Flexible Metal–Organic Framework for Ternary Gas Sieving Separation

    Qiubing Dong, Xin Zhang, Shuang Liu, Rui Biao Lin, Yanan Guo, Yunsheng Ma, Akira Yonezu, Rajamani Krishna, Gongpin Liu, Jingui Duan, Ryotaro Matsuda, Wanqin Jin, Banglin Chen

    Angewandte Chemie - International Edition   Vol. 59 ( 50 ) page: 22756 - 22762   2020.12

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    In comparison with the fast development of binary mixture separations, ternary mixture separations are significantly more difficult and have rarely been realized by a single material. Herein, a new strategy of tuning the gate-opening pressure of flexible MOFs is developed to tackle such a challenge. As demonstrated by a flexible framework NTU-65, the gate-opening pressure of ethylene (C H ), acetylene (C H ), and carbon dioxide (CO ) can be regulated by temperature. Therefore, efficient sieving separation of this ternary mixture was realized. Under optimized temperature, NTU-65 adsorbed a large amount of C H and CO through gate-opening and only negligible amount of C H . Breakthrough experiments demonstrated that this material can simultaneously capture C H and CO , yielding polymer-grade (>99.99 %) C H from single breakthrough separation. 2 4 2 2 2 2 2 2 2 4 2 2 2 2 4

    DOI: 10.1002/anie.202011802

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  14. Trapping and Releasing of Oxygen in Liquid by Metal–Organic Framework with Light and Heat

    Masashi Fujimura, Shinpei Kusaka, Ayaka Masuda, Akihiro Hori, Yuh Hijikata, Jenny Pirillo, Yunsheng Ma, Ryotaro Matsuda

    Small     2020.11

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    Nanoporous materials can adsorb small molecules into their nanospaces. However, the trapping of light gas molecules dissolved in solvents suffers from low concentration and poor adsorption affinity. Here, the reversible trapping and releasing of dissolved oxygen are shown through integrating photosensitization and chemical capturing abilities into a metal–organic framework (MOF), MOMF-1. 9,10-Di(4-pyridyl)anthracene (dpa) ligands in MOMF-1 generates singlet oxygen from triplet oxygen under photoirradiation without additional photosensitizers, and successively reacts with it to produce anthracene endoperoxide, forming MOMF-2, which is proved crystallographically. The reverse reaction also proceeds quantitatively by heating MOMF-2. Moreover, MOMF-1 exhibits excellent water resistance, and completely removes oxygen of ppm order concentrations in water. The new material shown in this report allows controlling of the amount of dissolved oxygen, which can be applicable in various fields relating to numerous oxidation phenomena.

    DOI: 10.1002/smll.202004351

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  15. Molecular simulation study on the flexibility in the interpenetrated metal-organic framework LMOF-201 using reactive force field

    Ankit Agrawal, Mayank Agrawal, Donguk Suh, Yunsheng Ma, Ryotaro Matsuda, Akira Endo, Wei Lun Hsu, Hirofumi Daiguji

    Journal of Materials Chemistry A   Vol. 8 ( 32 ) page: 16385 - 16391   2020.8

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    Framework flexibility is one of the most important characteristics of metal-organic frameworks (MOFs), making them highly suitable for adsorption applications. There have been a limited number of computational efforts to study flexible MOFs in the literature, and they are mostly focused on MIL-53. We studied a flexible MOF known as LMOF-201, which was found to exhibit guest-induced flexible properties; however, the mechanism of the appearance of flexibility is still unclear. First, we validated our simulation results by reproducing the experimental isotherm and powder X-ray diffraction measurements of experimental structures using grand canonical Monte Carlo (GCMC) and reactive force field (ReaxFF) molecular dynamics (MD) simulations. Then, we demonstrated the importance of the presence of a carbonyl oxygen atom in LMOF-201 to induce flexibility. The mechanism determined in this study will enable LMOF-201 to be considered for adsorption applications in the future.

    DOI: 10.1039/c9ta12065c

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  16. Augmenting the Carbon Dioxide Uptake and Selectivity of Metal-Organic Frameworks by Metal Substitution: Molecular Simulations of LMOF-202

    Ankit Agrawal, Mayank Agrawal, Donguk Suh, Shubo Fei, Amer Alizadeh, Yunsheng Ma, Ryotaro Matsuda, Wei Lun Hsu, Hirofumi Daiguji

    ACS Omega   Vol. 5 ( 28 ) page: 17193 - 17198   2020.7

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    Metal organic frameworks (MOFs) are promising porous materials for the adsorption of CO2. Here, we report the study of a luminescent MOF (LMOF), called LMOF-202. We have employed Grand Canonical Monte Carlo (GCMC) simulations to understand and explain the adsorption phenomena inside LMOF-202, and based on the phenomena happening at the molecular level, we have varied the metal ions in LMOF-202 to increase the CO2 affinity and selectivity of the material. We show that the CO2 adsorption capacity and selectivity can be increased by approximately 1.5 times at 1 bar and 298 K by changing the metal ion from Zn to Ba. We also report the feasibility of using this material to capture CO2 from flue gas under realistic conditions (1 bar and 298 K). This work shows that LMOF-202 merits further consideration as a carbon capture adsorbent.

    DOI: 10.1021/acsomega.0c01267

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  17. Pseudo-Gated Adsorption with Negligible Volume Change Evoked by Halogen-Bond Interaction in the Nanospace of MOFs Reviewed International journal

    Prakash Kanoo, Ryotaro Matsuda, Hiroshi Sato, Liangchun Li, Nobuhiko Hosono, Susumu Kitagawa

    Chemistry - A European Journal   Vol. 26 ( 10 ) page: 2148 - 2153   2020.2

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    The enhancement of gas adsorption utilizing weak interactions in porous compounds is highly demanding for the design of energy-efficient storage materials. Here, we present a rational design for such an adsorption process by using synergistic functions between dynamic motion in a local module and weak but specific host–guest interactions, that is, halogen-bond (XB) interactions in metal–organic frameworks (MOFs). We designed a new porous coordination polymer (PCP), that is, Br-PCP, the pore surfaces of which are decorated with −CH Br groups and could be useful for interaction with CO molecules. In accordance with our anticipation, in-situ studies suggest that the adsorption step at approximately 54 kPa during CO adsorption is indeed facilitated by XB interactions with little change in the structural volume. This approach of integrating flexible XB modules in rigid PCPs is applicable for designing advanced gas storage systems. 2 2 2

    DOI: 10.1002/chem.201904703

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  18. Swift and efficient nuclear spin conversion of molecular hydrogen confined in Prussian blue analogs

    Yuta Ohtsubo, Akio Mishima, Akihiro Hori, Ryotaro Matsuda, Ryo Ohtani, Masaaki Ohba

    Chemistry Letters   Vol. 49 ( 2 ) page: 149 - 152   2020.2

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    The ortho-isomer of molecular hydrogen (o-H ) was converted to the para-isomer (p-H ) within 600 s by using Prussian blue analogs, {M [Cr (CN) ] } (MCr; M = Mn and Ni), as nuclear-spin conversion catalysts. The swift conversion was confirmed by in-situ Raman micro-spectroscopy under an H gas atmosphere (100 kPa) in a low temperature range (2090 K). The o-p ratio observed in MCr deviated from the theoretical value based on the Boltzmann distribution of H in a free rotational state to the para-rich proportion, which suggested the promotion of the o-p conversion at higher temperature. 2 2 3 6 2 2 2 II III

    DOI: 10.1246/cl.190829

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  19. Direct observation of dimethyl sulfide trapped by MOF proving efficient removal of sulfur impurities

    Masashi Morita, Akira Yonezu, Shinpei Kusaka, Akihiro Hori, Yunsheng Ma, Ryotaro Matsuda

    RSC Advances   Vol. 10 ( 8 ) page: 4710 - 4714   2020.1

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    Here, we report the adsorptive removal of trace amounts of dimethyl sulfide (DMS) using metal-organic frameworks (MOFs). Cu -based MOFs with open metal sites (OMSs), [Cu (btc) ] (HKUST-1), where btc = 1,3,5-benzenetricarboxylate, and without OMSs, [Cu (bdc) (dabco)] (Cu-JAST-1), where bdc = 1,4-benzenedicarboxylate and dabco = 1,4-diazabicyclo[2.2.2]octane, were investigated for the removal of DMS to compare their performance with that of Ag-Y zeolite, which is currently widely used in industry. HKUST-1 exhibited a considerably higher adsorption capacity for DMS than the other adsorbents, which was confirmed by breakthrough measurements. The adsorption state of DMS with HKUST-1 was directly revealed by single-crystal X-ray diffraction (SXRD) analysis and in situ Raman spectroscopy. In addition, it was shown that DMS can be removed by HKUST-1 even under humid conditions. 2+ 3 2 2 2

    DOI: 10.1039/c9ra09702c

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  20. Accelerated C<inf>2</inf>H<inf>2</inf>/CO<inf>2</inf> Separation by a Se-Functionalized Porous Coordination Polymer with Low Binding Energy Reviewed International journal

    Qiubing Dong, Yanan Guo, Haifei Cao, Suna Wang, Ryotaro Matsuda, Jingui Duan

    ACS Applied Materials and Interfaces   Vol. 12 ( 3 ) page: 3764 - 3772   2020.1

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    High-quality pure acetylene (C H ) is a kind of crucial starting material for various value-added products. However, selective capture of C H from the main impurity of CO via porous absorbents is a great challenge, as they possess extremely similar kinetic diameters and boiling points, as well as the explosive and reactive properties of C H . Herein, we report a porous coordination polymer (PCP), (NTU-55), which assembled from the coordination between a Cu dimer and a newly designed ligand with a nonmetal selenium (Se) site. Static single-component adsorption and dynamic breakthrough experiments reveal that desolvated NTU-55 can completely adsorb C H from the C H /CO mixture (1/4, v/v) at 298 K, along with higher C H capacity and much lower binding energy. The origin of this separation, as comprehensively revealed by density functional theory (DFT) calculations, is derived from the interaction discriminatory of C H and CO toward accessible Se and Cu adsorption sites. To the best of our knowledge, this is the first time to find the positive effect of nonmetal Se sites for selective C H capture. 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2

    DOI: 10.1021/acsami.9b20623

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  21. Grafting free carboxylic acid groups onto the pore surface of 3d porous coordination polymers for high proton conductivity Reviewed

    Yuanmeng Tian, Gan Liang, Tao Fan, Jin Shang, Shanshan Shang, Yunsheng Ma, Ryotaro Matsuda, Mingxian Liu, Man Wang, Liangchun Li, Susumu Kitagawa

    Chemistry of Materials   Vol. 31 ( 20 ) page: 8494 - 8503   2019.10

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    Copyright © 2019 American Chemical Society. Development of proton conduction materials with a high performance via functionalization of porous coordination polymers (PCPs) is challenging yet promising. Herein, a facile and efficient method to synthesize multicarboxylate-group-functionalized rigid ligands has been developed. Interestingly, when utilizing these ligands to prepare PCPs, the peripheral carboxylate groups of the ligands selectively coordinate to the metal ions for constructing the PCP frameworks while ortho-dicarboxylic acid groups on the central benzene ring remain free in the pores. Single-crystal X-ray diffractions and various gas sorption analyses reveal the characteristics of high-density free carboxylic acid groups in the pores of these PCPs, not only forming hydrogen-bond clusters and three-dimensional hydrogen-bond networks potentially, but also stimulating the flexibility of these very robust PCP frameworks. Based on this unique structure, the PCP functionalized with four free carboxylic acids on every ligand (TJU-102) exhibits a high proton conductivity of 5.26 × 10-2 S cm-1 at 90 °C and 98% relative humidity. The activation energy for proton conduction of TJU-102 is ca. 0.59 eV, suggesting that the conduction mechanism is predominantly vehicular.

    DOI: 10.1021/acs.chemmater.9b02924

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  22. Dynamic Topochemical Reaction Tuned by Guest Molecules in the Nanospace of a Metal-Organic Framework Reviewed

    Kusaka Shinpei, Kiyose Atsushi, Sato Hiroshi, Hijikata Yuh, Hori Akihiro, Ma Yunsheng, Matsuda Ryotaro

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   Vol. 141 ( 40 ) page: 15742 - 15746   2019.10

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    DOI: 10.1021/jacs.9b07682

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  23. Reversible low-temperature redox activity and selective oxidation catalysis derived from the concerted activation of multiple metal species on Cr and Rh-incorporated ceria catalysts Reviewed

    Ikemoto Satoru, Huang Xiubing, Muratsugu Satoshi, Nagase Shoko, Koitaya Takanori, Matsui Hirosuke, Yokota Gen-ichi, Sudoh Takatoshi, Hashimoto Ayako, Tan Yuanyuan, Yamamoto Susumu, Tang Jiayi, Matsuda Iwao, Yoshinobu Jun, Yokoyama Toshihiko, Kusaka Shinpei, Matsuda Ryotaro, Tada Mizuki

    PHYSICAL CHEMISTRY CHEMICAL PHYSICS   Vol. 21 ( 37 ) page: 20868 - 20877   2019.10

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    DOI: 10.1039/c9cp04625a

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  24. One-Step Synthesis of an Adaptive Nanographene MOF: Adsorbed Gas-Dependent Geometrical Diversity Reviewed

    Suginome Shun, Sato Hiroshi, Hori Akihiro, Mishima Akio, Harada Yuki, Kusaka Shinpei, Matsuda Ryotaro, Pirillo Jenny, Hijikata Yuh, Aida Takuzo

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   Vol. 141 ( 39 ) page: 15649 - 15655   2019.10

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    DOI: 10.1021/jacs.9b07732

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  25. Microwave-Assisted Hydrothermal Synthesis of [Al(OH)(1,4-NDC)] Membranes with Superior Separation Performances. Reviewed International journal

    Yi Liu, Akihiro Hori, Shinpei Kusaka, Nobuhiko Hosono, Mingrun Li, Ang Guo, Dongying Du, Yanshuo Li, Weishen Yang, Yunsheng Ma, Ryotaro Matsuda

    Chemistry, an Asian journal   Vol. 14 ( 12 ) page: 2072 - 2076   2019.6

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    In this study, we report a facile ligand-assisted in situ hydrothermal approach for preparation of compact [Al(OH)(1,4-NDC)] (1,4-NDC=1,4-naphthalenedicarboxylate) MOF membranes on porous γ-Al2 O3 substrates, which also served as the Al3+ source of MOF membranes. Simultaneously, it was observed that the heating mode exerted significant influence on the final microstructure and separation performance of [Al(OH)(1,4-NDC)] membranes. Compared with the conventional hydrothermal method, the employment of microwave heating led to the formation of [Al(OH)(1,4-NDC)] membranes composed of closely packed nanorods with superior H2 /CH4 selectivity.

    DOI: 10.1002/asia.201900152

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  26. Creation of MOFs with open metal sites by partial replacement of metal ions with different coordination numbers Reviewed

    Harada Yuki, Hijikata Yuh, Kusaka Shinpei, Hori Akihiro, Ma Yunsheng, Matsuda Ryotaro

    DALTON TRANSACTIONS   Vol. 48 ( 8 ) page: 2545 - 2548   2019.2

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    DOI: 10.1039/c8dt04218g

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  27. Highly responsive nature of porous coordination polymer surfaces imaged by in situ atomic force microscopy. Reviewed International journal

    Nobuhiko Hosono, Aya Terashima, Shinpei Kusaka, Ryotaro Matsuda, Susumu Kitagawa

    Nature chemistry   Vol. 11 ( 2 ) page: 109 - 116   2019.2

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    The ability of porous coordination polymers to undergo reversible structural transformations in response to the presence of guest molecules has been intensively investigated for applications such as molecular separation, storage, sensing and signalling processes. Here we report on the direct observation of the highly guest-responsive nature of the surface of a single-crystalline porous coordination polymer, which consists of paddlewheel zinc clusters and two types of ligand, by in situ liquid-phase atomic force microscopy. Observations were carried out in solution at constant temperature (28 °C) by high-speed atomic force microscopy with lattice resolution. A sharp and reversible response to the presence or absence of biphenyl guest molecules was observed, under conditions that can scarcely induce the transformation of the bulk crystal. Additionally, by modulating the surface coordination equilibrium, layer-by-layer delamination events were captured in real time at every ~13 s per frame.

    DOI: 10.1038/s41557-018-0170-0

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  28. Selective Sensing of Fe3+ Ions Using a Water-stable Magnesium Coordination Polymer Reviewed

    Liu Ye, Xu Ji, Tang Xiaoyan, Ma Yunsheng, Yuan Rongxin, Matsuda Ryotaro

    CHEMISTRY LETTERS   Vol. 48 ( 2 ) page: 156 - 158   2019.2

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    DOI: 10.1246/cl.180921

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  29. Kinetics of Water Vapor Adsorption and Desorption in MIL-101 Metal-Organic Frameworks Reviewed

    Yanagita Kosuke, Hwang Junho, Shamim Jubair A, Hsu Wei-Lun, Matsuda Ryotaro, Endo Akira, Delaunay Jean-Jacques, Daiguji Hirofumi

    JOURNAL OF PHYSICAL CHEMISTRY C   Vol. 123 ( 1 ) page: 387 - 398   2019.1

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    DOI: 10.1021/acs.jpcc.8b08211

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  30. Gas-responsive porous magnet distinguishes the electron spin of molecular oxygen Reviewed

    Kosaka Wataru, Liu Zhaoyuan, Zhang Jun, Sato Yohei, Hori Akihiro, Matsuda Ryotaro, Kitagawa Susumu, Miyasaka Hitoshi

    NATURE COMMUNICATIONS   Vol. 9   2018.12

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    DOI: 10.1038/s41467-018-07889-1

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  31. Insights into inorganic buffer layer-assisted in situ fabrication of MOF films with controlled microstructures Reviewed

    Liu Yi, Matsuda Ryotaro, Kusaka Shinpei, Hori Akihiro, Ma Yunsheng, Kitagawa Susumu

    CRYSTENGCOMM   Vol. 20 ( 43 ) page: 6995 - 7000   2018.11

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    DOI: 10.1039/c8ce01681j

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  32. Theoretical Insight into Gate-Opening Adsorption Mechanism and Sigmoidal Adsorption Isotherm into Porous Coordination Polymer Reviewed

    Zheng Jia-Jia, Kusaka Shinpei, Matsuda Ryotaro, Kitagawa Susumu, Sakaki Shigeyoshi

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   Vol. 140 ( 42 ) page: 13958 - 13969   2018.10

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    DOI: 10.1021/jacs.8b09358

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  33. Tetrametallic Ln(III) (Ln = Gd, Dy) phosphonate clusters: Spin cooler and single-molecule magnet Reviewed

    Tang Xiaoyan, Hua Jingkun, Ma Yunsheng, Hori Akihiro, Yuan Rongxin, Matsuda Ryotaro

    INORGANICA CHIMICA ACTA   Vol. 482   page: 900 - 904   2018.10

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    DOI: 10.1016/j.ica.2018.07.040

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  34. Self-assembly of lattices with high structural complexity from a geometrically simple molecule Reviewed

    Yamagishi Hiroshi, Sato Hiroshi, Hori Akihiro, Sato Yohei, Matsuda Ryotaro, Kato Kenichi, Aida Takuzo

    SCIENCE   Vol. 361 ( 6408 ) page: 1242 - 1245   2018.9

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    DOI: 10.1126/science.aat6394

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  35. Switchable gate-opening effect in metal-organic polyhedra assemblies through solution processing Reviewed

    Craig Gavin A, Larpent Patrick, Kusaka Shinpei, Matsuda Ryotaro, Kitagawa Susumu, Furukawa Shuhei

    CHEMICAL SCIENCE   Vol. 9 ( 31 )   2018.8

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    DOI: 10.1039/c8sc02263a

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  36. Generation of thiyl radicals in a zinc(ii) porous coordination polymer by light-induced post-synthetic deprotection Reviewed

    Shinpei Kusaka, Ryotaro Matsuda, Susumu Kitagawa

    Chemical Communications   Vol. 54 ( 38 ) page: 4782 - 4785   2018.5

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    Kinetic stabilisation of unstable chemical species in nanospace is of potential importance in the field of materials and synthetic chemistry, and porous coordination polymers (PCPs) represent a facile platform to provide such reaction fields. Thiyl radicals are important reactive substances that often play a leading role in organic and bioorganic chemistry. However, their generation in nanospace has been barely investigated due to synthetic difficulties. Here, we report a facile methodology for the functionalisation of active thiyl substituents on PCP pore surfaces using a post-synthetic protection and deprotection technique. The thiyl radicals were generated inside a zinc(ii)-based PCP upon the deprotection of asymmetric disulfides, which were used as the protecting groups by ultraviolet light irradiation.

    DOI: 10.1039/c8cc01837e

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    Scopus

  37. Purely Physisorption-Based CO-Selective Gate-Opening in Microporous Organically Pillared Layered Silicates Reviewed

    Markus M. Herling, Martin Rieß, Hiroshi Sato, Liangchun Li, Thomas Martin, Hussein Kalo, Ryotaro Matsuda, Susumu Kitagawa, Josef Breu

    Angewandte Chemie - International Edition   Vol. 57 ( 2 ) page: 564 - 568   2018.1

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    Separation of gas molecules with similar physical and chemical properties is challenging but nevertheless highly relevant for chemical processing. By introducing the elliptically shaped molecule, 1,4-dimethyl-1,4-diazabicyclo[2.2.2]octane, into the interlayer space of a layered silicate, a two-dimensional microporous network with narrow pore size distribution is generated (MOPS-5). The regular arrangement of the pillar molecules in MOPS-5 was confirmed by the occurrence of a 10 band related to a long-range pseudo-hexagonal superstructure of pillar molecules in the interlayer space. Whereas with MOPS-5 for CO2 adsorption, gate-opening occurs at constant volume by freezing pillar rotation, for CO the interlayer space is expanded at gate-opening and a classical interdigitated layer type of gate-opening is observed. The selective nature of the gate-opening might be used for separation of CO and N2 by pressure swing adsorption.

    DOI: 10.1002/anie.201710717

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    Scopus

  38. Porous magnet responsive to spins of oxygen molecules Reviewed

    Wataru Kosaka, Zhaoyuan Liu, Jun Zhang, Yohei Sato, Akihiro Hori, Ryotaro Matsuda, Susumu Kitagawa, Hitoshi Miyasaka

    Nat. Commun.   Vol. 9   page: 5420(1~) - 5420(~9)   2018

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  39. Cooperative Bond Scission in a Soft Porous Crystal Enables Discriminatory Gate Opening for Ethylene over Ethane Reviewed

    Susan Sen, Nobuhiko Hosono, Jia-Jia Zheng, Shinpei Kusaka, Ryotaro Matsuda, Shigeyoshi Sakaki, Susumu Kitagawa

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   Vol. 139 ( 50 ) page: 18313 - 18321   2017.12

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    Here we report a soft porous crystal possessing hemilabile cross-links in its framework that exhibits exclusive gate opening for ethylene, enabling the discriminatory adsorption of ethylene over ethane. A Co-based porous coordination polymer (PCP) bearing vinylogous tetrathiafulvalene (VTTF) ligands, [Co(VTTF)], forms Co-S bonds as intermolecular cross-links in its framework in the evacuated closed state. The PCP recognizes ethylene via d-pi complexation on the accessible metal site that displaces and cleaves the Co-S bond to "unlock" the closed structure. This ethylene-triggered unlocking event facilitates remarkable nonporous-to-porous transformations that open up accessible void space. This structural transformation follows a two-step gate-opening process. Each phase, including the intermediate structure, was successfully characterized by single-crystal X-ray diffraction analysis, which revealed an intriguing "half-open" structure suggestive of a disproportionate gate-opening phenomenon. The gate-opening mechanism was also investigated theoretically; density functional theory and Monte Carlo calculations revealed that the unique "half-open" phase corresponds to a substantially stable intermediate over the possible transformation trajectories. While ethylene opens the gate, ethane does not . because it is unable to coordinate to the Co center. This feature is maintained even at pressures above 1 MPa and at a temperature of 303 K, demonstrating the potential of the "gate-locking/unlocking" mechanism that exploits the hemilabile cross-linking in soft porous crystals.

    DOI: 10.1021/jacs.7b10110

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  40. Tuning the flexibility of interpenetrated frameworks by a small difference in the fluorene moiety Reviewed

    Yunsheng Ma, Yuki Harada, Akihiro Hori, Yuh Hijikata, Liangchun Li, Ryotaro Matsuda

    DALTON TRANSACTIONS   Vol. 46 ( 44 ) page: 15200 - 15203   2017.11

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    [Zn-2(FDC)(2)(bpy)] (LMOF-202) and [Zn-2(OFDC)(2)(bpy)] (LMOF-201) (FDC: fluorene-2,7-dicarboxylate, OFDC: 9-fluorenone-2,7-dicarboxylate, bpy: 4,4'-bipyridine) have interpenetrated isostructures. However, their gas sorption behaviors indicate that LMOF-202 is rigid, whereas LMOF-201 is flexible. We found that the structural flexibility of LMOF-201 was due to the addition of only one oxygen atom into the ligand.

    DOI: 10.1039/c7dt03338a

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  41. Characteristic Features of CO2 and CO Adsorptions to Paddle-Wheel type Porous Coordination Polymer Reviewed

    Jia-Jia Zheng, Shinpei Kusaka, Ryotaro Matsuda, Susumu Kitagawa, Shigeyoshi Sakaki

    JOURNAL OF PHYSICAL CHEMISTRY C   Vol. 121 ( 35 ) page: 19129 - 19139   2017.9

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    Adsorptions of CO, N-2, NO, and CO2 in a paddle-wheel type porous coordination polymer (PCP) [Cu(aip)] (aip = 5-azidoisophthalate) were investigated with ONIOM[MP4(SDQ):omega B97XD] method using a model system consisting of two [Cu-2(O2CC6H4-R)(4)] units (R = H and Me) and one [Cu-2(O2CC6H4R)(4)] unit, namely, dimer and monomer models. The experimental CO adsorption position was reproduced well by the present calculation with the dimer model. For adsorptions of CO, N-2, NO, and CO2 in the dimer model, the position of gas molecule deviates from the normal one that is found in the monomer model and becomes more distant from the surrounding phenyl group(s) of the neighbor [Cu(aip)] unit. For all of these gas molecules, the calculated binding energy (BE) at the deviating adsorption position is larger than that at the normal one against our expectation that the normal position is the best for the gas adsorption. The deviation of gas adsorption position arises from the interaction between the organic linker (O2CC6H4-R moiety) and gas molecule. For all cases, the exchange repulsion with the organic linker decreases to a larger extent than the attractive electrostatic and dispersion interactions decrease when going from the normal position to the deviating one. To enhance the binding energy of gas molecule, the introduction of electron-donating substituent on phenyl moiety is computationally recommended for this PCP.

    DOI: 10.1021/acs.jpcc.7b02707

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  42. Density Gradation of Open Metal Sites in the Mesospace of Porous Coordination Polymers Reviewed

    Jingui Duan, Masakazu Higuchi, Jiajia Zheng, Shin-ichiro Noro, I-Ya Chang, Kim Hyeon-Deuk, Simon Mathew, Shinpei Kusaka, Easan Sivaniah, Ryotaro Matsuda, Shigeyoshi Sakaki, Susumu Kitagawa

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   Vol. 139 ( 33 ) page: 11576 - 11583   2017.8

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    The prevalence of the condensed phase, interpenetration, and fragility of ruesoporous coordination polymers (meso-PCPs) featuring dense open metal sites (OMSs) place strict limitations en their preparation, as revealed by experimental and `theoretical reticular chemistry investigations. Herein, we propose a rational design of stabilized high-porosity meso-PCPs, employing a 'low-symmetry ligand in combination with the shortest linker, formic acid. The resulting dimeric dusters (PCP-31 and PCP-32) exhibit high surface areas, ultrahigh porosities, and high OMS derisities (3.76 and 3.29 nmol g(-1) respectively), enabling highly selective- and effective separation of C2H2 from C2H2/CO2 mixtures at 298 K, as verified by binding energy (BE) and electrostatic potentials (ESP) calculations.

    DOI: 10.1021/jacs.7b05702

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  43. Flexible interlocked porous frameworks allow quantitative photoisomerization in a crystalline solid Reviewed

    Yongtai Zheng, Hiroshi Sato, Pengyan Wu, Hyung Joon Jeon, Ryotaro Matsuda, Susumu Kitagawa

    NATURE COMMUNICATIONS   Vol. 8   2017.7

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    Photochromic molecules have shown much promise as molecular components of stimuli-responsive materials, but despite recent achievements in various photoresponsive materials, quantitative conversion in photochemical reactions in solids is hampered by the lack of intrinsic structural flexibility available to release stress and strain upon photochemical events. This issue remains one of the challenges in developing solid-state photoresponsive materials. Here, we report a strategy to realize photoresponsive crystalline materials showing quantitative reversible photochemical reactions upon ultraviolet and visible light irradiation by introducing structural flexibility into crystalline porous frameworks with a twofold interpenetration composed of a diarylethene-based ligand. The structural flexibility of the porous framework enables highly efficient photochemical electrocyclization in a singlecrystal- to-single-crystal manner. CO2 sorption on the porous crystal at 195 K is reversibly modulated by light irradiation, and coincident X-ray powder diffraction/sorption measurements clearly demonstrate the flexible nature of the twofold interpenetrated frameworks.

    DOI: 10.1038/s41467-017-00122-5

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  44. Constant Volume Gate-Opening by Freezing Rotational Dynamics in Microporous Organically Pillared Layered Silicates Reviewed

    Baerwinkel Kilian, Herling Markus M., Riess Martin, Sato Hiroshi, Li Liangchun, Avadhut Yamini S., Kemnitzer Tobias W., Kalo Hussein, Senker Juergen, Matsuda Ryotaro, Kitagawa Susumu, Breu Josef

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   Vol. 139 ( 2 ) page: 904-909   2017.1

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    DOI: 10.1021/jacs.6b11124

  45. Electron Paramagnetic Resonance Study of Guest Molecule-Influenced Magnetism in Kagome Metal-Organic Framework Reviewed

    Mantas Simenas, Ryotaro Matsuda, Susumu Kitagawa, Andreas Poeppl, Juras Banys

    JOURNAL OF PHYSICAL CHEMISTRY C   Vol. 120 ( 48 ) page: 27462 - 27467   2016.12

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    We present a continuous-wave electron paramagnetic resonance (EPR) study of Cu(ipa) (H2O) (ipa stands for isophthalate ligand) metal organic framework (MOP) that is based on the kagome topology. The main structural unit of this compound is a copper paddle-wheel (PW) consisting of two Cu2+ ions interconnected via four carboxylate groups in the syn- syn fashion. X- and Q-band EPR measurements of this MOF allow us to probe distinct magnetic interactions of different magnitudes that originate from these dinuclear units. EPR experiments performed at different temperatures reveal that two Cu2+ ions in a single PW are antiferromagnetically coupled to the total spin S = 0 state with the exchange coupling constant J = 285 cm(-1). The fine structure pattern observed in the spectra indicates the thermal population of the excited triplet S = 1 spin states of the Cu2+ pairs. Spectral simulations are used to determine the fine and hyperfine structure tensors of the PW units. At higher temperatures a collapse of the fine structure to a single EPR line is observed, indicating the interdinuclear exchange of the S = 1 spin states mediated via the isophthalate linkers. Comparison of the EPR results with the structural X-ray diffraction data reveals that the dehydration of the compound opens an additional spin triplet exchange path joining apical positions of the PWs. We estimated the effective exchange coupling constants in the as-synthesized and dehydrated forms of the compound by simulating the observed powder patterns. It is shown that the additional path is reversibly closed after the dehydrated sample is allowed to interact with air, demonstrating a peculiar relationship between the adsorbed guest molecules and magnetic properties of kagome MOFs even at room temperature.

    DOI: 10.1021/acs.jpcc.6b09853

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  46. Rhodium-Organic Cuboctahedra as Porous Solids with Strong Binding Sites Reviewed

    Shuhei Furukawa, Nao Horike, Mio Kondo, Yuh Hijikata, Arnau Carne-Sanchez, Patrick Larpent, Nicolas Louvain, Stephane Diring, Hiroshi Sato, Ryotaro Matsuda, Ryuji Kawano, Susumu Kitagawe

    INORGANIC CHEMISTRY   Vol. 55 ( 21 ) page: 10843 - 10846   2016.11

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    The upbuilding of dirhodium tetracarboxylate paddlewheels into porous architectures is still challenging because of the inertness of equatorial carboxylates for ligand-exchange reaction. Here we demonstrate the synthesis of a new family of metal organic cuboctahedra by connecting dirhodium units through 1,3-benzenedicarboxylate and assembling cuboctahedra as porous solids. Carbon monoxide and nitric oxide were strongly trapped in the internal cavity thanks to the strong affinity of unsaturated axial coordination sites of dirhodium centers.

    DOI: 10.1021/acs.inorgchem.6b02091

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  47. Crystal Dynamics in Multi-stimuli-Responsive Entangled Metal-Organic Frameworks Reviewed

    Prakash Kanoo, Ritesh Haldar, Sandeep K. Reddy, Arpan Hazra, Satyanarayana Bonakala, Ryotaro Matsuda, Susumu Kitagawa, Sundaram Balasubramanian, Tapas Kumar Maji

    CHEMISTRY-A EUROPEAN JOURNAL   Vol. 22 ( 44 ) page: 15864 - 15873   2016.10

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:WILEY-V C H VERLAG GMBH  

    An understanding of solid-state crystal dynamics or flexibility in metal-organic frameworks (MOFs) showing multiple structural changes is highly demanding for the design of materials with potential applications in sensing and recognition. However, entangled MOFs showing such flexible behavior pose a great challenge in terms of extracting information on their dynamics because of their poor single-crystallinity. In this article, detailed experimental studies on a twofold entangled MOF (f-MOF-1) are reported, which unveil its structural response toward external stimuli such as temperature, pressure, and guest molecules. The crystallographic study shows multiple structural changes in f-MOF-1, by which the 3D net deforms and slides upon guest removal. Two distinct desolvated phases, that is, f-MOF-1a and f-MOF-1b, could be isolated; the former is a metastable one and transformable to the latter phase upon heating. The two phases show different gated CO2 adsorption profiles. DFT-based calculations provide an insight into the selective and gated adsorption behavior with CO2 of f-MOF-1b. The gate-opening threshold pressure of CO2 adsorption can be tuned strategically by changing the chemical functionality of the linker from ethanylene (-CH2-CH2-) in f-MOF-1 to an azo (-N=N-) functionality in an analogous MOF, f-MOF-2. The modulation of functionality has an indirect influence on the gate-opening pressure owing to the difference in inter-net interaction. The framework of f-MOF-1 is highly responsive toward CO2 gas molecules, and these results are supported by DFT calculations.

    DOI: 10.1002/chem.201602087

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  48. Metal-Organic Polyhedral Core as a Versatile Scaffold for Divergent and Convergent Star Polymer Synthesis Reviewed

    Nobuhiko Hosono, Mika Gochomori, Ryotaro Matsuda, Hiroshi Sato, Susumu Kitagawa

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   Vol. 138 ( 20 ) page: 6525 - 6531   2016.5

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    We herein report the divergent and convergent synthesis of coordination star polymers (CSP) by using metal organic polyhedrons (MOPs) as a multifunctional core. For the divergent route, copper-based great rhombicuboctahedral MOPs decorated with dithiobenzoate or trithioester chain transfer groups at the periphery were designed. Subsequent reversible addition fragmentation chain transfer (RAFT) polymerization of monomers mediated by the MOPs gave star polymers, in which 24 polymeric arms were grafted from the MOP core. On the other hand, the convergent route provided identical CSP architectures by simple mixing of a macroligand and copper ions. Isophthalic acid-terminated polymers (so-called macroligands) immediately formed the corresponding CSPs through a coordination reaction with copper(II) ions. This convergent route enabled us to obtain miktoarm CSPs with tunable chain compositions through ligand mixing alone. This powerful method allows instant access to a wide variety of multicomponent star polymers that conventionally have required highly skilled and multistep syntheses. MOP-core CSPs are a new class of star polymer that can offer a design strategy for highly processable porous soft materials by using coordination nanocages as a building component.

    DOI: 10.1021/jacs.6b01758

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  49. An Adsorbate Discriminatory Gate Effect in a Flexible Porous Coordination Polymer for Selective Adsorption of CO2 over C2H2 Reviewed

    Maw Lin Foo, Ryotaro Matsuda, Yuh Hijikata, Rajamani Krishna, Hiroshi Sato, Satoshi Horike, Akihiro Hori, Jingui Duan, Yohei Sato, Yoshiki Kubota, Masaki Takata, Susumu Kitagawa

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   Vol. 138 ( 9 ) page: 3022 - 3030   2016.3

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    The adsorptive separation of C2H2 and CO2 via porous materials is nontrivial due to the close similarities of their boiling points and kinetic diameters. In this work, we describe a new flexible porous coordination polymer (PCP) [Mn(bdc)(dpe)] (H(2)bdc = 1,4-benzenedicarboxylic acid, dpe = 1,2-di(4-pyridyl)ethylene) having zero-dimensional pores, which shows an adsorbate discriminatory gate effect. The compound shows gate opening, type abrupt adsorption for C2H2 but not for CO2, leading to an appreciable selective adsorption of CO2 over C2H2 at near ambient temperature (273 K). The origin of this unique selectivity, as unveiled by in situ adsorption-X-ray diffraction experiments and density functional theory calculations, is due to vastly different orientations between the phenylene ring of bdc and each gas in the nanopores. The structural change by photochemical transformation of this PCP via [2 + 2] photodimerization leads to the removal of inverse CO2/C2H2 selectivity, verifying the mechanism of the guest discriminatory gate effect.

    DOI: 10.1021/jacs.5b10491

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  50. A Convenient Strategy for Designing a Soft Nanospace: An Atomic Exchange in a Ligand with Isostructural Frameworks Reviewed

    Yunsheng Ma, Ryotaro Matsuda, Hiroshi Sato, Yuh Hijikata, Liangchun Li, Shinpei Kusaka, Mawlin Foo, Fengfeng Xue, George Akiyama, Rongxin Yuan, Susumu Kitagawa

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   Vol. 137 ( 50 ) page: 15825 - 15832   2015.12

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    Direct observation of gas molecules confined in the nanospace of porous materials by single-crystal X-ray diffraction (SXRD) technique is, significant because it leads to deep insight into the adsorption mechanism and the actual state of the adsorbents in molecular level. A recent study revealed that flexibility is one of the important factors to achieve periodic guest accommodation in the nanospace enabling direct observation of gas molecules. Here, we report a convenient strategy to tune the framework flexibility by just an atomic exchange in a ligand, which enables us to easily construct a soft nanospace as the best platform to study gas adsorption. Indeed, we succeeded to observe C2H2 and CO2 molecules confined in the pores of a flexible porous coordination polymer (PCP-N) in different configurations using SXRD measurement, whereas gas molecules in a rigid framework (PCP-C) isostructural to PCP-N were not seen crystallographically. The result of the coincident in situ powder X-ray diffraction and adsorption measurement for PCP-N unambiguously showed that the framework could flexibly transform to trap gas molecules with a commensurate fashion. In addition, for PCP-N, we found that the adsorbed gas molecules induced significant structural change involving dimensional change of the pore from one-dimensional to three-dimensional, and subsequently, additional gas molecules formed periodic molecular clusters in the nanospace.

    DOI: 10.1021/jacs.5b09666

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  51. High CO2/CH4 Selectivity of a Flexible Copper(II) Porous Coordination Polymer under Humid Conditions Reviewed

    Shin-ichiro Noro, Ryotaro Matsuda, Yuh Hijikata, Yasutaka Inubushi, Sadamu Takeda, Susumu Kitagawa, Yukiko Takahashi, Masashi Yoshitake, Kazuya Kubo, Takayoshi Nakamura

    CHEMPLUSCHEM   Vol. 80 ( 10 ) page: 1517 - 1524   2015.10

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    The development of highly efficient CO2 separation materials is very important for environmental preservation and energy conservation. Crystalline porous coordination polymers (PCPs)/metal-organic frameworks are one of a number of promising types of porous materials for CO2 separation because of their controllable pore size, shape and surface function. Simultaneously, the unique structural flexibility of PCPs affords both high CO2 selectivity and inexpensive regeneration. However, this family of materials suffers from the coexistence of water that destroys the framework of PCPs and its adsorption in the pores is greater than that of CO2, which results in a deterioration in CO2-separation performance. Herein, a flexible and hydrophobic CuII PCP that is stable towards water has been designed and synthesised. This PCP has extremely high adsorption selectivity for CO2 over CH4, derived from its structural flexibility. Furthermore, the obtained water-tolerant flexible PCP, under CO2/CH4 mixed-gas conditions, exhibits highly selective CO2 adsorption over CH4, even in the presence of water.

    DOI: 10.1002/cplu.201500278

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  52. Remarkable Oxygen Intake/Release of BaYMn2O5+delta Viewed from High-Temperature Crystal Structure Reviewed

    Teruki Motohashi, Taira Takahashi, Makoto Kimura, Yuji Masubuchi, Shinichi Kikkawa, Yoshiki Kubota, Yoji Kobayashi, Hiroshi Kageyama, Masaki Takata, Susumu Kitagawa, Ryotaro Matsuda

    JOURNAL OF PHYSICAL CHEMISTRY C   Vol. 119 ( 5 ) page: 2356 - 2363   2015.2

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    Crystal structure of double-perovskite type BaYMn2O5+delta was studied by high-temperature synchrotron X-ray diffraction (SXRD) under precisely controlled oxygen pressure to gain deeper understanding of the remarkable oxygen intake/release capability of this oxide. The in situ SXRD analysis at 750 degrees C revealed that this oxide undergoes a distinct structural change upon lowering oxygen pressure, from a slightly oxygen-deficient delta = 1 phase (BaYMn2O5.89; P(O-2) = 10(3) Pa) to an oxygen-vacancy ordered delta = 0.5 phase (BaYMn2O5.51; P(O-2) = 10 Pa). The BaYMn2O5.89 structure (orthorhombic Cmmm) involves statistical distribution of oxygen vacancies within the yttrium plane. Meanwhile, the BaYMn2O5.51 structure (orthorhombic Icma) contains arrays of pyramidal MnO5 and octahedral MnO6 forming an alternate ordering, which is stabilized by a particular Mn3+ orbital ordering with collective displacements of Y3+ arrays. Thus, the discontinuous change in the oxygen content can be attributed to the structural reconstruction with oxygen/vacancy redistribution accompanied by yttrium displacement organization.

    DOI: 10.1021/jp511648b

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  53. Porous coordination polymers with ubiquitous and biocompatible metals and a neutral bridging ligand Reviewed

    Shin-ichiro Noro, Junya Mizutani, Yuh Hijikata, Ryotaro Matsuda, Hiroshi Sato, Susumu Kitagawa, Kunihisa Sugimoto, Yasutaka Inubushi, Kazuya Kubo, Takayoshi Nakamura

    NATURE COMMUNICATIONS   Vol. 6   2015.1

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    The design of inexpensive and less toxic porous coordination polymers (PCPs) that show selective adsorption or high adsorption capacity is a critical issue in research on applicable porous materials. Although use of Group II magnesium(II) and calcium(II) ions as building blocks could provide cheaper materials and lead to enhanced biocompatibility, examples of magnesium(II) and calcium(II) PCPs are extremely limited compared with commonly used transition metal ones, because neutral bridging ligands have not been available for magnesium(II) and calcium(II) ions. Here we report a rationally designed neutral and charge-polarized bridging ligand as a new partner for magnesium(II) and calcium(II) ions. The three-dimensional magnesium(II) and calcium(II) PCPs synthesized using such a neutral ligand are stable and show selective adsorption and separation of carbon dioxide over methane at ambient temperature. This synthetic approach allows the structural diversification of Group II magnesium(II) and calcium(II) PCPs.

    DOI: 10.1038/ncomms6851

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  54. Catalytic Glucose Isomerization by Porous Coordination Polymers with Open Metal Sites Reviewed

    George Akiyama, Ryotaro Matsuda, Hiroshi Sato, Susumu Kitagawa

    CHEMISTRY-AN ASIAN JOURNAL   Vol. 9 ( 10 ) page: 2772 - 2777   2014.10

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    Highly efficient catalytic isomerization reactions from glucose to fructose in aqueous media using porous coordination polymers (PCPs) or metal-organic frameworks (MOFs) is reported for the first time. The catalytic activity of PCPs functionalized with NH2, (CH3)(2), NO2, and SO3H groups on the pore surface is systematically tested. The catalytic activity can be tuned by the acidity of open metal sites (OMSs) by modifying the organic linkers with the functional groups. As a result, it is demonstrated that MIL-101 functionalized with SO3H not only shows high conversion of glucose but also selectively produces fructose. Further, catalytic one-pot conversion of amylose to fructose is achieved, thanks to the high stability of the framework in an acidic solution. These results show that MOF/PCP compounds having OMSs are promising materials for various useful heterogeneous catalytic reactions, in particular in the biomass field.

    DOI: 10.1002/asia.201402119

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  55. Amine-Responsive Adaptable Nanospaces: Fluorescent Porous Coordination Polymer for Molecular Recognition Reviewed

    Ritesh Haldar, Ryotaro Matsuda, Susumu Kitagawa, Subi J. George, Tapas Kumar Maji

    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   Vol. 53 ( 44 ) page: 11772 - 11777   2014.10

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:WILEY-V C H VERLAG GMBH  

    Flexible and dynamic porous coordination polymers (PCPs) with well-defined nanospaces composed of chromophoric organic linkers provide a scaffold for encapsulation of versatile guest molecules through noncovalent interactions. PCPs thus provide a potential platform for molecular recognition. Herein, we report a flexible 3D supramolecular framework {[Zn(ndc)(o-phen)]center dot DMF}(n) (o-phen= 1,10-phenanthroline, ndc=2,6-napthalenedicarboxylate) with confined nanospaces that can accommodate different electron-donating aromatic amine guests with selective turn-on emission signaling. This system serves as a molecular recognition platform through an emission-readout process. Such unprecedented tunable emission with different amines is attributed to its emissive charge-transfer (CT) complexation with o-phen linkers. In certain cases this CT emission is further amplified by energy transfer from the chromophoric linker unit ndc, as evidenced by single-crystal X-ray structural characterization.

    DOI: 10.1002/anie.201405619

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  56. Coordination Programming in the Design of Porous Coordination Polymers: Tuning of the Electronic Activity of Frameworks for Selective Nitrogen Monoxide Trapping Reviewed

    Wataru Kosaka, Kayo Yamagishi, Ryotaro Matsuda, Susumu Kitagawa, Masaki Takata, Hitoshi Miyasaka

    CHEMISTRY LETTERS   Vol. 43 ( 6 ) page: 890 - 892   2014.6

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    A change of building block from [Ru2(II),(II)(p-FPhCO2)(4)] to [Ru-2(II,II)(4-F-2-OMePhCO2)(4)] in a phenazine hz)-bridged [Ru-2(II,II)] chain compound led to a high selectivity toward nitrogen monoxide (NO) in the adsorption characteristics. High selectivity was observed despite the fact that electronically negative sites that enable close contact with NO molecules are not present in the pores, in contrast to [Ru-2(II,II)(4-Cl-2-OMePhCO2)(4)(phz)], which also exhibited selective NO adsorption.

    DOI: 10.1246/cl.140190

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  57. Microporous structures having phenylene fin: Significance of substituent groups for rotational linkers in coordination polymers Reviewed

    Ryotaro Matsuda, Wataru Kosaka, Ryo Kitaura, Yoshiki Kubota, Masaki Takata, Susumu Kitagawa

    MICROPOROUS AND MESOPOROUS MATERIALS   Vol. 189   page: 83 - 90   2014.5

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    Microporous coordination polymers having various shaped apertures were synthesized and crystallographically characterized using substituted terephthalate ligands. The substituents exert a notable influence on the channel size and shape depending on the orientations and disordering of the phenylene units such as a fin. This is a new aspect of porous coordination polymers, which would provide important information for a precise design of the micropore. (C) 2013 Elsevier Inc. All rights reserved.

    DOI: 10.1016/j.micromeso.2013.10.029

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  58. A Crystalline Porous Coordination Polymer Decorated with Nitroxyl Radicals Catalyzes Aerobic Oxidation of Alcohols Reviewed

    Liangchun Li, Ryotaro Matsuda, Iku Tanaka, Hiroshi Sato, Prakash Kanoo, Hyung Joon Jeon, Maw Lin Foo, Atsushi Wakamiya, Yasujiro Murata, Susumu Kitagawa

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   Vol. 136 ( 21 ) page: 7543 - 7546   2014.5

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    A porous coordination polymer (PCP) has been synthesized employing an organic ligand in which a stable free radical, isoindoline nitroxide, is incorporated. The crystalline PCP possesses one-dimensional channels decorated with the nitroxyl catalytic sites. When O-2 gas or air was used as the oxidant, this PCP was verified to be an efficient, recyclable, and widely applicable catalyst for selective oxidation of various alcohols to the corresponding aldehydes or ketones.

    DOI: 10.1021/ja5019095

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  59. MATERIALS CHEMISTRY Selectivity from flexibility Reviewed

    Ryotaro Matsuda

    NATURE   Vol. 509 ( 7501 ) page: 434 - 435   2014.5

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    DOI: 10.1038/509434a

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  60. Self-Accelerating CO Sorption in a Soft Nanoporous Crystal Reviewed

    Hiroshi Sato, Wataru Kosaka, Ryotaro Matsuda, Akihiro Hori, Yuh Hijikata, Rodion V. Belosludov, Shigeyoshi Sakaki, Masaki Takata, Susumu Kitagawa

    SCIENCE   Vol. 343 ( 6167 ) page: 167 - 170   2014.1

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    Carbon monoxide (CO) produced in many large-scale industrial oxidation processes is difficult to separate from nitrogen (N-2), and afterward, CO is further oxidized to carbon dioxide. Here, we report a soft nanoporous crystalline material that selectively adsorbs CO with adaptable pores, and we present crystallographic evidence that CO molecules can coordinate with copper(II) ions. The unprecedented high selectivity was achieved by the synergetic effect of the local interaction between CO and accessible metal sites and a global transformation of the framework. This transformable crystalline material realized the separation of CO from mixtures with N-2, a gas that is the most competitive to CO. The dynamic and efficient molecular trapping and releasing system is reminiscent of sophisticated biological systems such as heme proteins.

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  61. Functional Hybrid Porous Coordination Polymers Reviewed

    Maw Lin Foo, Ryotaro Matsuda, Susumu Kitagawa

    CHEMISTRY OF MATERIALS   Vol. 26 ( 1 ) page: 310 - 322   2014.1

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    Porous coordination polymers (PCPs) have attracted vast interest in recent years because of their possibility for rational design of crystal structures and functional properties. An emerging trend in PCP research is hybridization, which is the subject of this review. We have divided hybrid PCPs into three broad classes: class I, isomorphous mixed metal/ligand PCPs; class II, core@shell PCPs; class III, PCP superset of guest or PCPs with accommodated guests. In this Review, we examine 62 representative hybrid PCPs in the area of gas adsorption/separation/storage, luminescence, catalysis, drug delivery, and ionic conductivity with representative examples of each class to understand the underlying principles of hybridization for PCPs and their advantages over conventional PCPs. The future directions and applications of hybrid PCPs are postulated.

    DOI: 10.1021/cm402136z

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  62. Highly proton conductive nanoporous coordination polymers with sulfonic acid groups on the pore surface Reviewed

    Padmini Ramaswamy, Ryotaro Matsuda, Wataru Kosaka, George Akiyama, Hyung Joon Jeon, Susumu Kitagawa

    CHEMICAL COMMUNICATIONS   Vol. 50 ( 9 ) page: 1144 - 1146   2014

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    Three new sulfonated porous coordination polymers (PCPs)/metal-organic frameworks (MOFs) have been synthesized using solvothermal methods. These PCPs possess porous structures with non-coordinating sulfonic acid groups or sulfonate with dimethyl ammonium cations and exhibit high proton conductivity at a low humidity of 60% RH (relative humidity) at ambient temperature.

    DOI: 10.1039/c3cc47980c

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  63. The densely fluorinated nanospace of a porous coordination polymer composed of perfluorobutyl-functionalized ligands Reviewed

    Hyung Joon Jeon, Ryotaro Matsuda, Prakash Kanoo, Hiroshi Kajiro, Liangchun Li, Hiroshi Sato, Yongtai Zheng, Susumu Kitagawa

    CHEMICAL COMMUNICATIONS   Vol. 50 ( 74 ) page: 10861 - 10863   2014

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    A perfluorobutyl-functionalized two-dimensional porous coordination polymer (PCP), {[Cu(bpbtp)(L)(DMF)]center dot(DMF)}(n) (H(2)bpbtp = 2,5-bis(perfluorobutyl) terephthalic acid, L = 2,5-bis(perfluorobutyl)-1,4-bis(4-pyridyl)benzene, DMF = N, N-dimethylformamide) has been synthesized and structurally characterized. The pore surface of the PCP is decorated with pendant perfluorobutyl groups which fabricate a densely fluorinated nanospace resulting in unique gas sorption properties.

    DOI: 10.1039/c4cc04505j

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  64. Selective NO trapping in the pores of chain-type complex assemblies based on electronically activated paddlewheel-type [Ru2II,II]/ [Rh2II,II] dimers Reviewed

    Wataru Kosaka, Kayo Yamagishi, Akihiro Hori, Hiroshi Sato, Ryotaro Matsuda, Susumu Kitagawa, Masaki Takata, Hitoshi Miyasaka

    Journal of the American Chemical Society   Vol. 135 ( 49 ) page: 18469 - 18480   2013.12

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    The design of porous materials that undergo selective adsorption of a specific molecule is a critical issue in research on porous coordination polymers or metal-organic frameworks. For the purpose of the selective capture of molecules possessing an electron-acceptor character such as nitric oxide (NO), one-dimensional chain compounds possessing a high donor character have been synthesized using 4-chloroanisate-bridged paddlewheel-type dimetal(II, II) complexes with M = Ru and Rh and phenazine (phz) as the chain linker: [M 2(4-Cl-2-OMePhCO2)4(phz)]·n(CH 2Cl2) (M = Ru, 1
    Rh, 2). These compounds are isostructural and are composed of chains with a [-{M2}-phz-] repeating unit and CH2Cl2 occupying the void space between the chains. Compounds 1 and 2 change to a new phase (1-dry and 2-dry) upon evacuating the crystallization solvent (CH2Cl2) and almost lose their pores in the drying process: no void space in 1-dry and 31.8 Å3, corresponding to 2.9% of the cell volume, in 2-dry. Nevertheless, the compounds show a unique gas accommodation ability. Accompanied by a structural transformation (i.e., the first gate-opening) at low pressures of &lt
    10 kPa, both compounds show a typical physisorption isotherm for O 2 (90 K) and CO2 (195 K), with the adsorption amount of ca. 2-4 gas molecules per [M2] unit. In addition, the adsorption isotherm for NO (121 K) involves the first gate-opening followed by a second gate-opening anomaly at NO pressures of ≈52 kPa for 1-dry and ≈21 kPa for 2-dry. At the first gate-opening, the absorbed amount of NO is ca. 4 molecules per [M2] unit, and then it reaches 8.4 and 6.3 for 1-dry and 2-dry, respectively, at 95 kPa. Only the isotherm for NO exhibits hysteresis in the desorption process, and some of the NO molecules are trapped in pores even after evacuating at 121 K, although it recovers to the original dried sample on heating to room temperature. The adsorbed NO molecules accrue a significant electron donation from the host framework even in the [Rh2] derivative, indicating that such simple porous compounds with electron-donor characteristics are useful for the selective adsorption of NO. © 2013 American Chemical Society.

    DOI: 10.1021/ja4076056

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  65. Reversible Chemisorption of Sulfur Dioxide in a Spin Crossover Porous Coordination Polymer Reviewed

    Zulema Arcis-Castillo, Francisco J. Munoz-Lara, M. Carmen Munoz, Daniel Aravena, Ana B. Gaspar, Juan F. Sanchez-Royo, Eliseo Ruiz, Masaaki Ohba, Ryotaro Matsuda, Susumu Kitagawa, Jose A. Real

    INORGANIC CHEMISTRY   Vol. 52 ( 21 ) page: 12777 - 12783   2013.11

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    The chemisorption of sulfur dioxide (SO2) on the Hofmann-like spin crossover porous coordination polymer (SCO-PCP) {Fe(pz)[Pt(CN)(4)]} has been investigated at room temperature. Thermal analysis and adsorption-desorption isotherms showed that ca. 1 mol of SO2 per mol of {Fe(pz)[Pt(CN)(4)]) was retained in the pores. Nevertheless, the SO2 was loosely attached to the walls of the host network and completely released in 24 h at 298 K. Single crystals of {Fe(pz)[Pt(CN)(4)]}center dot nSO(2) (n approximate to 0.25) were grown in water solutions saturated with SO2, and its crystal structure was analyzed at 120 K. The SO2 molecule is coordinated to the Pt-II ion through the sulfur atom ion, Pt-S = 2.585(4) angstrom. This coordination slightly stabilizes the low-spin state of the Fe-II ions shifting the critical temperatures of the spin transition by 8-12 K. DFT calculations have been performed to rationalize these observations.

    DOI: 10.1021/ic4020477

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  66. In Situ Generation of Functionality in a Reactive Haloalkane-Based Ligand for the Design of New Porous Coordination Polymers Reviewed

    Prakash Kanoo, Ryotaro Matsuda, Hiroshi Sato, Liangchun Li, Hyung Joon Jeon, Susumu Kitagawa

    INORGANIC CHEMISTRY   Vol. 52 ( 19 ) page: 10735 - 10737   2013.10

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    Herein, we report new porous coordination polymers (PCPs) via a facile synthetic approach called "in situ generation of functionality in the ligand". Upon a synthetic process of PCPs, a neutral (-CH2OH) or a cationic functionality (-CH2[4,4'-bipyridine](+)) was generated on a isophthalate ligand from a reactive haloalkane (-CH2Br) moiety, affording two new PCPs. The PCPs have two-dimensional layered structures with large potential solvent-accessible voids for CO2 adsorption.

    DOI: 10.1021/ic401924d

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  67. Design and Synthesis of Porous Coordination Polymers Showing Unique Guest Adsorption Behaviors Reviewed

    Ryotaro Matsuda

    BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN   Vol. 86 ( 10 ) page: 1117 - 1131   2013.10

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    Gas storage and separation are becoming a high priority area of research due to economic, industrial, and environmental reasons. The last two decades have therefore witnessed dramatic growth in the search for more efficient and adaptable nanoporous materials. In particular, much attention has been focused on porous coordination polymers (PCPs) or metal organic frameworks (MOFs) as new nanoporous materials. Based on the unlimited combination of metal ions and organic ligands, PCPs can provide infinite variety of nanospace in their pores. As molecular adsorption is dependent on the size, shape, and surface nature of nanospace, many unique molecular adsorption or trapping phenomena have been reported in this class of compounds. In this account, I focus on how thoughtful design can lead to the synthesis of porous coordination polymers that demonstrate unprecedented adsorption behavior not found in other porous materials. Examples include selective adsorption of acetylene over carbon dioxide in the CPL series of PCPs, using charge-transfer to induce selective adsorption of nitric oxide and oxygen in TCNQ (7,7,8,8-tetracyano-p-quinodimethane) based PCP and light-induced on-demand adsorption and structural transformations in CID-based PCPs. The guidelines underpinning such unique, highly selective guest adsorption are discussed.

    DOI: 10.1246/bcsj.20130157

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  68. Spin-Dependent Molecular Orientation of O-2-O-2 Dimer Formed in the Nanoporous Coordination Polymer Reviewed

    Akihiro Hori, Tatsuo C. Kobayashi, Yoshiki Kubota, Akira Matsuo, Koichi Kindo, Jungeun Kim, Kenichi Kato, Masaki Takata, Hirotoshi Sakamoto, Ryotaro Matsuda, Susumu Kitagawa

    JOURNAL OF THE PHYSICAL SOCIETY OF JAPAN   Vol. 82 ( 8 )   2013.8

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    In a model system of an O-2-O-2 dimer confined in the nanopores of Cu-1,4-cyclohexanedicarboxylic acid, the molecular orientation associated with the spin state was observed by precise synchrotron radiation structure analysis. The obtained charge density level structures revealed that the molecular orientation varied with increasing temperature, coupling with the spin states of the O-2-O-2 dimer. The magnetic properties previously reported were consistently explained by the S = 1 dimer model taking into account the molecular arrangements. The obtained gap parameters are different from those of the O-2-O-2 dimer confined in the nanopores of Cu-2,3-pyrazinedicarboxylate-pyrazine, which is explained by the pore deformation due to the adsorption, depending on the pore size and/or flexibility of the coordination polymer.

    DOI: 10.7566/JPSJ.82.084703

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  69. CO2 superabsorption in a paddlewheel-type Ru dimer chain compound: gate-open performance dependent on inter-chain interactions Reviewed

    Wataru Kosaka, Kayo Yamagishi, Hiroki Yoshida, Ryotaro Matsuda, Susumu Kitagawa, Masaki Takata, Hitoshi Miyasaka

    CHEMICAL COMMUNICATIONS   Vol. 49 ( 16 ) page: 1594 - 1596   2013

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    A porous one-dimensional coordination chain compound, [Ru-2(p-F-PhCO2)(4)(phz)] (1'; p-F-PhCO2- = para-fluorobenzoate; phz = phenazine) derived by drying its nitrobenzene-solvated compound, specifically adsorbs CO2 at 195 K in a stepwise sorption manner.

    DOI: 10.1039/c2cc36153a

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  70. Topological Difference in 2D Layers Steers the Formation of Rigid and Flexible 3D Supramolecular Isomers: Impact on the Adsorption Properties Reviewed

    Prakash Kanoo, Ryotaro Matsuda, Ryo Kitaura, Susumu Kitagawa, Tapas Kumar Maji

    INORGANIC CHEMISTRY   Vol. 51 ( 17 ) page: 9141 - 9143   2012.9

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    .Starting with the same precursors, pyridine-2,3-dicarboxylate (pyrdc) and 4,4'-bipyridyl (bipy), two 3D porous coordination polymers, ([Cu(bipy)(0.5)(pyrdc)]center dot 3H(2)O} (1) and ([Cu(bipy)(0.5)(pyrdc)].0.5bipy center dot 3H(2)O} (2), have been synthesized by changing the solvent system from MeOH/H2O to EtOH/H2O. Single-crystal structure analysis revealed that 1 and 2 are supramolecular isomers with 3D pillared-layer structures having 1D channel systems. Isomer 1 has a flexible structure and shows gated adsorption behavior, while framework 2 has a rigid backbone and exhibits the adsorption properties of typical microporous materials.

    DOI: 10.1021/ic300695v

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  71. Effect of functional groups in MIL-101 on water sorption behavior Reviewed

    George Akiyama, Ryotaro Matsuda, Hiroshi Sato, Akihiro Hori, Masaki Takata, Susumu Kitagawa

    MICROPOROUS AND MESOPOROUS MATERIALS   Vol. 157   page: 89 - 93   2012.7

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    Four MIL-101-type porous coordination polymers were synthesized containing different substituents (-H, -NO2, -NH2, -SO3H) in the ligand and their water sorption properties were investigated. All of the compounds adsorbed huge amounts of water (ca. 0.8-1.2 g g(-1)) and the adsorbed water can be released at relatively low temperatures (ca. 353 K). In addition, the trapping pressure of water adsorption was found to be controlled by changing the substituents, varying the hydrophobicity of the functional groups. (C) 2012 Elsevier Inc. All rights reserved.

    DOI: 10.1016/j.micromeso.2012.01.015

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  72. Guest-to-Host Transmission of Structural Changes for Stimuli-Responsive Adsorption Property Reviewed

    Nobuhiro Yanai, Takashi Uemura, Masafumi Inoue, Ryotaro Matsuda, Tomohiro Fukushima, Masahiko Tsujimoto, Seiji Isoda, Susumu Kitagawa

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   Vol. 134 ( 10 ) page: 4501 - 4504   2012.3

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    We show that structural changes of a guest molecule can trigger structural transformations of a crystalline host framework. Azobenzene was introduced into a flexible porous coordination polymer (PCP), and cis/trans isomerizations of the guest azobenzene by light or heat successfully induced structural transformations of the host PCP in a reversible fashion. This guest-to-host structural transmission resulted in drastic changes in the gas adsorption property of the host guest composite, displaying a new strategy for creating stimuli-responsive porous materials.

    DOI: 10.1021/ja2115713

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  73. Inclusion and dielectric properties of a vinylidene fluoride oligomer in coordination nanochannels Reviewed

    Nobuhiro Yanai, Takashi Uemura, Wataru Kosaka, Ryotaro Matsuda, Tetsuhiro Kodani, Meiten Koh, Takashi Kanemura, Susumu Kitagawa

    DALTON TRANSACTIONS   Vol. 41 ( 14 ) page: 4195 - 4198   2012

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    The dynamics of oligo(vinylidene fluoride) (OVDF) confined in regular nanochannels of a porous coordination polymer (PCP) was studied by means of dielectric spectroscopy. The OVDF chains in the PCP nanopores showed two Arrhenius-type relaxation processes at lower temperatures than the relaxation temperature observed for the neat OVDF, showing the enhanced mobility of the confined OVDF.

    DOI: 10.1039/c2dt11891b

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  74. Selective CO2 uptake and inverse CO2/C2H2 selectivity in a dynamic bifunctional metal-organic framework Reviewed

    Wenbin Yang, Andrew J. Davies, Xiang Lin, Mikhail Suyetin, Ryotaro Matsuda, Alexander J. Blake, Claire Wilson, William Lewis, Julia E. Parker, Chiu C. Tang, Michael W. George, Peter Hubberstey, Susumu Kitagawa, Hirotoshi Sakamoto, Elena Bichoutskaia, Neil R. Champness, Sihai Yang, Martin Schroeder

    CHEMICAL SCIENCE   Vol. 3 ( 10 ) page: 2993 - 2999   2012

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    The unique bifunctional porous metal-organic framework, [Co(HLdc)]center dot 1.5MeOH center dot dioxane, incorporates both free-standing carboxyl and pyridyl groups within its pores. Gas adsorption measurements on the desolvated framework reveal unusual selective CO2 adsorption over C2H2 and CH4 linked to a framework phase change from a narrow pore (np) to a large pore (lp) form, mediated by CO2 uptake at 195 K. This phase transition has been monitored by in situ powder X-ray diffraction and IR spectroscopy, and modelled by Grand Canonical Monte Carlo simulations revealing that the reversible np to lp transition is linked to the rotation of pyridyl rings acting as flexible "pore gates".

    DOI: 10.1039/c2sc20443f

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  75. Photochemical cycloaddition on the pore surface of a porous coordination polymer impacts the sorption behavior Reviewed

    Hiroshi Sato, Ryotaro Matsuda, Mohammad Hedayetullah Mir, Susumu Kitagawa

    CHEMICAL COMMUNICATIONS   Vol. 48 ( 64 ) page: 7919 - 7921   2012

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    Photochemical [2 + 2] cycloaddition reactions in a two-dimensional interdigitated porous crystalline framework proceed in a single-crystal-to-single-crystal manner, and one-dimensional channels show structural changes that have a significant impact on the CO2 sorption.

    DOI: 10.1039/c2cc31083j

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  76. Highly rigid and stable porous Cu(I) metal-organic framework with reversible single-crystal-to-single-crystal structural transformation Reviewed

    Sudip Mohapatra, Hiroshi Sato, Ryotaro Matsuda, Susumu Kitagawa, Tapas Kumar Maji

    CRYSTENGCOMM   Vol. 14 ( 12 ) page: 4153 - 4156   2012

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    A simple room temperature reaction of Cu(NO3)(2), and 2,3-pyrazinedicarboxylic acid (H(2)pyzdc) in the presence of dihydroxyfumaric acid (DHFA) resulted in the formation of a highly stable 3D Cu(I) coordination polymer, {[Cu-2(pyzdc)]center dot 0.83H(2)O}(n) where DHFA acts as a reducing agent. It possesses a 1D water filled channel along the crystallographic c direction and the framework shows reversible single-crystal-to-single-crystal structural transformation upon dehydration and rehydration.

    DOI: 10.1039/c2ce06701c

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  77. Systematic mechanochemical preparation of a series of coordination pillared layer frameworks Reviewed

    Hirotoshi Sakamoto, Ryotaro Matsuda, Susumu Kitagawa

    DALTON TRANSACTIONS   Vol. 41 ( 14 ) page: 3956 - 3961   2012

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    A detailed investigation into the mechanochemical synthesis of coordination pillared-layer frameworks (CPLs), particularly CPL-1, was carried out. In the case of CPL-1, a two-step reaction was observed (from the starting reactants to the final product). In the conventional solution process, no intermediate state was detected. We found that moisture is essential in both the reaction steps. After the final product was washed, it showed the same sorption ability as the product prepared from a solution process. We further demonstrated the systematic preparation of other CPLs (CPL-2, 3, 4, 5, and 15) by the mechanochemical method under humid conditions, even though some of the ligands are almost insoluble in water. Our findings indicate that mechanochemical synthesis is a promising alternative method for the systematic and large-scale production of PCPs. Its advantages include the following: reduced pollution, low cost, simplicity of the process, ease of handling, efficient reaction rate, selectivity, and the issue of low solubility of reactants is overcome.

    DOI: 10.1039/c2dt12012g

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  78. Gas detection by structural variations of fluorescent guest molecules in a flexible porous coordination polymer Reviewed

    Nobuhiro Yanai, Koji Kitayama, Yuh Hijikata, Hiroshi Sato, Ryotaro Matsuda, Yoshiki Kubota, Masaki Takata, Motohiro Mizuno, Takashi Uemura, Susumu Kitagawa

    NATURE MATERIALS   Vol. 10 ( 10 ) page: 787 - 793   2011.10

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    The development of a new methodology for visualizing and detecting gases is imperative for various applications. Here, we report a novel strategy in which gas molecules are detected by signals from a reporter guest that can read out a host structural transformation. A composite between a flexible porous coordination polymer and fluorescent reporter distyrylbenzene ( DSB) selectively adsorbed CO(2) over other atmospheric gases. This adsorption induced a host transformation, which was accompanied by conformational variations of the included DSB. This read-out process resulted in a critical change in DSB fluorescence at a specific threshold pressure. The composite shows different fluorescence responses to CO(2) and acetylene, compounds that have similar physicochemical properties. Our system showed, for the first time, that fluorescent molecules can detect gases without any chemical interaction or energy transfer. The host-guest coupled transformations play a pivotal role in converting the gas adsorption events into detectable output signals.

    DOI: 10.1038/NMAT3104

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  79. Cellulose Hydrolysis by a New Porous Coordination Polymer Decorated with Sulfonic Acid Functional Groups Reviewed

    George Akiyama, Ryotaro Matsuda, Hiroshi Sato, Masaki Takata, Susumu Kitagawa

    ADVANCED MATERIALS   Vol. 23 ( 29 ) page: 3294 - +   2011.8

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    A MIL-101-based porous coordination polymer (PCP) containing sulfonic acid groups is synthesized. The sulfonic groups are exposed on the pore surface and act as strong Bronsted acid sites. This solid acid PCP catalytically hydrolyzes cellulose into mono- and disaccharides and shows high durability in the catalytic reaction.

    DOI: 10.1002/adma.201101356

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  80. Soft Secondary Building Unit: Dynamic Bond Rearrangement on Multinuclear Core of Porous Coordination Polymers in Gas Media Reviewed

    Joobeom Seo, Charlotte Bonneau, Ryotaro Matsuda, Masaki Takata, Susumu Kitagawa

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   Vol. 133 ( 23 ) page: 9005 - 9013   2011.6

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    A new synthetic approach to prepare flexible porous coordination polymers (PCPs) by the use of soft secondary building units (SBUs) which can undergo multiple reversible metal-ligand bonds breaking is reported. We have prepared a zinc paddle-wheel-based two-fold interpenetrated PCP, {[Zn(2)(tp)(2)(L(2))]center dot 2.5DMF center dot 0.5water}(n) (2a, H(2)tp = terephthanlic acid; L(2) = 2,3-difluoro-1,4-bis(4-pyridyl)benzene), showing dynamic structural transformations upon the removal and rebinding of guest molecules. The X-ray structures at different degrees of desolvation indicate the highly flexible nature of the framework. The framework deformations involve slippage of the layers and movement of the two interpenetrated frameworks with respect to each other. Interestingly, the coordination geometry of a zinc paddle-wheel unit (one of the popular SBUs) is considerably changed by bond breaking between zinc and oxygen atoms during the drying process. Two zinc atoms in the dried form 24 reside in a distorted tetrahedral geometry. Compound 24 has no void volume and favors the uptake of O(2) over Ar and N(2) at 77 K The 02 and Ar adsorption isotherms of 24 show gate-opening-type adsorption behaviors corroborating the structure determination. The CO(2) adsorption isotherm at 195 K exhibits multiple steps originating from the flexibility of the framework The structural transformations of the zinc dusters in the framework upon sorption of guest molecules are also characterized by Raman spectroscopy in which the characteristic bands corresponding to v(sym) (COO(-)) vibration were used.

    DOI: 10.1021/ja201484s

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  81. Relationship between Channel and Sorption Properties in Coordination Polymers with Interdigitated Structures Reviewed

    Yuh Hijikata, Satoshi Horike, Masayuki Sugimoto, Hiroshi Sato, Ryotaro Matsuda, Susumu Kitagawa

    CHEMISTRY-A EUROPEAN JOURNAL   Vol. 17 ( 18 ) page: 5138 - 5144   2011.4

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    Porous coordination polymers constructed from Zn2+ and isophthalate with linear bipyridyl-type ligands were synthesized. [Zn(ip)(bpb)](n) (CID-21; ip = isophthalate, bpb = 1,4-bis(4-pyridyl)benzene), [Zn(ip)(bpt)](n) (CID-22; bpt= 3,6-bis(4-pyridyl)-1,2,4,5-tetrazine), and [Zn(ip)(bpa)](n) (CID-23; bpa= 1,4-bis(4-pyridyl)acetylene) all have interdigitated structures of layers and similar void volumes (approximate to 27%). In these compounds, 1D bottleneck-type channels run along the perpendicular direction of the layer stacking and their properties are strongly dominated by the dipyridyl linker ligands. Because of the difference in packing of 2D layers, CID-21 and CID-22 have relatively rigid porous structures, whereas CID-23 has greater flexibility, as indicated by the results of powder X-ray diffraction studies. The micropores of CID-22 surrounded by tetrazine moieties adsorb polar molecules, such as methanol and water. The higher affinity of CID-22 for water than CID-21 is supported by a theoretical study. The 1D channel of CID-23 is wider than that of the other two compounds, which enables the incorporation of aromatic molecules. This is because the shape of the bpa linker ligand generates a wider pore diameter (8.6 angstrom). Only CID-23 can adsorb a benzene molecule and the isotherm of benzene has a gate-openingtype profile. This offers proof of the guest accommodation process through large structural transformation from a nonporous to a porous structure. The flexibility and restricted pore space of CID-23, at 298 K, allows only benzene, but not cyclohexane, to enter the channels. The porous structure exhibits clear selectivity for these similar guests. The incorporation of an elongated dipyridyl linker ligand in the 2D coordination layers provides a strategy for the design of microporous compounds with different flexibilities, microporous environments, and separation abilities.

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  82. Impact of Metal Ion Dependence on the Porous and Electronic Properties of TCNQ-Dianion-Based Porous Coordination Polymers Reviewed

    Satoru Shimomura, Nobuhiro Yanai, Ryotaro Matsuda, Susumu Kitagawa

    INORGANIC CHEMISTRY   Vol. 50 ( 1 ) page: 172 - 177   2011.1

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    A series of TCNQ-dianion-based porous coordination polymers [M(TCNQ)bpy] (M = Fe, Zn, Mn, Co, Cd) have been synthesized and characterized. The synthesis reactions of these compounds are promoted by the addition of ascorbic acid, which is the key to obtaining a high yield. They form almost identical three-dimensional pillared layer structures with the M-TCNQ two-dimensional layers linked by bpy pillar ligands. The electronic properties of these compounds vary depending on the constitutional metal ions and guest molecules. We found that the electronic interaction between metal ions and TCNQ moieties in the frameworks strongly impacted the electronic properties of the compounds.

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  83. A pillared-bilayer porous coordination polymer with a 1D channel and a 2D interlayer space, showing unique gas and vapor sorption Reviewed

    Prakash Kanoo, Golam Mostafa, Ryotaro Matsuda, Susumu Kitagawa, Tapas Kumar Maji

    CHEMICAL COMMUNICATIONS   Vol. 47 ( 28 ) page: 8106 - 8108   2011

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    A new 2D pillared-bilayer porous coordination polymer (PCP) has been synthesized and structurally characterized that shows selective adsorption of CO2 over other gases (N-2, O-2, Ar, H-2, CH4) and guest selective single/double-step adsorption of vapor correlated to the successive confinement of adsorbates in a 1D channel and a 2D interlayer space.

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  84. Reporting structural transformation of soft porous crystals for detection of CO2 Reviewed

    Nobuhiro Yanai, Koji Kitayama, Yuh Hijikata, Hiroshi Sato, Ryotaro Matsuda, Yoshiki Kubota, Masaki Takata, Motohiro Mizuno, Takashi Uemura, Susumu Kitagawa

    Nat. Mater.     page: .   2011

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  85. Exceptional Thermal Stability in a Supramolecular Organic Framework: Porosity and Gas Storage Reviewed

    Wenbin Yang, Alex Greenaway, Xiang Lin, Ryotaro Matsuda, Alexander J. Blake, Claire Wilson, William Lewis, Peter Hubberstey, Susumu Kitagawa, Neil R. Champness, Martin Schroeder

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   Vol. 132 ( 41 ) page: 14457 - 14469   2010.10

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    Reaction of beta-amino-beta-(pyrid-4-yl)acrylonitrile with the aromatic dicarboxaldehydes 9,10-bis(4formylphenyl)anthracene and terephthalaldehyde affords the dihydropyridyl products 9,10-bis(4-((3,5dicyano-2,6-dipyridyl)dihydropyridyl)phenyl)anthracene (L(1)) and 1,4-bis(4-(3,5-dicyano-2,6-dipyridyl)dihydropyridyl)benzene (L(2)), respectively. In the solid state [L(1)]center dot 2.5DMF center dot 3MeOH (SOF-1) crystallizes in the monoclinic space group P2(1)/C and forms a 3D stable supramolecular organic framework via strong N-H center dot center dot center dot N(py) hydrogen bonds and pi-pi interactions. The material incorporates pyridyl-decorated channels and shows permanent porosity in the solid state. The pore volumes of the desolvated framework SOF-1a calculated from the N(2) isotherm at 125 K and the CO(2) isotherm at 195 K are 0.227 and 0.244 cm(3)g(-1) respectively. The N(2) absorption capacity of SOF-1a at 77 K is very low, with an uptake of 0.63 mmol g(-1) at 1 bar, although saturation N(2) adsorption at 125 K is 6.55 mmol g(-1) (or 143 cm(3) g(-1)). At ambient temperature, SOF-1 a shows significant CO(2) adsorption with approximately 3 mol of CO(2) absorbed per mole of host at 16 bar and 298 K, corresponding to 69 cm(3) g(-1) at STP. SOF-1a also adsorbs significant amounts of C(2)H(2), with an uptake of 124 cm3 (STP) g(-1) (5.52 mmol g(-1)) at 1 bar at 195 K. Methane uptake at 195 K and 1 bar is 69 cm3 (STP) g(-1). Overall, gas adsorption measurements on desolvated framework SOF-1a reveal not only high capacity uptakes for C(2)H(2) and CO(2), compared to other crystalline molecular organic solids, but also an adsorption selectivity in the order C(2)H(2) &gt; CO(2) &gt; CH(4) &gt; N(2). Overall, C(2)H(2)(270 K)/CH(4)(273 K) selectivity is 33.7 based on Henry&apos;s Law constant, while the C(2)H(2) (270 K)/CO(2)(273 K) ratio of uptake at 1 bar is 2.05. The less bulky analogue L2 crystallizes in the triclinic space group PT as two different solvates [L(2)]center dot 2DMF center dot 5C(6)H(6) (S2A) and [L(2)]center dot 2DMF center dot 4MeOH (S2B) as pale yellow tablets and blocks, respectively. Each L(2) molecule in S2A participates in two N-H center dot center dot center dot O hydrogen bonds between dihydropyridyl rings and solvent DMF molecules. Packing of these layers generates 1D nanochannels along the crystallographic a and b axes which host DMF and benzene molecules. In S2B, each L(2) ligand participates in hydrogen bonding via an N-H center dot center dot center dot O interaction between the N-H of the dihydropyridyl ring and the O of a MeOH and also via an N-H center dot center dot center dot O interaction between the N center of a pyridine ring and the H-O of a second MeOH molecule. The presence of the L(2)-HO Me hydrogen bonds prevents ligand-ligand hydrogen bonding. As a result, S2B crystallizes as one-dimensional chains rather than as an extended 3D network. Thermal removal of solvents from S2A results in conversion to denser phase S2C which shows no effective permanent porosity.

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  86. Temperature responsive channel uniformity impacts on highly guest-selective adsorption in a porous coordination polymer Reviewed

    Ryotaro Matsuda, Takashi Tsujino, Hiroshi Sato, Yoshiki Kubota, Kunimitsu Morishige, Masaki Takata, Susumu Kitagawa

    CHEMICAL SCIENCE   Vol. 1 ( 3 ) page: 315 - 321   2010.9

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    Selective adsorption, so called "molecular sieving", is one of the significant functions of porous materials because it can play an important role in separation processes to obtain highly pure gases or petroleum. One of the next outstanding challenges of porous materials is the achievement of controllable "molecular sieving" in response to external environments. Here, we show a new temperature responsive 1-dimensional porous compound (CPL-11) which changes its structural uniformity in response to ambient temperature, which gives rise to changes in the effective pore size. As a result of the structural responsiveness, the seeming adsorption properties of CPL-11 are apparently opposite to conventional porous compounds expected from thermodynamic law, resulting in a highly selective adsorption for O-2 compared to Ar. This unexpected adsorption behavior indicates that the adsorption properties can be controlled by changing the channel uniformity of a porous framework depending on the ambient temperature.

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  87. Magnetic properties of nitric oxide molecules physisorbed into nano-sized pores of MCM-41 Reviewed

    Masaki Mito, Tsuyoshi Tatano, Yuki Komorida, Takayuki Tajiri, Hiroyuki Deguchi, Seishi Takagi, Shigemi Kohiki, Masaaki Ohba, Ryotaro Matsuda, Susumu Kitagawa

    MICROPOROUS AND MESOPOROUS MATERIALS   Vol. 132 ( 3 ) page: 464 - 469   2010.8

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    We physisorbed nitric oxide (NO) molecules with spin (S) of 1/2 into the nano-sized pores of the mesoporous medium MCM-41, which allows molecule adsorption of the multi-layer form. The adsorption and desorption isotherms were observed at 121.5 K. and the effects of adsorption efficacy (i.e., the filling ratio, n) on the magnetic properties were investigated. Changes in the condensation state in the temperature region of 100-120 K were observed through the magnetic measurements, and the resultant phase diagram against n resembled that obtained for the physisorption of oxygen (O(2)) molecules with S=1. For T &lt; 90 K, two NO molecules dimerized independently of n and diamagnetic dinitrogen dioxide (N(2)O(2)) was formed. The two-dimensional magnetic state, seen for O(2) physisorption, was not observed in the present system, probably due to the prominent electric polarity of the NO molecule. (C) 2010 Elsevier Inc. All rights reserved.

    DOI: 10.1016/j.micromeso.2010.03.028

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  88. Photoactivation of a nanoporous crystal for on-demand guest trapping and conversion Reviewed

    Hiroshi Sato, Ryotaro Matsuda, Kunihisa Sugimoto, Masaki Takata, Susumu Kitagawa

    NATURE MATERIALS   Vol. 9 ( 8 ) page: 661 - 666   2010.8

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    Porous compounds are ubiquitous and indispensable in daily life as adsorbents and catalysts. The discovery of a new porous compound with unique properties based on intrinsic nanosized space and surface functionalities is scientifically and technologically important. However, the functional species used in this context are limited to those that are sufficiently inert to not spoil the porous structures. Here, we show a new strategy to achieve a crystalline porous material with the pore surface regularly decorated with highly reactive &apos;bare&apos; nitrenes that are photonically generated from stable &apos;dormant&apos; precursors at will. The bare triplet nitrenes were accessible to and reacted with adsorbed oxygen or carbon monoxide molecules, which showed not only activation of the pore surface, but also a high probability of chemical trapping and conversion of guest molecules by light stimulation on demand.

    DOI: 10.1038/NMAT2808

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  89. Selective sorption of oxygen and nitric oxide by an electron-donating flexible porous coordination polymer Reviewed

    Satoru Shimomura, Masakazu Higuchi, Ryotaro Matsuda, Ko Yoneda, Yuh Hijikata, Yoshiki Kubota, Yoshimi Mita, Jungeun Kim, Masaki Takata, Susumu Kitagawa

    NATURE CHEMISTRY   Vol. 2 ( 8 ) page: 633 - 637   2010.8

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    Porous coordination polymers are materials formed from metal ions that are bridged together by organic linkers and that can combine two seemingly contradictory properties-crystallinity and flexibility. Porous coordination polymers can therefore create highly regular yet dynamic nanoporous domains that are particularly promising for sorption applications. Here, we describe the effective selective sorption of dioxygen and nitric oxide by a structurally and electronically dynamic porous coordination polymer built from zinc centres and tetracyanoquinodimethane (TCNQ) as a linker. In contrast to a variety of other gas molecules (C(2)H(2), Ar, CO(2), N(2) and CO), O(2) and NO are accommodated in its pores. This unprecedented preference arises from the concerted effect of the charge-transfer interaction between TCNQ and these guests, and the switchable gate opening and closing of the pores of the framework. This system provides further insight into the efficient recognition of small gas molecules.

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  90. Flexibility of Porous Coordination Polymers Strongly Linked to Selective Sorption Mechanism Reviewed

    Satoru Shimomura, Ryotaro Matsuda, Susumu Kitagawa

    CHEMISTRY OF MATERIALS   Vol. 22 ( 14 ) page: 4129 - 4131   2010.7

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    DOI: 10.1021/cm101410h

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  91. Highly Porous and Stable Coordination Polymers as Water Sorption Materials Reviewed

    George Akiyama, Ryotaro Matsuda, Susumu Kitagawa

    CHEMISTRY LETTERS   Vol. 39 ( 4 ) page: 360 - 361   2010.4

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    Three MIL-100-type porous coordination polymers were synthesized using different types of anions and their water sorption properties were investigated. All of the compounds adsorbed huge amounts of water (0.6g g(-1)) at a moderate humidity (P/P-0 &lt; 0.6), and one of the compounds showed the same adsorption property even after two thousand replicate water sorption tests. In addition, the pressure of water adsorption was found to be controlled by counter anions incorporated in the structure, which was attributed to the hydration energy of the anions.

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  92. Incommensurate guest adsorption in bellows-shaped one-dimensional channels of porous coordination polymers Reviewed

    Ryotaro Matsuda, Ryo Kitaura, Yoshiki Kubota, Tatsuo C. Kobayashi, Masaki Takata, Susumu Kitagawa

    MICROPOROUS AND MESOPOROUS MATERIALS   Vol. 129 ( 3 ) page: 296 - 303   2010.4

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    Adsorption isotherms of N(2), O(2), CO(2), and Xe on a flexible microporous coordination polymer, CPL-2 [Cu(2)(pzdc)(2)(bpy)]center dot(pzdc = pyrazine-2,3-dicarboxylate; bpy = 4,4&apos;-bipyridine), possessing bellows-shaped one-dimensional channels were measured. A nonintegral number of each of the N(2), O(2), CO(2), and Xe molecules can be accommodated in each unit pore, which indicates that all guest molecules are accommoda dated in the so-called "incommensurate fashion". in situ synchrotron X-ray powder diffraction patterns of CPL-2 with guest molecules were recorded. The unit cells were determined from each pattern. It Was found that the host CPL-2 exhibits different crystal transformation with the accommodation of each guest molecule. This indicates that, even in the case of incommensurate adsorption, the flexible framework of a microporous coordination polymer can transform each pore to suit different guest molecules. (C) 2009 Elsevier Inc. All rights reserved.

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  93. Systematic Construction of Porous Coordination Pillared-layer Structures and Their Sorption Properties Reviewed

    Hirotoshi Sakamoto, Ryo Kitaura, Ryotaro Matsuda, Susumu Kitagawa, Yoshiki Kubota, Masaki Takata

    CHEMISTRY LETTERS   Vol. 39 ( 3 ) page: 218 - 219   2010.3

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    Two novel coordination polymers, {[Cu-2(pzdc)(2)L]center dot mH(2)O}n where pzdc is pyrazine-2,3-dicarboxylate and L is 2,7-diazapyrene (CPL-3) and 1,2-azopyridine (CPL-4), respectively, having 3D pillared-layer structure were prepared and the compounds showed gas adsorption properties depending on L.

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  94. Chemistry of Porous Coordination Polymers Having Multimodal Nanospace and Their Multimodal Functionality Reviewed

    Joobeom Seo, Hirotoshi Sakamoto, Ryotaro Matsuda, Susumu Kitagawa

    JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY   Vol. 10 ( 1 ) page: 3 - 20   2010.1

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    Remarkable advances in the recent development of porous coordination polymers (PCPs) or metal organic frameworks (MOFs) have paved the way toward functional chemistry having potential application such as molecular storage, separation, and catalysis. Moreover flexible PCPs, which are structurally transformable depending upon guest molecules adsorption/desorption, have received much attention because they provide unique properties, dissimilar to those of zeolites. PCPs can be categorized into structurally monomodal and multimodal classes. Monomodal PCPs possess single uniform pores in the framework. In contrast, multimodal PCPs have more than two types of pores in the framework. Interpenetrated PCPs can possess more than two types of pores with different sizes and shapes in the same framework depending on relative position of individual motifs, resulting in multimodal PCPs. Moreover, interpenetrated PCPs have several advantages, such as high thermal stability, flexibility, and ultramicropore for effective adsorption. In this review, chemistry of PCPs based on monomodal and multimodal PCPs are summarized and discussed.

    DOI: 10.1166/jnn.2010.1494

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  95. Periodic molecular boxes in entangled enantiomorphic lcy nets Reviewed

    Yohei Takashima, Charlotte Bonneau, Shuhei Furukawa, Mio Kondo, Ryotaro Matsuda, Susumu Kitagawa

    CHEMICAL COMMUNICATIONS   Vol. 46 ( 23 ) page: 4142 - 4144   2010

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    In this contribution, we present a coordination framework built from a novel (Zn(4)O)(O(2)C)(6) metaprismatic unit showing the interpenetration of a pair of enantiomorphic lcy nets that exhibits commensurate sorption properties.

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  96. High-Field Magnetization Process of O(2) Adsorbed in a Microporous Coordination Polymer CPL-1 at Various Temperatures Reviewed

    A. Hori, T. C. Kobayashi, A. Matsuo, K. Kindo, R. Matsuda, S. Kitagawa

    INTERNATIONAL CONFERENCE ON MAGNETISM (ICM 2009)   Vol. 200   2010

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    High-field magnetization measurements have been performed at various temperatures on the molecular oxygen adsorbed in a microporous coordination polymer CPL-1. Molecular oxygen with S = 1 forms O(2)-O(2) dimer in the nanochannels of CPL-1. The magnetic properties can be explained by not the S = 1 Heisenberg antiferromagnetic dimer model but the O(2)-O(2) dimer model taking into account the spin-dependent intermolecular potential. This feature is attributed to the fact that the magnetic interaction between O(2) is comparable to the van der Waals force.

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  97. Modification of flexible part in Cu2+ interdigitated framework for CH4/CO2 separation Reviewed

    Yasutaka Inubushi, Satoshi Horike, Tomohiro Fukushima, George Akiyama, Ryotaro Matsuda, Susumu Kitagawa

    CHEMICAL COMMUNICATIONS   Vol. 46 ( 48 ) page: 9229 - 9231   2010

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    The structural flexibility of Cu2+ interdigitated layer type framework was controlled and the compound represented clear separation property of CH4/CO2 at range of 0-1.0 MPa and recovery of adsorbed CO2 above 0.1 MPa.

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  98. Control of Interpenetration for Tuning Structural Flexibility Influences Sorption Properties Reviewed

    Sareeya Bureekaew, Hiroshi Sato, Ryotaro Matsuda, Yoshiki Kubota, Raita Hirose, Jungeun Kim, Kenichi Kato, Masaki Takata, Susumu Kitagawa

    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   Vol. 49 ( 42 ) page: 7660 - 7664   2010

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    DOI: 10.1002/anie.201002259

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  99. The RIKEN Materials Science Beamline at SPring-8: Towards Visualization of Electrostatic Interaction Reviewed

    Kenichi Kato, Raita Hirose, Michitaka Takemoto, Sunyeo Ha, Jungeun Kim, Masakazu Higuchi, Ryotaro Matsuda, Susumu Kitagawa, Masaki Takata

    SRI 2009: THE 10TH INTERNATIONAL CONFERENCE ON SYNCHROTRON RADIATION INSTRUMENTATION   Vol. 1234   page: 875 - +   2010

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    In order to visualize molecular interaction by the experimental electrostatic potential analysis we have optimized the optical parameters and developed the high-resolution Debye-Scherrer camera at the RIKEN materials science beamline, BL44B2 of SPring-8. For the purpose the camera was designed to be equipped with the hybrid X-ray detector system. One is the conventional detector, the imaging plate readout off-line to carry out high d (interplanar spacing)-resolution measurements and the other is the CCD detector, which can be operated in a camera at variable distances for high angle-resolution measurements. In addition we have been developing an in-situ properties measurement system to visualize the electrostatic interaction completely synchronized with material functions.

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  100. Y. Takashima, C. Bonneau, S. Furukawa, M. Kondo, R. Matsuda, S. Kitagawa

    Periodic molecular, boxes in, angled, nantiomorphic, lcy nets

    Chem. Commun., 46, 4142-4144 (2010)     page: .   2010

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  101. New Interpenetrated Copper Coordination Polymer Frameworks having Porous Properties Reviewed

    Prakash Kanoo, Ryotaro Matsuda, Masakazu Higuchi, Susumu Kitagawa, Tapas Kumar Maji

    CHEMISTRY OF MATERIALS   Vol. 21 ( 24 ) page: 5860 - 5866   2009.12

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    Two new 3-fold inter-penetrated 3D microporous metal-organic coordination polymers (MOCPs) of Cu(II), [Cu(3)(blpy)(1.5)(2,6-ndc)(3)](n) (1) and {[Cu(bpe)0.5(2,6-ndc)]center dot 0.5H(2)O}(n) (2) (bipy = 4,4&apos;-bipyridine; bpe 1,2-bis(4-pyridyl)ethane; and 2,6-ndc = 2,6-naphthalenedicarboxylate), have been synthesized using a mixed-ligand system and Structurally characterized by single-crystal X-ray diffraction study. Room-temperature reaction of Cu(II) with bipy and 2,6-ndc affords 1, whereas reaction with bpe and 2,6-ndc yields 2. Structure determination reveals that in both cases, a 2D square grid made by Cu(II) and 2,6-ndc with the aid Of Cu(2)(CO(2))(4) paddlewheel building block is connected by bipy (1) or bpe (2) organic pillar results 3D alpha-polonium type frameworks. Framework I is rigid and robust without any guest molecules, whereas 2 is flexible, realized by the guest induced structural transformations. Both the frameworks show high thermal stability. Framework I and dehydrated form of 2, i.e 2&apos;contains 16.6% and 21.4% void space, respectively and Langmuir surface area calculated from nitrogen adsorption study for 1 and 2&apos; is 113.0 and 337.5 m(2)/g, respectively. Both the frameworks can store approximately 1 wt% of molecular hydrogen at 77 K and 15 bar, in particular, the density of adsorbed hydrogen in 1 is one of the highest reported so far in porous MOCPS. Compounds 1 and 2&apos; can also store 11.0 and 13.2 wt % carbon dioxide at 195 K.

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  102. A Pillared-Layer Coordination Polymer with a Rotatable Pillar Acting as a Molecular Gate for Guest Molecules Reviewed

    Joobeom Seo, Ryotaro Matsuda, Hirotoshi Sakamoto, Charlotte Bonneau, Susumu Kitagawa

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   Vol. 131 ( 35 ) page: 12792 - 12800   2009.9

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    The design of pore properties utilizing flexible motifs and functional groups is of importance to obtain porous coordination polymers with desirable functions. We have prepared a 3D pillared-layer coordination polymer, {[Cd(2)(pzdc)(2)L(H(2)O)(2)]center dot 5(H(2)O)center dot(CH(3)CH(2)OH)}(n) (1, H(2)pzdc = 2,3-pyrazinedicarboxylic acid; L = 2,5-bis(2-hydroxyethoxy)-1,4-bis(4-pyridyl)benzene) showing (i) a rotatable pillar bearing ethylene glycol side chains acting as a molecular gate with locking/unlocking interactions triggered by guest inclusion between the side chains, (ii) framework flexibility with slippage of the layers, and (iii) coordinatively unsaturated metal centers as guest accessible sites through the removal of the water coligands. The framework clearly shows reversible single-crystal-to-single-crystal transformations in response to the removal and rebinding of guest molecules, the observation of these processes has provided fundamental clues to the understanding of the sorption profiles. The X-ray structures indicate that the 3D host framework is retained during the transformations, involving mainly rotation of the pillars and slippage of the layers. The structure of dried form 2, [Cd(2)(pzdc)(2)L](n), has no void volume and no water coligands. Interestingly, the adsorption isotherm of water for 2 at 298 K exhibits three distinct steps coinciding with the framework functions. Compound 2 favors the uptake of CO(2) (195 K) over N(2) (77 K) and O(2) (77 K). Above all, we report on a molecular gate with a rotational module exhibiting a locking/unlocking system which accounts for gate-opening type sorption profiles.

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  103. Bistability of Magnetization without Spin-Transition in a High-Spin Cobalt(II) Complex due to Angular Momentum Quenching Reviewed

    Gergely Juhasz, Ryotaro Matsuda, Shinji Kanegawa, Kaori Inoue, Osamu Sato, Kazunari Yoshizawa

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   Vol. 131 ( 13 ) page: 4560 - +   2009.4

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    [Co(NO3)(2)L] (L: 2,6-di(pyrazol-1-yl)pyrazine) (1) exhibits an abrupt transition with hysteresis in magnetic susceptibility between 228 and 240 K. The results of spectroscopic and XRD measurements showed that I is in the high spin state in the whole temperature range. Therefore the observed hysteresis is not due to a spin transition but corresponds to a partial quenching of the angular momentum contribution to the magnetic susceptibility. Crystallographic measurements on the low- and high-temperature form of 1, combined with DFT calculations, showed that a symmetric twisting of the coordinating nitrate ions upon the transition is the most important factor in the orbital quenching mechanism. Utilizing such quenching to control magnetic properties can be a new approach to engineer transition metal complexes with magnetic functionalities without changing their spin or oxidation state.

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  104. Hindered Rotation of Methane Molecules in the One-Dimensional Nanochannel of a Porous Coordination Polymer Reviewed

    Yoshiki Kubota, Masaki Takata, Ryo Kitaura, Ryotaro Matsuda, Tatsuo C. Kobayashi, Susumu Kitagawa

    JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY   Vol. 9 ( 1 ) page: 69 - 76   2009.1

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    The crystal structure of a microporous coordination polymer with adsorbed methane gas was determined by in situ synchrotron powder diffraction of the gas adsorption and the MEM (maximum entropy method)/Rietveld method. Methane molecules were found to be adsorbed forming a one-dimensional array in the nanochannels of the polymer. The MEM charge density distribution of the adsorbed methane molecules indicated some protrusions which were not observed in that of a spherical atom of adsorbed argon. This was interpreted as a mixed distribution of two uniaxially rotating molecules with different pivotal axes. The methane molecules displayed hindered rotation depending on the shape of the nanopore surface. This result indicates the capability to control the molecular arrangement and orientation by the adsorption of gas molecules on the precisely designed nanopores of coordination polymers.

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  105. Heterogeneously Hybridized Porous Coordination Polymer Crystals: Fabrication of Heterometallic Core-Shell Single Crystals with an In-Plane Rotational Epitaxial Relationship Reviewed

    Shuhei Furukawa, Kenji Hirai, Keiji Nakagawa, Yohei Takashima, Ryotaro Matsuda, Takaaki Tsuruoka, Mio Kondo, Rie Haruki, Daisuke Tanaka, Hirotoshi Sakamoto, Satoru Shimomura, Osami Sakata, Susumu Kitagawa

    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   Vol. 48 ( 10 ) page: 1766 - 1770   2009

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    DOI: 10.1002/anie.200804836

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  106. A Porous Coordination Polymer with Accessible Metal Sites and its Complementary Coordination Action Reviewed

    Hirotoshi Sakamoto, Ryotaro Matsuda, Sareeya Bureekaew, Daisuke Tanaka, Susumu Kitagawa

    CHEMISTRY-A EUROPEAN JOURNAL   Vol. 15 ( 20 ) page: 4985 - 4989   2009

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  107. Nanochannels of two distinct cross-sections in a porous Al-based coordination polymer Reviewed

    Angiolina Comotti, Silvia Bracco, Piero Sozzani, Satoshi Horike, Ryotaro Matsuda, Jinxi Chen, Masaki Takata, Yoshiki Kubota, Susumu Kitagawa

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   Vol. 130 ( 41 ) page: 13664 - 13672   2008.10

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    A new aluminum naphthalenedicarboxylate Al(OH)(1,4-NDC)center dot 2H(2)O compound has been synthesized. The crystal structure exhibits a three-dimensional framework composed of infinite chains of corner-sharing octahedral AI(OH)(2)O(4) with 1,4-naphthanedicarboxylate ligands forming two types of channels with squared-shape cross-section. The large channels present a cross-section of 7.7 x 7.7 angstrom(2), while the. are removed, no structural transformation small channels are about 3.0 x 3.0 angstrom(2) When water molecules occurs, generating a robust structure with permanent porosity and remarkable thermal stability. 2D (1)H-(13)C heteronuclear correlation NMR measurements, together with the application of Lee-Goldburg homonuclear decoupling, were applied, for the first time, to porous coordination polymers revealing the spatial relationships between the (1)H and (13)C spin-active nuclei of the framework. To demonstrate the open pore structure and the easy accessibility of the nanochannels to the gas phase, highly sensitive hyperpolarized (HP) xenon NMR, under extreme xenon dilution, has been applied. Xenon can diffuse selectively into the large nanochannels, while the small ones show no substantial uptake of xenon due to severe restrictions along the channels that prevent the diffusion. Two-dimensional exchange experiments showed the exchange time to be as short as 15 ms. Through variable-temperature HP (129)Xe NMR experiments we were able to achieve an unprecedented description of the large nanochannel space and surface, a physisorption energy of 10 kJ mol(-1), and the chemical shift value of xenon probing the internal surfaces. The large pore channels are straight, parallel, and independent, allowing one-dimensional anisotropic diffusion of gases and vapors. Their walls are composed of the naphthalene moieties that create an unique environment for selective sorption. These results prompted us to measure the storage capacity toward methanol, acetone, benzene, and carbon dioxide. The selective adsorption of methanol and acetone vs that of water, together with the permanent porosity and high thermal stability, makes this compound a suitable matrix for separation and purification.

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  108. Magnetic and photo-magnetic properties of Co dinuclear complexes Reviewed

    Osamu Sato, Satoshi Miura, Hiroyuki Maruyama, Yanjuan Zhang, Dayu Wu, Wen Zhang, Haitao Xu, Ryotaro Matsuda, Haoling Sun, Jun Tao

    INORGANICA CHIMICA ACTA   Vol. 361 ( 12-13 ) page: 3659 - 3662   2008.9

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    The magnetic and photo-magnetic properties of Co dinuclear compounds were studied. The Co compounds, [{Co(tpa)}(2)(dhbq)](BF(4))(3) center dot 2H(2)O and [{Co(tpa)}(2)(dhbq)](ClO(4))(3) center dot 2H(2)O, have the structure [(tpa)Co(III-LS)-(mu-dhbq)(3) -Co(III-LS)(tpa)](3) (where LS, H(2)dhbq, tpa denote low-spin, 2,5-di-hydroxy-1,4-benzoquinone and tris(2-pyridylmethyl)amine, respectively) at room temperature. On heating, these compounds exhibit valence-tautomeric inter-conversion; [(tpa)Co(III-LS) -(mu-dhbq)(3) -Co(III-LS)(tpa)](3) reversible arrow [(tpa)Co(II-HS)-(mu-dhbq)(2) -Co(III-LS)(tpa)](3) (where HS denotes high-spin). Furthermore, both of these compounds exhibit photo-induced valence tautomerism at low temperature (&lt; 60 K). These results show that the electronic structures of these complexes can be controlled by modifying the counter anions. (c) 2008 Elsevier B.V. All rights reserved.

    DOI: 10.1016/j.ica.2008.03.089

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  109. Storage and sorption properties of acetylene in jungle-gym-like open frameworks Reviewed

    Daisuke Tanaka, Masakazu Higuchi, Satoshi Horike, Ryotaro Matsuda, Yoshinori Kinoshita, Nobuhiro Yanai, Susumu Kitagawa

    CHEMISTRY-AN ASIAN JOURNAL   Vol. 3 ( 8-9 ) page: 1343 - 1349   2008

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    The acetylene-sorption properties of six porous coordination polymers (PCPs), [M-2(L)(2)(dabco)](n) (dabco = 1,4-diazabicyclo[2.2.2]octane, M = Cu2+ (1), Zn2+ (2), L = 1,4-benzenedicarboxylate (bdc; 1a, 2a), 1,4-naphthalenedicarboxylate (ndc; 1b, 2b), 9,10-anthracenedicarboxylate (adc; 1c, 2c)), were investigated. The acetylene sorption isotherms of 1 and 2 measured at 195 K are of type I and show a steep increase at low relative pressures. The sorption properties of carbon dioxide at 195 K were also investigated. Compounds 1 and 2 showed a large difference in onset pressure between acetylene sorption isotherms, although the difference between the carbon dioxide sorption isotherms is not so significant. In particular, 2c displayed a remarkable affinity for acetylene. The acetylene sorption isotherm at 298 K showed that the adsorption amounts for 2c and 2b at 298 K, 1 atm (101 and 106 mL g(-1), respectively) were higher than those of other conventional porous materials. Notably, of the compounds 1 and 2, the porous crystals 2c had the highest affinity for acetylene.

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  110. Chemistry of coordination space of porous coordination polymers Reviewed

    Susumu Kitagawa, Ryotaro Matsuda

    COORDINATION CHEMISTRY REVIEWS   Vol. 251 ( 21-24 ) page: 2490 - 2509   2007.11

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    Recently, syntheses of epoch-making space materials using coordination compounds are underway by various groups. The rational synthetic strategy of the space of coordination compounds provides unique structures and functions, which have not been found in traditional materials. Now, we intend to focus on this scientific field from a new viewpoint. We define coordination space as the space where the coordination bond plays an important role in the formation of the spatial structures and where various physical properties are exhibited. In this article, we focus on the coordination spaces provided by porous coordination polymers, and their uniqueness is illustrated with current representative results. (C) 2007 Elsevier B. V. All rights reserved.

    DOI: 10.1016/j.ccr.2007.07.009

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  111. Guest-specific function of a flexible undulating channel in a 7,7,8,8-tetracyano-p-quinodimethane dimer-based porous coordination polymer Reviewed

    Satoru Shimomura, Satoshi Horike, Ryotaro Matsuda, Susumu Kitagawa

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   Vol. 129 ( 36 ) page: 10990 - +   2007.9

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    We have designed and synthesized a flexible porous coordination polymer with highly selective capacity to separate benzene from cyclohexane. The undulating channel providing the suitable space for the benzene and the H-pi interaction between the host framework and the guest molecules result in this high selectivity.

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  112. Photo-induced valence tautomerism in Co complexes Reviewed

    Osamu Sato, Aili Cui, Ryotaro Matsuda, Jun Tao, Shinya Hayami

    ACCOUNTS OF CHEMICAL RESEARCH   Vol. 40 ( 5 ) page: 361 - 369   2007.5

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    A number of photofunctional molecular compounds have been developed recently. Typical examples of these are phototunable valence tautomeric compounds, which are now attracting great attention. When the charge-transfer bands of some Co valence tautomeric compounds are excited at low temperature, metastable redox isomers can be created after irradiation. The lifetimes of the metastable states can be more than several hours. These transformations can involve changes in the magnetic properties of the compounds, as well as their color. Hence, these compounds can be regarded as novel photomagnetic materials. The photoresponsive behaviors of these valence tautomeric compounds are similar to those of spin-crossover complexes (light-induced excited spin-state trapping effects).

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  113. Three-dimensional porous coordination polymer functionalized with amide groups based on tridentate ligand: Selective sorption and catalysis Reviewed

    Shinpei Hasegawa, Satoshi Horike, Ryotaro Matsuda, Shuhei Furukawa, Katsunori Mochizuki, Yoshinori Kinoshita, Susumu Kitagawa

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   Vol. 129 ( 9 ) page: 2607 - 2614   2007.3

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    To create a functionalized porous compound, amide group is used in porous framework to produce attractive interactions with guest molecules. To avoid hydrogen-bond formation between these amide groups our strategy was to build a three-dimensional (3D) coordination network using a tridentate amide ligand as the three-connector part. From Cd(NO3)(2)center dot 4H(2)O and a three-connector ligand with amide groups a 3D porous coordination polymer (PCP) based on octahedral Cd(II) centers, {[Cd(4-btapa)(2)(NO3)(2)]center dot 6H(2)O center dot 2DMF}(n) (1a), was obtained (4-btapa = 1,3,5-benzene tricarboxylic acid tris[N-(4-pyridyl)amide]). The amide groups, which act as guest interaction sites, occur on the surfaces of channels with dimensions of 4.7 x 7.3 A(2). X-ray powder diffraction measurements showed that the desolvated compound (1b) selectively includes guests with a concurrent flexible structural (amorphous-to-crystalline) transformation. The highly ordered amide groups in the channels play an important role in the interaction with the guest molecules, which was confirmed by thermogravimetric analysis, adsorption/desorption measurements, and X-ray crystallography. We also performed a Knoevenagel condensation reaction catalyzed by 1a to demonstrate its selective heterogeneous base catalytic properties, which depend on the sizes of the reactants. The solid catalyst 1a maintains its crystalline framework after the reaction and is easily recycled.

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  114. A flexible interpenetrating coordination framework with a bimodal porous functionality Reviewed

    Tapas Kumar Maji, Ryotaro Matsuda, Susumu Kitagawa

    NATURE MATERIALS   Vol. 6 ( 2 ) page: 142 - 148   2007.2

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    Introducing a functional part into open-framework materials that tunes the pore size/shape and overall porous activity will open new routes in framework engineering and in the fabrication of new materials. We have designed and synthesized a bimodal microporous twofold interpenetrating network {[Ni(bpe)(2)(N(CN)(2))](N(CN)(2))(5H2O)}(n) (1), with two types of channel for anionic N(CN)(2)(-) (dicyanamide) and neutral water molecules, respectively. The dehydrated framework provides a dual function of specific anion exchange of free N(CN)(2)(-) for the smaller N-3(-) anions and selective gas sorption. The N-3-exchanged framework leads to a dislocation of the mutual positions of the two interpenetrating frameworks, resulting in an increase in the effective pore size in one of the counterparts of the channels and a higher accommodation of adsorbate than in the as-synthesized framework (1), showing the first case of controlled sorption properties in flexible porous frameworks.

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  115. Chemical reaction-inspired crystal growth of a coordination polymer toward morphology design and control Reviewed

    Shigeyuki Masaoka, Daisuke Tanaka, Hiroyuki Kitahata, Sumiko Araki, Ryotaro Matsuda, Kenichi Yoshikawa, Kenichi Kato, Masaki Takata, Susumu Kitagawa

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   Vol. 128 ( 49 ) page: 15799 - 15808   2006.12

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    This paper reports a novel crystal growth system of a coordination framework {[Cu-3(CN)(3){hat(CN)(3)(OEt)(3)}]}n (1) (hat-(CN)(3)(OEt)(3)) 2,6,10-tricyano-3,7,11-triethoxy-1,4,5,8,9,12-hexaazatriphenylene). The coordination polymer is crystallized through the reaction of 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12hexaazatriphenylene (hat-(CN)(6)), ethanol, and copper(I) complex, involving the breaking and forming of covalent bonds. The crystal morphologies obtained in the present system contain dumbbells, cogwheels, and superlattices. Moreover, in the growth perpendicular to the c-axis, periodic ramification at regular interval is observed, affording superlattice morphologies. Observation of the growth of dumbbell crystals shows that the growth rates parallel and perpendicular to the crystallographic c-axis are quite different: the former shows a drastic change with the reaction duration, while the latter is almost constant. These results are reproduced as a simple reaction-diffusion system, indicating that chemical reactions on crystal surfaces play an important role in determining the macroscopic crystal morphologies.

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  116. TCNQ dianion-based coordination polymer whose open framework shows charge-transfer type guest inclusion Reviewed

    Satoru Shimomura, Ryotaro Matsuda, Takashi Tsujino, Takashi Kawamura, Susumu Kitagawa

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   Vol. 128 ( 51 ) page: 16416 - 16417   2006.12

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    DOI: 10.1021/ja0660047

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  117. Immobilization of sodium ions on the pore surface of a porous coordination polymer Reviewed

    S Horike, R Matsuda, D Tanaka, M Mizuno, K Endo, S Kitagawa

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   Vol. 128 ( 13 ) page: 4222 - 4223   2006.4

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    A porous coordination polymer (PCP) with immobilization of sodium cations on the pore surface has been synthesized, by employing a bifunctional carboxylate/sulfonate ligand, and structurally characterized. The porous framework with 1D channels of the dimension of 4.9 × 4.9 ?2 shows high thermal stability (?330 °C), affording Type I adsorption isotherms for CO2, acetone, and benzene. The chemical shift of 13C NMR and characteristic adsorption energy (βE0) of acetone adsorbed in this compound represent the Lewis acidity of this framework. Copyright ? 2006 American Chemical Society.

    DOI: 10.1021/ja0606879

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  118. Metastable sorption state of a metal-organic porous material determined by in situ synchrotron powder diffraction Reviewed

    Yoshiki Kubota, Masaki Takata, Ryotaro Matsuda, Ryo Kitaura, Susumu Kitagawa, Tatsuo C. Kobayashi

    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   Vol. 45 ( 30 ) page: 4932 - 4936   2006

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    DOI: 10.1002/anie.200600976

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  119. Dynamic motion of building blocks in porous coordination polymers Reviewed

    Satoshi Horike, Ryotaro Matsuda, Daisuke Tanaka, Seijiro Matsubara, Motohiro Mizuno, Kazunaka Endo, Susumu Kitagawa

    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   Vol. 45 ( 43 ) page: 7226 - 7230   2006

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    DOI: 10.1002/anie.200603196

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  120. Formation and characterization of crystalline molecular arrays of gas molecules in a 1-dimensional ultramicropore of a porous copper coordination polymer Reviewed

    R Kitaura, R Matsuda, Y Kubota, S Kitagawa, M Takata, TC Kobayashi, M Suzuki

    JOURNAL OF PHYSICAL CHEMISTRY B   Vol. 109 ( 49 ) page: 23378 - 23385   2005.12

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    Molecules and atoms confined in a nanospace may have properties distinctly different from those of the bulk fluid, owing to the formation of a specific molecular array characteristic of nanospace. In situ synchrotron powder X-ray diffraction measurements have been used to observe confined guest molecules such as N(2), O(2), Ar, and CH(4) in the well-regulated ultramicropore of a copper coordination polymer, 1 ([Cu(2),(pzdc)(2)pyz]: pzdc = 2,3-pyrazinedicarboxylate and pyz = pyrazine). The obtained crystal structures indicate that guest molecules are confined in a linear fashion to form crystal ine-like regular ordered arrays, in contrast to the situation in the gas and liquid state, even at temperatures above the boiling point, and the ordered arrays are characteristic of the kind of gas molecule and the geometrical and potential properties of the ultramicropore of 1.

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  121. Guest-induced asymmetry in a metal-organic porous solid with reversible single-crystal-to-single-crystal structural transformation Reviewed

    TK Maji, G Mostafa, R Matsuda, S Kitagawa

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   Vol. 127 ( 49 ) page: 17152 - 17153   2005.12

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    A metal-organic honeycomb-like 2D pillared-bilayer open framework has been constructed which shows dynamic sponge-like single-crystal-to-single-crystal transformation upon dehydration and rehydration. The dehydrated acentric nonporous phase transformed to the porous centric phase with the selective adsorbate concomitant with the structural transformation correlated with the single-crystal structure determination. Copyright ? 2005 American Chemical Society.

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  122. Flexible microporous coordination polymers Reviewed

    K Uemura, R Matsuda, S Kitagawa

    JOURNAL OF SOLID STATE CHEMISTRY   Vol. 178 ( 8 ) page: 2420 - 2429   2005.8

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    In a decade, many porous coordination polymers have been synthesized, providing a variety of properties ranging from storage, separation and exchange of guests in their cavities, magnetism, conductivity and catalysis by their frameworks. Recent advent of flexible porous coordination polymers, which exhibit elastic guest accommodation in contrast to rigid three-dimensional (3-D) frameworks of conventional porous materials, have acquired a position as a new class of porous materials. Such flexible porous properties induce highly selective guest accommodation and magnetic modulation, which could now be a unique class of practical materials. In this review, we introduce recent flexible porous coordination polymers (3-17) and their functional properties, categorizing with the four types of pores with framework deformation. (c) 2005 Published by Elsevier Inc.

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  123. Highly controlled acetylene accommodation in a metal-organic microporous material Reviewed

    R Matsuda, R Kitaura, S Kitagawa, Y Kubota, RV Belosludov, TC Kobayashi, H Sakamoto, T Chiba, M Takata, Y Kawazoe, Y Mita

    NATURE   Vol. 436 ( 7048 ) page: 238 - 241   2005.7

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    Metal - organic microporous materials(1-4) (MOMs) have attracted wide scientific attention owing to their unusual structure and properties, as well as commercial interest due to their potential applications in storage(5-9), separation(10,11) and heterogeneous catalysis(12,13). One of the advantages of MOMs compared to other microporous materials, such as activated carbons, is their ability to exhibit a variety of pore surface properties such as hydrophilicity and chirality, as a result of the controlled incorporation of organic functional groups into the pore walls(11,13-15). This capability means that the pore surfaces of MOMs could be designed to adsorb specific molecules; but few design strategies for the adsorption of small molecules have been established so far. Here we report high levels of selective sorption of acetylene molecules as compared to a very similar molecule, carbon dioxide, onto the functionalized surface of a MOM. The acetylene molecules are held at a periodic distance from one another by hydrogen bonding between two non-coordinated oxygen atoms in the nanoscale pore wall of the MOM and the two hydrogen atoms of the acetylene molecule. This permits the stable storage of acetylene at a density 200 times the safe compression limit of free acetylene at room temperature.

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  124. Flexible coordination polymers as novel porous materials Reviewed

    Tapas Kumar Maji, Ryotoro Matsuda, Susumu Kitagawa

    Studies in Surface Science and Catalysis   Vol. 156   page: 497-504   2005.1

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    In this manuscript, we report synthesis and crystal structure of a novel coordination polymer of Cd(II), {[Cd(pzdc)(bpp)(H2O)]3 2O}n (3) and porous functionalities of {[Cd(pzdc)(azpy)]2H2O}n (1), {[Cd(pzdc)(bpee)]1.5H2O}n(2) and 3 [where pzdc = pyrazine-2,3-dicarboxylate, azpy = 4,4' -azopyridine; bpee = 1,2-bis-(4-pyridyl)ethylene and bpp =1,3-bis(4-pyridyl)propane]. Structure determination reveals that complex 3 is a 3D porous framework with one dimensional micro-channel along the crystallographic c-axis (channel size: 8.4*4.2 ?; Vvoid = 17.2%), where each Cd(II) is in distorted octahedral environment and attached with two pzdc, two bpp ligand and one water molecule. The TGA analysis shows that the dehydrated framework is stable up to 180°C and XRPD measurement suggests that the dehydrated materials become amorphous, but with exposure to the water vapor regenerates the original framework. Adsorption measurement shows that water molecules are adsorbed in two-step process, whereas MeOH molecules in a single step and both the sorption phenomena occur with large hysteresis. ? 2005 Elsevier B.V. All rights reserved.

  125. Dynamics of guests in microporous coordination polymers studied by solid state NMR and X-ray analysis Reviewed

    Satoshi Horike, Ryotaro Matsuda, Susumu Kitagawa

    Studies in Surface Science and Catalysis   Vol. 156   page: 725-732   2005.1

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    Molecular motions of methanol and aromatic molecules (benzene, toluene, p-xylene) adsorbed in 1D nanochannels of pillared-layer coordination polymers with paramagnetic metal ions have been studied by2H NMR together with X-ray crystallography. NMR spectra at various temperatures and Rietveld analyses of powder X-ray diffractions represented that the characteristic shape and periodic potential of each micropore confined guests in highly restricted motions and ordering even though the guests are physisorbed. ? 2005 Elsevier B.V. All rights reserved.

  126. Direct observation of hydrogen molecules adsorbed onto a microporous coordination polymer Reviewed

    Y Kubota, M Takata, R Matsuda, R Kitaura, S Kitagawa, K Kato, M Sakata, TC Kobayashi

    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   Vol. 44 ( 6 ) page: 920 - 923   2005

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    Trapped hydrogen molecules in the nanochannels of a copper coordination polymer were successfully observed by the synchrotron powder-diffraction method. The adsorbed molecules are located near one corner of the rectangular nanochannels, and the pockets of the pore walls are suited to the size of the hydrogen molecules (see picture). These results could provide guidelines for the design of hydrogen-storage materials.

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  127. Magnetic properties of molecular oxygen adsorbed in micro-porous metal-organic solids Reviewed

    TC Kobayashi, A Matsuo, M Suzuki, K Kindo, R Kitaura, R Matsuda, S Kitagawa

    PROGRESS OF THEORETICAL PHYSICS SUPPLEMENT   Vol. 159 ( 159 ) page: 271 - 279   2005

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    The magnetic properties of O-2 adsorbed in nanochannels of porous metal-organic solids CPL-1 and CPL-p1 have been investigated by means of high-field magnetization process measurement. The contribution from adsorbed 02 shows the metamagnetic-like behavior in both compounds. We propose "the field-induced rearrangement mechanism" as the explanation for the metamagnetic-like behavior. It is known for the O-2-O-2 dimer that the magnetic interaction depends strongly on the intermolecular distance and the orientation of molecular axes. It is considered naturally that the stable arrangement with saturated magnetic moment in the sufficient high field is different from the H-structure which is stable at zero field.

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  128. Direct Observation of Hydrogen Molecules adsorbed in a Coordination Polymer

    Kubota Yoshiki, Takata Masaki, Matsuda Ryotaro, Kitaura Ryo, Kitagawa Susumu, Kobayashi Tatsuo C., Kato Kenichi, Sakata Makoto

    ACTA CRYSTALLOGRAPHICA A-FOUNDATION AND ADVANCES   Vol. 61   page: C403-C403   2005

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  129. Dynamics of guests in microporous coordination polymers studied by solid state NMR and X-ray analysis Reviewed

    S Horike, R Matsuda, S Kitagawa

    NANOPOROUS MATERIALS IV   Vol. 156   page: 725 - 732   2005

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    Molecular motions of methanol and aromatic molecules (benzene, toluene, p-xylene) adsorbed in ID nanochannels of pillared-layer coordination polymers with paramagnetic metal ions have been studied by H-2 NMR together with X-ray crystallography. NMR spectra at various temperatures and Rietveld analyses of powder X-ray diffractions represented that the characteristic shape and periodic potential of each micropore confined guests in highly restricted motions and ordering even though the guests are physisorbed.

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  130. Flexible coordination polymers as novel porous materials Reviewed

    TK Maji, R Matsuda, S Kitagawa

    NANOPOROUS MATERIALS IV   Vol. 156   page: 497 - 504   2005

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    In this manuscript, we report synthesis and crystal structure of a novel coordination polymer of Cd(II), {[Cd(pzdc)(bpp)(H2O)](3)H2O}(n) (3) and porous functionalities of ([Cd(pzdc)(azpy)[2H(2)O}(n). (1), {[Cd(pzdc)(bpee)]1.5H(2)O}(n) (2) and 3 [where pzdc pyrazine-2,3-dicarboxylate, azpy = 4,4'-azopyridine; bpee = 1,2-bis-(4-pyridyl)ethylene and bpp = 1,3-bis(4-pyridyl)propane]. Structure determination reveals that complex 3 is a 3D porous framework with one dimensional micro-channel along the crystallographic c-axis (channel size: 8.4 x 4.2 angstrom; V-void = 17.2%), where each Cd(II) is in distorted octahedral environment and attached with two pzdc, two bpp ligand and one water molecule. The TGA analysis shows that the dehydrated framework is stable up to 180 degrees C and XRPD measurement suggests that the dehydrated materials become amorphous, but with exposure to the water vapor regenerates the original framework. Adsorption measurement shows that water molecules are adsorbed in two-step process, whereas MeOH molecules in a single step and both the sorption phenomena occur with large hysteresis.

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  131. Motion of methanol adsorbed in porous coordination polymer with paramagnetic metal ions Reviewed

    Satoshi Horike, Ryotaro Matsuda, Ryo Kitaura, Susumu Kitagawa, Takahiro Iijima, Kazunaka Endo, Yoshiki Kubota, Masaki Takata

    Chemical Communications   Vol. 10   page: 2152-2153   2004.11

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    Molecular motions of methanol adsorbed in 1D nano-channels of pillared-layer coordination polymer with paramagnetic metal ions have been studied by 2H NMR together with X-ray crystallography.

  132. Guest shape-responsive fitting of porous coordination polymer with shrinkable framework Reviewed

    Ryotaro Matsuda, Ryo Kitaura, Susumu Kitagawa, Yoshiki Kubota, Tatsuo C. Kobayashi, Satoshi Horike, Masaki Takata

    Journal of the American Chemical Society   Vol. 126   page: 14063-14070   2004.11

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    measured (pzdc = pyrazine-2,3-dicarboxylate, bpy = 4,4′-bipyridine) (where G = H2O for CPL-2 ⊃ H2O, G = benzene for CPL-2 ⊃ benzene, and G = void for the apohost). The structures of apohost and CPL-2 ⊃ benzene were determined from Rietveld analysis. Adsorption of benzene in the channels induced a remarkable contraction in the crystal (b axis; 6.8%, volume; 4.9%), although the channels were occupied by the benzene molecules. This crystal transformation provides a new pore structure that is well suited for benzene molecules, and we denote it as a "shape-responsive fitting" transformation. This type of pore gives rise to a new guideline: frameworks can be composed of flexible motifs that are linked via strong bond and/or stiff motifs that are connected via weaker bonds.

  133. Guest shape-responsive fitting of porous coordination polymer with shrinkable framework Reviewed

    R Matsuda, R Kitaura, S Kitagawa, Y Kubota, TC Kobayashi, S Horike, M Takata

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   Vol. 126 ( 43 ) page: 14063 - 14070   2004.11

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    In situ synchrotron X-ray powder diffraction patterns of porous coordination polymers {[Cu-2-(pzdc)(2)(bpy)](.)G} have been measured (pzdc = pyrazine-2,3-dicarboxylate, bpy = 4,4'-bipyridine) (where G = H2O for CPL-2 superset of H2O, G = benzene for CPL-2 superset of benzene, and G = void for the apohost). The structures of apohost and CPL-2 superset of benzene were determined from Rietveld analysis. Adsorption of benzene in the channels induced a remarkable contraction in the crystal (b axis; 6.8%, volume; 4.9%), although the channels were occupied by the benzene molecules. This crystal transformation provides a new pore structure that is well suited for benzene molecules, and we denote it as a "shape-responsive fitting" transformation. This type of pore gives rise to a new guideline: frameworks can be composed of flexible motifs that are linked via strong bond and/or stiff motifs that are connected via weaker bonds.

    DOI: 10.1021/ja046925m

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  134. Rational design and crystal structure determination of a 3-D metal-organic jungle-gym-like open framework Reviewed

    Ryo Kitaura, Fumiyasu Iwahori, Ryotaro Matsuda, Susumu Kitagawa, Yoshiki Kubota, Masaki Takata, Tatsuo C. Kobayashi

    Inorganic Chemistry   Vol. 43   page: 6522-6524   2004.10

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    A new three-dimensional (3-D) jungle-gym-like open metal-organic framework has been synthesized from a two-dimensional (2-D) layer compound using a heterogeneous pillar insertion reaction. Both the starting 2-D layer and the resulting 3-D open compounds have been characterized using X-ray crystallography.

  135. Rational design and crystal structure determination of a 3-D metal-organic jungle-gym-like open framework Reviewed

    R Kitaura, F Iwahori, R Matsuda, S Kitagawa, Y Kubota, M Takata, TC Kobayashi

    INORGANIC CHEMISTRY   Vol. 43 ( 21 ) page: 6522 - 6524   2004.10

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    A new three-dimensional (3-D) jungle-gym-like open metal-organic framework has been synthesized from a two-dimensional (2-D) layer compound using a heterogeneous pillar insertion reaction. Both the starting 2-D layer and the resulting 3-D open compounds have been characterized using X-ray crystallography.

    DOI: 10.1021/ic049005d

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  136. Expanding and shrinking porous modulation based on pillared-layer coordination polymers showing selective guest adsorption Reviewed

    Tapas Kumar Maji, Kazuhiro Uemura, Ho Chol Chang, Ryotaro Matsuda, Susumu Kitagawa

    Angewandte Chemie - International Edition   Vol. 43   page: 3269-3272   2004.6

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    Rationally designed and synthesized, two novel pillar-layered 3D microporous frameworks {[Cd(pzdc)(azpy)]?2H2O}n, (1, left) and {[Cd(pzdc)(bpee)]?1.5H2O}n, (2, right) have high thermal stability and highly selective adsorption properties. Removal of guest water molecules results in the expansion of 1 but the contraction of 2.

  137. Immobilization of a metallo Schiff base into a microporous coordination polymer Reviewed

    Ryo Kitaura, Goro Onoyama, Hirotoshi Sakamoto, Ryotaro Matsuda, Sin Ichiro Noro, Susumu Kitagawa

    Angewandte Chemie - International Edition   Vol. 43   page: 2684-2687   2004.5

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    Wall decoration: Coordinatively unsaturated metal centers (CuII, CoII, and NiII) can be embedded in the pore wall of a microporous coordination polymer containing Schiff base type metalloligands [M(salphdc)]2- (H4salphdc = N,N' -o- phenylenebis(salicylideneimine-5,5' -dicarboxylic acid)). These coordination polymers possess large 1D channels with dimensions of approximately 14 * 14 ?2 (see structure).

  138. Magnetism of a one-dimensional array of oxygen in a micro-porous metal-organic solid Reviewed

    A. Matsuo, T. C. Kobayashi, M. Suzuki, K. Kindo, R. Kitaura, R. Matsuda, H. C. Chang, S. Kitagawa

    Journal of Magnetism and Magnetic Materials     page: 272-276   2004.5

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    The magnetic properties of molecular oxygen adsorbed in the micro-porous metal-organic solids have been investigated. Adsorbed O2 molecules form a ladder structure in the nanochannels of CPL-1. The temperature dependence of susceptibility and the high-field magnetization process indicate the nonmagnetic ground state of the adsorbed O2 at low temperatures. ? 2003 Elsevier B.V. All rights reserved.

  139. Magnetism of a one-dimensional array of oxygen in a micro-porous metal-organic solid Reviewed

    A. Matsuo, T. C. Kobayashi, M. Suzuki, K. Kindo, R. Kitaura, R. Matsuda, H. -C. Chang, S. Kitagawa

    JOURNAL OF MAGNETISM AND MAGNETIC MATERIALS   Vol. 272   page: E643 - E645   2004.5

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    The magnetic properties of molecular oxygen adsorbed in the micro-porous metal-organic solids have been investigated. Adsorbed O-2 molecules form a ladder structure in the nanochannels of CPL-1. The temperature dependence of susceptibility and the high-field magnetization process indicate the nonmagnetic ground state of the adsorbed O-2 at low temperatures. (C) 2003 Elsevier B. V. All rights reserved.

    DOI: 10.1016/j.jmmm.2003.11.327

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  140. Expanding and shrinking porous modulation based on pillared-layer coordination polymers showing selective guest adsorption Reviewed

    TK Maji, K Uemura, HC Chang, R Matsuda, S Kitagawa

    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   Vol. 43 ( 25 ) page: 3269 - 3272   2004

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    Rationally designed and synthesized, two novel pillar-layered 3D microporous frameworks {[Cd(pzdc)(azpy)]?2H2O}n, (1, left) and {[Cd(pzdc)(bpee)]?1.5H2O}n, (2, right) have high thermal stability and highly selective adsorption properties. Removal of guest water molecules results in the expansion of 1 but the contraction of 2.

    DOI: 10.1002/anie.200453923

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  141. Motion of methanol adsorbed in porous coordination polymer with paramagnetic metal ions Reviewed

    S Horike, R Matsuda, R Kitaura, S Kitagawa, T Iijima, K Endo, Y Kubota, M Takata

    CHEMICAL COMMUNICATIONS   Vol. 10 ( 19 ) page: 2152 - 2153   2004

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    Molecular motions of methanol adsorbed in 1D nanochannels of pillared-layer coordination polymer with paramagnetic metal ions have been studied by H-2 NMR together with X-ray crystallography.

    DOI: 10.1039/b406883a

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  142. Immobilization of a metallo Schiff base into a microporous coordination polymer Reviewed

    R Kitaura, G Onoyama, H Sakamoto, R Matsuda, S Noro, S Kitagawa

    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   Vol. 43 ( 20 ) page: 2684 - 2687   2004

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    Wall decoration: Coordinatively unsaturated metal centers (CuII, CoII, and NiII) can be embedded in the pore wall of a microporous coordination polymer containing Schiff base type metalloligands [M(salphdc)]2- (H4salphdc = N,N′-o- phenylenebis(salicylideneimine-5,5′-dicarboxylic acid)). These coordination polymers possess large 1D channels with dimensions of approximately 14 × 14 ?2 (see structure).

    DOI: 10.1002/anie.200352596

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MISC 89

  1. Selective Adsorption of Trace Amount of Sulfur Containing Molecules Using Nanoporous Metal Complexes with Open Metal Sites

    米津章, 森田将司, 森田将司, 日下心平, 堀彰宏, 松田亮太郎

    日本化学会春季年会講演予稿集(CD-ROM)   Vol. 100th   2020

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  2. CO <inf>2</inf> storage on metal-organic frameworks

    Yunsheng Ma, Hideki Tanaka, Ryotaro Matsuda

    Green Energy and Technology     page: 331 - 358   2019.1

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    © Springer Nature Singapore Pte Ltd. 2019. Metal-organic frameworks (MOFs) have received continuous attention because of their highly porous, diversified structures and potential applications as novel adsorbents. In this chapter, the recent progress in developing MOFs for CO 2 capture is reviewed. Several strategies being used to improve CO 2 adsorption uptake at low pressure are highlighted. These strategies are generation of interaction sites in the pores as well as controlling of pore size of MOFs, building of flexible MOFs, and construction of water-stable MOFs. In addition, the high-pressure CO 2 adsorption in highly porous MOFs is reviewed. At last, the studies of CO 2 -loaded structures with crystallographic technique are summarized.

    DOI: 10.1007/978-981-13-3504-4_12

    Scopus

  3. 配位不飽和銅イオンを有するナノポーラス金属錯体による希薄硫黄分子吸着

    米津章, 森田将司, 森田将司, 日下心平, 堀彰宏, 馬運声, 松田亮太郎

    日本吸着学会研究発表会講演要旨集   Vol. 33rd   2019

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  4. 配位不飽和サイトを有するナノポーラス金属錯体による希薄硫黄ガスの吸着除去

    米津章, 森田将司, 森田将司, 日下心平, 堀彰宏, MA Yunsheng, 松田亮太郎

    日本化学会春季年会講演予稿集(CD-ROM)   Vol. 99th   2019

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  5. ポルフィリン部位を有する光応答性ナノポーラス金属錯体の吸着特性

    坂田直弥, 森田将司, 森田将司, 小原勇輝, 荒瀬秀和, 堀彰宏, 松田亮太郎

    日本化学会春季年会講演予稿集(CD-ROM)   Vol. 99th   2019

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  6. 光応答性ナノポーラス金属錯体の合成と吸着特性

    坂田直弥, 森田将司, 森田将司, 小原勇輝, 荒瀬秀和, 堀彰宏, 松田亮太郎

    錯体化学会討論会講演要旨集   Vol. 69th   2019

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  7. ナノポーラス錯体によるジメチルスルフィドの吸着除去

    米津章, 森田将司, 森田将司, 堀彰宏, MA Yunsheng, 松田亮太郎, 松田亮太郎, 松田亮太郎

    日本化学会春季年会講演予稿集(CD-ROM)   Vol. 98th   2018

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  8. 配位不飽和サイトを有するナノポーラス金属錯体によるジメチルスルフィドの吸着除去

    米津章, 森田将司, 森田将司, 堀彰宏, MA Yunsheng, 松田亮太郎, 松田亮太郎

    錯体化学会討論会講演要旨集   Vol. 68th   2018

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  9. 配位不飽和サイトを有するナノポーラス金属錯体による希薄ガスの吸着除去

    米津章, 森田将司, 森田将司, 日下心平, 堀彰宏, 馬運声, 松田亮太郎

    日本吸着学会研究発表会講演要旨集   Vol. 32nd   2018

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  10. 多孔性金属錯体(MOF)の材料研究と応用展開 Invited

    堀彰宏, 松田亮太郎

    工業材料   Vol. 1 ( 3 ) page: 58-62   2017.2

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  11. 多孔性金属錯体によるナノ空間の科学 Invited

    堀彰宏, 松田亮太郎

    ゼオライト(日本ゼオライト学会設立記念号)   Vol. 33 ( 1 ) page: 28-39   2016

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  12. Highly selective adsorption and separation of energy-related gases on soft metal-organic frameworks

    Ryotaro Matsuda, Hiroshi Sato, Susumu Kitagawa

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   Vol. 248   2014.8

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  13. ダブルペロブスカイト型BaYMn<sub>2</sub>O<sub>5+δ</sub>の結晶構造から見た顕著な酸素吸収放出

    本橋輝樹, 高橋平, 鱒渕友治, 吉川信一, 久保田佳基, 小林洋治, 陰山洋, 高田昌樹, 高田昌樹, 北川進, 松田亮太郎

    日本セラミックス協会年会講演予稿集(CD-ROM)   Vol. 2014   2014

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  14. 新しい吸着材料:多孔性金属錯体による光ガス吸着

    松田 亮太郎

    新技術説明会     2013.2

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  15. ダブルペロブスカイト型BaYMn<sub>2</sub>O<sub>5+δ</sub>(0≦δ≦1)の低酸素分圧下における高温結晶構造

    高橋平, 本橋輝樹, 鱒渕友治, 吉川信一, 久保田佳基, 小林洋治, 陰山洋, 高田昌樹, 高田昌樹, 北川進, 松田亮太郎

    日本セラミックス協会秋季シンポジウム講演予稿集(CD-ROM)   Vol. 26th   2013

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  16. 錯体結晶が拓くナノ空間の化学

    松田 亮太郎

    玉尾皓平先生(京都大学名誉教授)古稀記念シンポジウム     2012.11

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  17. 多孔性金属錯体の合成と選択的分子吸着機能に関する研究

    松田 亮太郎

    第26回日本吸着学会研究発表会     2012.11

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  18. 開殻化学種を細孔表面に有する多孔性金属錯体の合成と機能

    松田亮太郎, 佐藤弘志, LI Liangchun, 北川進

    錯体化学会討論会講演要旨集   Vol. 62nd   page: 76   2012.9

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  19. 同時計測で見出すPCPのエキゾチック吸着

    松田 亮太郎

    研究セミナー「エキゾチック分子集合体の新展開」     2012.8

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  20. Unusual Sorption Behavior of Porous Coordination Polymers Having Transformable Building Units

    Ryotaro Matsuda, Hiroshi Sato, Susumu Kitagawa

    International Symposium on Zeolites and Microporous Crystals (ZMPC2012)     2012.7

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  21. 規則性高ポテンシャルナノ・メゾ空間による新分子変換場の創出・多重エネルギー変換ナノ・メゾ空間デバイス

    松田 亮太郎

    CRDS俯瞰ワークショップ(ナノテクノロジー・材料分野)     2012.6

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  22. Stimuli Responsive Porous Coordination Polymers Having Selective Guest Sorption Functions

    Ryotaro Matsuda, Hiroshi Sato, Joobeom Seo, Susumu Kitagawa

    The Third Symposium on Future Challenges for Carbon-based Nanoporous Materials:Adsorption and Energy     2012.5

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  23. Photoresponsive Porous Coordination Polymers for On Demand Type Molecular Adsorption Reviewed

    Ryotaro Matsuda, Hiroshi Sato, Susumu Kitagawa

    The 6th Pacific Basin Conference on Adsorption Science and Technology (PBAST-6)     2012.5

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  24. 高選択的分子吸着能を有する多孔性金属錯体の設計と合成

    松田 亮太郎

    日本化学会第92春季年会(2012)     2012.3

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  25. ダイナミックな構造変化を伴う多孔性配位高分子の吸着 ダイナミックな構造変化を伴う多孔性配位高分子の吸着

    松田 亮太郎, 佐藤 弘志, Seo Joobeo, 北川 進

    第 25 回日本吸着学会 研究発表会・吸着学会創立 25 周年記念シンポジウム     2011.11

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  26. ソフトコアを用いた新規多孔性金属錯体のガス分離特性

    松田亮太郎, SEO Joobeom, 佐藤弘志, 北川進

    錯体化学会討論会講演要旨集   Vol. 61st   page: 12   2011.9

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  27. Unusual porous functions of stimuli responsive porous coordination polymers Reviewed

    Ryotaro Matsuda, Hiroshi Sato, Joobeom Seo, Susumu Kitagawa

    XXII Congress and General Assembly of the International Union of Crystallography     2011.8

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  28. Highly Selective Guest Adsorption in the Nanospace of Porous Coordination Polymers

    松田 亮太郎

    分子科学研究所3研究室合同研究発表会     2011.7

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    DOI: 10.4019/bjscc.57.45

  29. 新しい機能性ナノ空間材料 ~多孔性配位高分子の科学~

    松田亮太郎

    平成23年度先端技術研修     2011.6

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  30. オンデマンド型ガス吸着に向けた光応答性多孔性配位高分子の開発

    松田 亮太郎, 北川 進

    創造機能化学第116委員会(平成23年度6月期研究調査報告会)     2011.6

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  31. 結合の開裂と再構築に基づく細孔拡大型構造変化を示す多孔性金属錯体

    松田亮太郎, 佐藤弘志, 高坂亘, 北川進

    日本化学会第90春季年会(2010)     2011.3

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  32. 25aPS-37 Magnetic properties and arrangements of molecular oxygen adsorbed in a MFI zeolite

    Hori A, Wanikawa Y, Kubota Y, Kuwana K, Kobayashi T. C, Matsuo A, Kindo K, Hakuman M, Nakai K, Kim J, Kato K, Takata M, Matsuda R, Kitagawa S

    Meeting abstracts of the Physical Society of Japan   Vol. 66 ( 1 )   2011.3

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  33. Guest-Induced Structural Transformations and Specific Guest Adsorption of Flexible Porous Coordination Polymers Reviewed

    Ryotaro Matsuda, Hiroshi Sato, Sareeya Bureekaew, Joobeom Seo, Susumu Kitagawa

    The Pacifichem 2010     2010.12

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  34. オンデマンド型ガス吸着に向けた光応答性多孔性配位高分子の合成

    松田 亮太郎, 佐藤 弘志, 北川 進

    第24回日本吸着学会研究発表会     2010.11

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  35. 刺激応答性細孔-多様な機能を発現するPCPのデザインと合成-

    松田亮太郎

    ERATO北川統合細孔プロジェクト一般公開シンポジウム     2010.10

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  36. Photo-responsive Porous Coordination Polymers

    Ryotaro Matsuda, Hiroshi Sato, Susumu Kitagawa

    2nd iCeMS Retreat     2010.10

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  37. Unusual guest-selective adsorption on soft/flexible porous coordination polymers

    Ryotaro Matsuda, Seo Joobeom, Hiroshi Sato, Susumu Kitagawa

    60th Anniversary Conference on Coordination Chemistry     2010.9

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  38. 柔軟性錯体の固溶体を用いたガス吸着能の系統的制御

    福島知宏, 堀毛悟史, 松田亮太郎, 北川進

    錯体化学討論会講演要旨集   Vol. 60th   page: 258   2010.9

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  39. Highly guest selective adsorption on functionalized porous coordination polymers Reviewed

    Ryotaro Matsuda, Joobeom Seo, Satoru Shimomura, Hiroshi Sato, Susumu Kitagawa

    International Conference on Nanoscopic Colloid and Surface Science (NCSS2010)     2010.9

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  40. Guest-Induced Structural Transformations of Flexible Porous Coordination Polymers Investigated by Coincident Adsorption/XRPD Measurement Reviewed

    Ryotaro Matsuda, Sareeya Bureekaew, Hiroshi Sato, Joobeom Seo, Susumu Kitagawa

    2nd International Conference on Metal-Organi Frameworks and_Open Framework Compounds     2010.9

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  41. 多孔性配位高分子のナノ空間への高選択的ゲスト吸着

    松田亮太郎

    第60回錯体化学討論会     2010.9

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  42. Design of gas adsorption functions of soft/flexible porous coordination polymers

    Ryotaro Matsuda

    NCBS/iCeMS Joint symposium     2010.8

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  43. 26aWL-8 Magnetic properties of molecular oxygen adsorbed in MFI zeolite

    Kuwana K, Kobayashi T. C, Hori A, Matsuo A, Kindo K, Hakuman M, Nakai K, Matsuda R, Kitagawa S

    Meeting abstracts of the Physical Society of Japan   Vol. 65 ( 2 )   2010.8

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  44. 26aWL-9 The molecular arrangement of O_2 absorbed in MFI zeolite

    Wanikawa Y, Kubota Y, Hori A, Kuwana K, Kobayashi T. C, Hakuman M, Nakai K, Kim J, Kato K, Takata M, Matsuda R, Kitagawa S

    Meeting abstracts of the Physical Society of Japan   Vol. 65 ( 2 )   2010.8

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  45. Unusual sorption behavior on soft/flexible porous coordination polymers

    Ryotaro Matsuda

    Kitagawa iCeMS/ERATO-Yaghi CNSI Joint Symposium “Framework materials in the future”     2010.6

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  46. Multi-step Adsorption of Flexible Porous Coordination Polymers Investigated by Coincident Measurements of Adsorption and X-ray Powder Diffraction Reviewed

    Ryotaro Matsuda, Sareeya Bureekaew, Joobeom Seo, Hiroshi Sato, Susumu Kitagawa

    10th International Conference on Fundamentals of Adsorption (FOA10)     2010.5

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  47. New Nanospace-Chemistry by Porous Coordination Polymers

    MATSUDA RYOTARO, YANAI NOBUHIRO, KITAGAWA SUSUMU

    觸媒 = Catalyst   Vol. 52 ( 3 ) page: 178 - 183   2010.4

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  48. 22pEF-8 Correlation between magnetic properties and arrangements of molecular oxygen adsorbed in a microporous coordination polymer Cu-CHD

    Hori A, Kobayashi T. C, Kubota Y, Matsuo A, Kindo K, Kim J, Kato K, Takata M, Sakamoto H, Matsuda R, Kitagawa S

    Meeting abstracts of the Physical Society of Japan   Vol. 65 ( 1 )   2010.3

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  49. 22pPSA-36 The molecular arrangement of O_2 absorbed in MFI zeolite

    Wanikawa Y, Kubota Y, Hori A, Kuwana K, Kobayashi T. C, Hakuman M, Nakai K, Kim J, Kato K, Takata M, Matsuda R, Kitagawa S

    Meeting abstracts of the Physical Society of Japan   Vol. 65 ( 1 )   2010.3

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  50. 22pPSA-35 Magnetic properties of molecular oxygen adsorbed in MFI zeolite

    Kuwana K, Hori A, Kobayashi T. C, Matsuo A, Kindo K, Hakuman M, Nakai K, Matsuda R, Kitagawa S

    Meeting abstracts of the Physical Society of Japan   Vol. 65 ( 1 )   2010.3

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  51. 柔軟性錯体の固溶体における構造とガス吸着能との相関

    福島知宏, 堀毛悟史, 松田亮太郎, 北川進, 北川進, 北川進

    分子科学討論会講演プログラム&amp;要旨(Web)   Vol. 4th   page: ROMBUNNO.4P052 (WEB ONLY)   2010

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  52. 吸着/粉末X線回折同時測定による多孔性配位高分子の多段階吸着挙動の解明

    松田 亮太郎, ブリケオ サリーヤ, 徐 宙範, 佐藤 弘志, 坂本 裕俊, 北川 進

    第62回コロイドおよび界面化学討論会     2009.9

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  53. 多孔性金属錯体の化学を基盤とした高機能多孔性物質の開発

    松田 亮太郎

    グローバルCOE 有機若手ワークショップ     2009.9

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  54. 27aQJ-9 High-Field Magnetization process of O_2 Adsorbed in a Microprous Coordination Polymer CPL-1 at Various Temperatures

    Hori A, Kobayashi T. C, Matsuo A, Kindo K, Matsuda R, Kitagawa S

    Meeting abstracts of the Physical Society of Japan   Vol. 64 ( 2 )   2009.8

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  55. Syntheses and adsorption properties of porous coordination polymers constructed with 5-dimethylaminoisophthalate.

    福島知宏, 中川啓史, 松田亮太郎, 北川進

    日本化学会講演予稿集   Vol. 89th ( 1 ) page: 352   2009.3

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  56. 27pPSB-34 High field magnetization process of O_2 adsorbed in microporous coordination polymers Zn_2(TCBP)

    Matsuo A, Hori A, Toda Y, Sakamoto H, Higuchi M, Matsuda R, Kitagawa S, Kobayashi T. C, Kindo K

    Meeting abstracts of the Physical Society of Japan   Vol. 64 ( 1 )   2009.3

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  57. 27pPSB-42 The arrangement of O_2 adsorbed in coordination polymer Zn_2(TcBP)

    Hori A, Toda Y, Kobayashi T. C, Minakata C, Kubota Y, Takata M, Sakamoto H, Matsuda R, Higuchi M, Kitagawa S, Schroder M

    Meeting abstracts of the Physical Society of Japan   Vol. 64 ( 1 )   2009.3

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  58. 新しい機能性ナノ空間の創造 ~多孔性金属錯体の科学と実際~

    松田 亮太郎

    アルプスサイエンスセミナー2008     2008.11

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  59. 温度に依存した動的構造均一性を示す多孔性金属錯体の選択的分子吸着

    松田亮太郎, 辻野貴志, 坂本裕俊, 久保田佳基, 森重國光, 高田昌樹, 北川進

    錯体化学討論会講演要旨集   Vol. 58th   page: 125   2008.9

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  60. 温度応答型動的構造均一性を示す多孔性金属錯体の選択的分子吸着

    松田亮太郎, 辻野貴志, 坂本裕俊, 久保田佳基, 高田昌樹, 森重國光, 北川進

    コロイドおよび界面化学討論会講演要旨集   Vol. 61st   page: 282   2008.8

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  61. 光およびゲスト分子応答性を示すコバルト-鉄シアノ錯体の構造相転移と磁気特性

    松田 亮太郎, Sun Hao-Ling, 井上 香織, 佐藤 治

    第57回錯体化学討論会     2007.9

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  62. HIGHLY STABLE AND SELECTIVE ACETYLENE ADSORPTION IN A MICROPOROUS COORDINATION POLYMER

    R. Matsuda, S. Kitagawa, Y. Kubota, M. Takata

    The 41st IUPAC World Chemistry Congress     2007.8

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  63. 雰囲気応答型鉄シアノ錯体の磁気特性と構造変化のその場測定

    松田 亮太郎

    特定領域研究「配位空間の化学」平成19年度第1回全体会議     2007.5

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  64. 雰囲気応答性を示す鉄-コバルトシアノ錯体の構造相転移と磁気特性のその場測定

    松田 亮太郎, 佐藤治

    日本化学会第87春季年会     2007.3

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  65. 機能性多孔性金属錯体の合成と特異的吸着現象の発現

    松田 亮太郎

    特定領域研究「配位空間の化学」平成18年度第1回全体会議     2006.6

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  66. 27pPSB-26 High field magnetization process of arrayed oxygen molecules in a nano-channel

    Matsuo A, Chiba T, Matsuda R, Uemura T, Kitagawa S, Kobayashi T.C, Kindo K

    Meeting abstracts of the Physical Society of Japan   Vol. 61 ( 1 )   2006.3

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  67. アセチレンを閉じこめる物質--多孔性配位高分子の開発

    松田 亮太郎, 北川 進

    化学   Vol. 61 ( 2 ) page: 33 - 36   2006.2

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  68. 多孔性配位高分子結晶中におけるアセチレンの特異的吸着挙動

    松田亮太郎, 北浦良, 北川進, 久保田佳基, 小林達夫, 高田昌樹, 美田佳三

    錯体化学討論会講演要旨集   Vol. 55th   page: 69   2005.9

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  69. 吸着量に依存する多孔性配位高分子結晶の構造転移と吸着挙動

    松田亮太郎, 北浦良, 北川進, 久保田佳基, 小林達夫, 高田昌樹

    コロイドおよび界面化学討論会講演要旨集   Vol. 58th   page: 200   2005.8

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  70. 20pYF-2 Chemistry and Physics in Nano-channels of Metal Complexes

    Kitagawa S, Matsuda R

    Meeting abstracts of the Physical Society of Japan   Vol. 60 ( 2 )   2005.8

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  71. 21pPSB-1 High field magnetizatoin process of adsorbed oxygen molecules chain in a nano-channel

    Matsuo A, Matsuda R, Chiba T, Uemura T, Kitagawa S, Kobayashi T, Kindo K

    Meeting abstracts of the Physical Society of Japan   Vol. 60 ( 2 )   2005.8

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  72. 20pYF-3 Anomalous magnetic properties of O_2-O_2 dimer

    Kobayashi T. C, Chiba T, Matsuo A, Kindo K, Matsuda R, Kitagawa S

    Meeting abstracts of the Physical Society of Japan   Vol. 60 ( 2 )   2005.8

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  73. 27pYK-1 Direct observation of hydrogen molecules adsorbed onto a microporous coordination polymer

    Kubota Yoshiki, Takata Masaki, Matsuda Ryotaro, Kitaura Ryo, Kitagawa Susumu, Kobayashi Tatsuo, Kato Kenichi, Sakata Makoto

    Meeting abstracts of the Physical Society of Japan   Vol. 60 ( 1 )   2005.3

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  74. 多孔性錯体のゲスト形状応答型構造転移

    松田 亮太郎, 北浦 良, 北川 進, 小林 達夫, 久保田 佳基, 高田 昌樹

    第54回錯体化学討論会     2004.9

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  75. 多孔性金属錯体のアセチレン吸着挙動及びその構造の直接観察

    松田亮太郎, 北川進, 北浦良, 久保田佳基, 小林達夫, 高田昌樹

    コロイドおよび界面化学討論会講演要旨集   Vol. 57th   page: 195   2004.8

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  76. 吸着に伴って収縮する多孔性錯体ーその特異的吸着構造と性質ー

    松田 亮太郎, 北川 進

    日本化学会第83春季年会     2004.3

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  77. 27aPS-97 Magnetism of adsorbed O_2 in porous Cu complex assemblies

    Suzuki M, Hosokawa K, Matsuda R, Kitaura R, Matsuo A, Kindo K, Kitagawa S, Kobayashi T. C

    Meeting abstracts of the Physical Society of Japan   Vol. 59 ( 1 )   2004.3

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  78. Novel Crystalline Porous Compounds Based on Metal Complexes - Structures and Functions

    MATSUDA Ryotaro, KITAGAWA Susumu

    X-RAYS   Vol. 46 ( 1 ) page: 53 - 58   2004.2

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    Coordination Polymers (CPs) are opening up a new field in porous materials. A large number of CPs have been so far synthesized and characterized because of their versatile applicability to gas storage, molecular sieves, size- or shape-selective catalysis, and ion exchange. Moreover, CPs, in spite of their crystalline form, are suitable for creating flexible and dynamic porous frameworks, which are hardly realized by inorganic zeolites and carbon materials. We described here the several unique structures and functions of CPs.

    DOI: 10.5940/jcrsj.46.53

  79. 多孔性配位高分子のベンゼン吸着による細孔収縮型構造相転移

    松田亮太郎, 堀毛悟史, 北浦良, 北川進, 高田昌樹

    分子構造総合討論会講演要旨集(CD-ROM)   Vol. 2003   page: 4PP120   2003.9

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  80. 非対称配位子を持つ多孔性配位高分子結晶の構造と吸着及び誘電特性

    松田亮太郎, 北浦良, 北川進, 小林達夫, 久保田佳基, 高田昌樹

    錯体化学討論会講演要旨集   Vol. 53rd   page: 388   2003.9

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  81. Magnetism of adsorbed O_2 in Cu complex with microporous

    Suzuki M, Kobayashi T. C, Matsuo A, Kindo K, Mita Y, Kobayashi M, Matsuda R, Kitaura R, Kitagawa S

    Meeting abstracts of the Physical Society of Japan   Vol. 58 ( 2 )   2003.8

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  82. ECO TECHNOLOGY 新しいナノ細孔材料による気体分子集積科学

    北川 進, 松田 亮太郎

    月刊エコインダストリー   Vol. 8 ( 7 ) page: 36 - 46   2003.7

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  83. 電気双極子を有する配位子を用いた新規多配位高分子の合成と構造

    松田亮太郎, 北浦良, 張浩徹, 北川進

    日本化学会第82春季年会     2003.3

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  84. Molecular oxygen ladder I : Synthesis of porous metal complex assemblies toward the bottom-up construction and their oxygen adsorption properties

    Kitagawa S, Matsuda R, Kitaura R, Chang H-C, Kobayashi T. C, Takata M

    Meeting abstracts of the Physical Society of Japan   Vol. 58 ( 1 )   2003.3

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  85. Molecular oxygen ladder IV : Raman scattering of adsorbed oxygen

    Kobayashi T. C, Suzuki M, Mita Y, Kobayashi M, Kitaura R, Matsuda R, Chang H. C, Kitagawa S

    Meeting abstracts of the Physical Society of Japan   Vol. 58 ( 1 )   2003.3

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  86. Oxygen molecule ladder III : magnetism

    Kindo K, Matsuo A, Kobayashi T. C, Suzuki M, Matsuda R, Kitaura R, Chang H. C, Kitagawa S

    Meeting abstracts of the Physical Society of Japan   Vol. 58 ( 1 )   2003.3

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  87. Oxygen molecule ladder II : Direct observation of adsorbed gas molecules by the MEM charge density study

    Kubota Yoshiki, Takata Masaki, Kitaura Ryo, Matsuda Ryotaro, Kitagawa Susumu, Chang Ho Chol, Kobayashi Tatsuo C, Sakata Makoto

    Meeting abstracts of the Physical Society of Japan   Vol. 58 ( 1 )   2003.3

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  88. Novel Porous Materials : Novel and Unique Functions of Metal-Complex-Assemblies

    KITAGAWA Susumu, MATSUDA Ryotaro

    Petrotech   Vol. 26 ( 2 ) page: 97 - 104   2003.2

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  89. 多孔性配位高分子錯体の吸着に伴う伝導及び誘電特性変化

    松田亮太郎, 張浩徹, 水谷義, 北川進

    分子構造総合討論会講演要旨集   Vol. 2002   page: 628   2002.10

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Research Project for Joint Research, Competitive Funding, etc. 3

  1. ナノポーラス金属錯体に内包された水の吸着 International coauthorship

    2017.10 - 2023.3

    科学技術振興機構  戦略的創造研究推進事業CREST 

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    Authorship:Coinvestigator(s)  Grant type:Competitive

    Grant amount:\70882500 ( Direct Cost: \54525000 、 Indirect Cost:\16357500 )

    水吸着を示すPCPの開発

  2. 実用的ガス分離PCPの合成と分離特性に関する研究開発

    2016.4 - 2018.3

    科学技術振興機構  戦略的創造研究推進事業ACCEL 

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    Grant type:Competitive

    選択的ガス分離を示すPCPの開発

  3. 超活性種の自在発生による未知化学種の実現と吸着・物質科学の新展開

    2014.10 - 2018.3

    戦略的創造研究推進事業さきがけ 

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    Grant type:Competitive

    ナノ空間での新物質探索。

KAKENHI (Grants-in-Aid for Scientific Research) 8

  1. ナノポーラス錯体によるダイナミック熱スイッチ材料の創製

    Grant number:20K20564  2020.7 - 2023.3

    科学研究費補助金   挑戦的研究(開拓)

    松田 亮太郎

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    Authorship:Principal investigator  Grant type:Competitive

    Grant amount:\26000000 ( Direct Cost: \20000000 、 Indirect Cost:\6000000 )

    本研究では、多孔性金属錯体(MOF)を用いて、ナノ空間物質へのガス吸脱着現象を利用した全く新しい熱制御材料の開発に挑戦する。MOFの「吸着・脱着機能」と「熱スイッチ機能」を統合することで、まったく新しい「ダイナミック熱スイッチ機能」を有する物質を創製する。環境の圧力や温度を変化させることで自在に熱流量や伝熱方向の制御が可能な新物質により、「吸着化学」と「熱科学」を融合した新しい学問領域を開拓する。

  2. Gas recognition and observation of the structural change in adsorption process in porous coordination polymers

    Grant number:20H02575  2020.4 - 2023.3

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    Authorship:Coinvestigator(s)  Grant type:Competitive

    Grant amount:\390000 ( Direct Cost: \300000 、 Indirect Cost:\90000 )

  3. Development of cluster type molecular adsorption in the nanospace of porous metal complexes

    Grant number:19H02734  2019.4 - 2022.3

    Grant-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research(B)

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    Authorship:Principal investigator  Grant type:Competitive

    Grant amount:\17810000 ( Direct Cost: \13700000 、 Indirect Cost:\4110000 )

  4. Theoretical design and experimental realization of multifunctional nanoporous materials for advanced energy and medical applications International coauthorship

    Grant number:17H03122  2017.4 - 2020.3

    Belosludov Rodion

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    The obtained results provide a new route to study the electronic, dynamic and thermodynamic properties of nanoporous materials with complex compositions of adsorbed gases. It allows us to calculate the gas storage capacity and thermodynamic stability without recourse to any empirical parameter fitting. The role and nature of weak interactions into nanoporous materials was evaluated in order to permit atomistic-level control in the design of porous structures. The gas storage capacity and thermodynamic conditions of selected nanoporous materials were calculated. Understanding the guest-host interactions on the stability of nanoporous materials provide the molecular-level keys to explain the complex structure-property relationship of these materials. The project involve collaboration between experimental and theoretical groups by providing information to experimentalists. This support the experimental exploration of ecologically clean storage materials and drug delivery systems.

  5. Creation of light and adsorption energy transformation materials utilizing dynamic properties of the metal complex nanospaces

    Grant number:16H06032  2016.4 - 2019.3

    Grant-in-Aid for Scientific Research  Grant-in-Aid for Young Scientists(A)

    Matsuda Ryotaro

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    Authorship:Principal investigator  Grant type:Competitive

    Grant amount:\26130000 ( Direct Cost: \20100000 、 Indirect Cost:\6030000 )

    We performed a creation and exploration of porous materials that can adsorb molecules by light energy based on porous coordination polymers (PCP) composed of metal ions and organic ligands. We have succeeded to obtain new compounds that could transform their structure by the light stimulation, and their adsorption functions were able to be controlled as well. In addition, we synthesized new materials in which highly active species such as carbenes could be generated in the nanospace by light stimulation. It was found that these materials could selectively adsorb molecules owing to the interaction between the active species and guest molecules. Consequently, we found that it is possible to design nanospace-materials that adsorb molecules by light as well as the operation of temperature or pressure.

  6. Creation of pseudo liquid phase of perfluoroalkane in the nanospace realizing an innovative gas adsorption at room temperature.

    Grant number:25620187  2013.4 - 2015.3

    Grant-in-Aid for Scientific Research 

    MATSUDA Ryotaro

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    Authorship:Principal investigator  Grant type:Competitive

    Grant amount:\4030000 ( Direct Cost: \3100000 、 Indirect Cost:\930000 )

    Porous coordination polymers (PCPs) or metal-organic frameworks (MOFs) assembled from various organic ligands and metal ions/clusters have been fascinating to materials scientists due to their potential applications in gas storage, separation, catalysis, conductivity etc. In this work, we have succeeded in the synthesis of new PCPs having fluorinated nanospace. We found that the fluorinated nanospace showed unusual guest uptake phenomena which provide a new guideline for the design of nanoporous materials showing selective gas adsorption.

  7. 多中心原子価互変異性錯体による双安定分子クラスターの開発

    Grant number:19027043  2007

    科学研究費補助金   特定領域研究

    佐藤 治

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    Authorship:Coinvestigator(s)  Grant type:Competitive

    原子価互変異性とはレドックス活性な配位子を有する遷移金属錯体で観測される現象で、中心金属と配位子間の電荷移動に基づいた酸化還元異性体間における相互変換のことである。これは、熱のや光などの外部刺激により誘起され、また異性化の前後で磁性や光学特性が劇的に変化するため、これを利用した分子スケールでの記録材料への応用が期待されている。本研究では、元素相乗効果の発現と将来の高密度記録材料への応用を目指し、室温ヒステリシスと光応答性を示す原子価互変異性複核錯体の開発を試み、新規コバルト錯体[{Co(dpqa)}_2(dhbq)]・(PF_6)_3を合成した。[{Co(dpqa)}_2(dpqa)}_2(dhbq)}]・(PF_6)_3の磁化率測定の結果、約170Kで原子価異性相転移を示すことが分かった。相転移に伴う電子状態の変化はCo^<III-LS>-dhbq^<3->-Co^<III-LS>→Co^<III-LS>-dhbq^<2->-Co^<II-HLS>と表せる。さらに、[{Co(dpqa)}_2(dhbq)]・(PF_6)_3の光応答性いついて検討した。吸収スペクトルの測定により金属-配位子間電荷移動バンドが550nm付近に存在することがわかっている。そこで、5Kにおいて波長532nmの単色光を照射した。その結果、x_M^T値の上昇が見られた。このことは、原子価異性(Co^<III-LS>-dhbq^<2->-Co^<II-HLS>→Co^<III-LS>-dhbq^<3->-Co^<III-LS>)が光により誘起されたことを示している。準安定状態(Co^<III-LS>-dhbq<3->-Co<III-LS>)は5Kで数時間以上の寿命を持っていた。また、準安定状態は約80K付近まで温度を上げると最安定状態Co^<III-LS>-dhbq<2->-Co^<II-HLS>に緩和することが分かった。また、この変化は繰り返し観測でき、可逆であった。同様な温度変化による原子価異性と光誘起原子価異性は[{Co(TPA)}_2(dhbq)]・(CLO_4)_3でも観測された。[{Co(TPA)}_2(dhbq)]・(CLO_4)_3の磁化率は約370K付近で変化し、この温度で原子価異性Co<III-LS>-dhbq^<3->-Co^<III-LS>→Co^<III-LS>-dhbq^<2->-Co^<II-HS>が誘起されていることが分かった。

  8. 多孔性金属錯体による動的光応答空間の構築と光連動性細孔機能の発現

    Grant number:18750117  2006 - 2007

    科学研究費補助金  若手研究(B)

    松田 亮太郎

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    Authorship:Principal investigator  Grant type:Competitive

    Grant amount:\3600000 ( Direct Cost: \3600000 )

    本研究課題は多孔性金属錯体による動的光応答空間の構築と光連動性機能発現を実現することにより、細孔構造と細孔機能が1対1の関係で結びつけられているという従来の概念を覆し、外的刺激による細孔空間構造の制御の実現を目的としたものである。
    光応答構造相転移および、外部雰囲気応答性の評価のために、まずLIESST錯体である[Na_<0.122>Co_<1.439>Fe(CN)_6]-5.1H_2O(1)、[Co^<III>(4,4-dmobpy)_2]_3[Fe^<II>(CN)_6]_2[BPh_4](2)(4,4-dmobpy=4,4'-dimethoxy-2,2'-bipyridine)、および[FeL_2][BF_4]_2(3)(L=2,6-di(1H-pyyrazol-1-yl)isonicotinic acid)を合成した。続いて前年度に構築した雰囲気可変型磁気測定システムを用いLIESST挙動と雰囲気応答性の精密評価を行った。その結果、錯体(2)は室温から400Kまで昇温する過程において、溶媒の脱着を伴った急激なスピン転移を示す事を明らかにした。また上記した化合物に関して低温において、光を照射しながら磁性及びIR測定を行った結果、光によって電子移動が誘起されるという興味深い結果を得ることができた。
    光照射による細孔状態の変化を見積もるために、錯体(3)に関してレーザー光照射状態とレーザー光非照射状態のそれぞれの状態において放射光を用いた粉末X線回折測定を行い、回折パターンの解析を行った。
    その結果、光照射によりスピン転移が誘起され吸着可能な細孔構造が拡大する事が明らかとなった。
    このように本研究課題は、光照射という外部刺激によって吸着可能な細孔空間構造を制御できる事を初めて明らかにし細孔物質科学における新領域を開拓したといえる。

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Teaching Experience (On-campus) 1

  1. 無機合成化学

    2017

 

Academic Activities 2

  1. 第1回錯体化学会フロンティアセミナー:次世代電池を指向する金属錯体材料の最前線

    Role(s):Planning, management, etc.

    錯体化学会  2021.12

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    Type:Academic society, research group, etc. 

  2. 分子研研究会「錯体化学から始まる学術展開の可能性」 International contribution

    Role(s):Planning, management, etc., Panel moderator, session chair, etc.

    錯体化学会・松田亮太郎  2020.3

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    Type:Academic society, research group, etc.