Updated on 2022/03/25

写真a

 
KUSAKA Shinpei
 
Organization
Graduate School of Engineering Materials Chemistry 2 Assistant Professor
Graduate School
Graduate School of Engineering
Undergraduate School
School of Engineering Chemistry and Biotechnology
Title
Assistant Professor

Degree 1

  1. 博士(理学) ( 2013.3   東京大学 ) 

Research Areas 2

  1. Nanotechnology/Materials / Inorganic/coordination chemistry

  2. Nanotechnology/Materials / Inorganic/coordination chemistry

Research History 2

  1. Nagoya University   Graduate School of Engineering Materials Chemistry 2   Assistant Professor

    2020.8

  2. Nagoya University   Graduate School of Engineering Materials Chemistry 2   Designated assistant professor

    2018.4 - 2020.7

 

Papers 33

  1. Design of a MOF based on octa-nuclear zinc clusters realizing both thermal stability and structural flexibility Reviewed International coauthorship

    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:English   Publisher:Chemical Communications  

    An octa-nuclear zinc (Zn8) cluster-based two-fold interpenetrated metal-organic framework (MOF) of [(CH3)2NH2]2[Zn8O3(FDC)6]·7DMF (denoted as Zn8-as; H2FDC = 9H-fluorene-2,7-dicarboxylic acid; DMF = N,N-dimethylformamide) was synthesized by the reaction of a hard base of a curved dicarboxylate ligand (H2FDC) with the borderline acid of Zn(ii) under solvothermal conditions. Zn8-as shows significant crystal volume shrinkage upon heating, yielding a solvate-free framework of [(CH3)2NH2]2[Zn8O3(FDC)6] (Zn8-de). Zn8-de displays gated adsorption for C2H2 and type-I adsorption for CO2, attributed to the framework flexibility and the different interactions between the gas molecules and the host framework.

    DOI: 10.1039/d1cc05893b

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

    Ono Katsuya, Kusaka Shinpei, Matsuda Ryotaro

    Chemistry Letters   Vol. 50 ( 12 ) page: 1987 - 1989   2021.12

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:The Chemical Society of Japan  

    <p>We demonstrate selective photo-reactions observed between the two different chemical species bearing carbon-carbon double bonds in MOF <b>1</b>. 1,2-Bis(4-pyridyl)ethylene (bpe) was fixed in <b>1</b> as the organic linker, which reacted with tetramethylethylene (TME) as the guest molecule. As a result, a specific product from the radical reaction was selectively generated, whereas various side products were observed when reacted in solution. Our strategy to realize selective reactions would contribute to enforce the applicability of solid-phase reactions in synthetic chemistry.</p>

    DOI: 10.1246/cl.210525

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  3. Stabilization of radical active species in a MOF nanospace to exploit unique reaction pathways Reviewed International coauthorship

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

    CHEMICAL COMMUNICATIONS   Vol. 57 ( 91 ) page: 12115 - 12118   2021.11

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:Chemical Communications  

    We synthesized a metal-organic framework (MOF) using a ligand bearing haloalkoxy chains as a radical precursor. The radicals generated in the MOF upon photoirradiation were stable even at 250 K or under an O2 atmosphere, despite radicals generated from the ligand decomposing at 200 K; thus, the regular arrangement of radicals effectively stabilized them. Moreover, a unique photoproduct was obtained only in the MOF, indicating that the confinement effect in the nanospace enabled a specific reaction that did not occur in the bulk state. We propose a new platform for exploring chemical reactions and materials based on reactive species. This journal is

    DOI: 10.1039/d1cc04267j

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

    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:English   Publishing type:Research paper (scientific journal)   Publisher:Chemistry - An Asian Journal  

    In this study, we report an efficient fabrication method for the membrane of a metal-organic framework (MOF) (Kgm−OEt) which is one kind of kagomé-type MOF with a two-dimensional (2D) sheet structure having one-dimensional (1D) channels suitable for separation of H2 from other larger gases. The Kgm−OEt seed layer was created on an Al2O3 substrate using layer-by-layer (LBL) growth, then a membrane was fabricated by secondary growth. The membrane on a 3-aminopropyltriethoxysilane (APTEs)-treated substrate obtained in this method was continuous and defect-free with the crystal orientation suitable for gas transportation, while the membrane grown on an unmodified substrate was loosely packed with unfavorable crystal orientation.

    DOI: 10.1002/asia.202100507

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

    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:English   Publishing type:Research paper (scientific journal)   Publisher:Journal of the American Chemical Society  

    Triplet carbenes (TCs) are of great interest due to their magnetic properties and reactivity, which descend from TCs' unique electronic state. However, the reactivity and stability of TCs are usually a trade-off, and it is difficult to achieve both at the same time. In this work, we were able to enhance the thermal stability of a TC species while maintaining its reactivity by confining them in the nanospace of a metal-organic framework (MOF). We synthesized a new MOF using a TC precursor; subsequently, TCs were generated by photostimulation. The TCs generated in the MOF nanospace were detectable up to 170 K, whereas their non-MOF-confined counterparts (bare ligand) could not be detected above 100 K. In addition, the reactivity of TC generated in MOF with O2 was drastically improved compared to that of bare ligand. Our approach is generally applicable to the stabilization of highly reactive species, whose reactivity needs to be preserved.

    DOI: 10.1021/jacs.1c02430

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  6. Trapping and Releasing of Oxygen in Liquid by Metal–Organic Framework with Light and Heat Invited Reviewed International journal

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

    Small   Vol. 17 ( 22 ) page: e2004351 - 2004351   2021.6

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:Wiley  

    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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    Other Link: https://onlinelibrary.wiley.com/doi/full-xml/10.1002/smll.202004351

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

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

    SMALL   Vol. 17 ( 22 )   2021.6

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    Electrochemical reduction of CO2 in aqueous media is an important reaction to produce value-added carbon products in an environmentally and economically friendly manner. Various molecule-based catalytic systems for the reaction have been reported thus far. The key features of state-of-the-art catalytic systems in this field can be summarized as follows: 1) an iron-porphyrin-based scaffold as a catalytic center, 2) a dinuclear active center for the efficient activation of a CO2 molecule, and 3) a hydrophobic channel for the accumulation of CO2. This article reports a novel approach to construct a catalytic system for CO2 reduction with the aforementioned three key substructures. The self-assembly of a newly designed iron-porphyrin complex bearing bulky substituents with noncovalent interaction ability forms a highly ordered crystalline solid with adjacent catalytically active sites and hydrophobic pores. The obtained crystalline solid serves as an electrocatalyst for CO2 reduction in aqueous media. Note that a relevant iron-porphyrin complex without bulky substituents cannot form a porous structure with adjacent active sites, and the catalytic performance of the crystals of this relevant iron-porphyrin complex is substantially lower than that of the newly developed catalytic system. The present study provides a novel strategy for constructing porous crystalline solids for small-molecule conversions.

    DOI: 10.1002/smll.202006150

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

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

    Chemistry Letters   Vol. 50 ( 4 ) page: 640 - 643   2021.4

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:The Chemical Society of Japan  

    <p>Here we report enhanced CO<sub>2</sub> molecular recognition ability by incorporating insertion reaction into a metal porphyrin complex in a metal-organic framework (MOF). PCN-222(Cu)-INA was synthesized by the reaction of PCN-222(Cu) [Zr<sub>6</sub>O<sub>8</sub>(H<sub>2</sub>O)<sub>8</sub>(Cu-TCPP)<sub>2</sub>], where Cu-TCPP = Cu(II) tetrakis(4-carboxyphenyl)porphyrin, and isonicotinic acid (INA). PCN-222(Cu)-INA exhibited a 1.5 times larger CO<sub>2</sub> adsorption amount than PCN-222(Cu) at 298 K and 1 bar. The mechanism involving insertion reaction of CO<sub>2</sub> into Cu–N bonds enhanced the adsorption, which was revealed by <i>in situ</i> IR spectroscopy and theoretical calculations.</p>

    DOI: 10.1246/cl.200785

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

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

    Journal of the American Chemical Society   Vol. 143 ( 11 ) page: 4329 - 4338   2021.3

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:American Chemical Society (ACS)  

    DOI: 10.1021/jacs.0c13310

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

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

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

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    Authorship:Lead author   Language:English   Publishing type:Research paper (scientific journal)  

    <p>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...</p>

    DOI: 10.1039/d0fd00002g

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  11. Hysteresis in the gas sorption isotherms of metal–organic cages accompanied by subtle changes in molecular packing Reviewed

    Gavin A. Craig, Patrick Larpent, Hinano Urabe, Alexandre Legrand, Mickaele Bonneau, Shinpei Kusaka, Shuhei Furukawa

    Chemical Communications   Vol. 56 ( 25 ) page: 3689 - 3692   2020.3

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:Royal Society of Chemistry ({RSC})  

    DOI: 10.1039/d0cc00932f

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

    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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    Language:Japanese   Publishing type:Research paper (scientific journal)   Publisher:Royal Society of Chemistry (RSC)  

    <p>OMSs in HKUST-1 can strongly trap DMS even under humid conditions, which was directly proved by <italic>in situ</italic> single-crystal X-ray diffraction and Raman measurements.</p>

    DOI: 10.1039/c9ra09702c

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

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

    Journal of the American Chemical Society   Vol. 141 ( 40 ) page: 15742 - 15746   2019.10

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    Authorship:Lead author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:American Chemical Society (ACS)  

    DOI: 10.1021/jacs.9b07682

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  14. 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 International journal

    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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  15. 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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    Language:Japanese   Publishing type:Research paper (scientific journal)   Publisher:AMER CHEMICAL SOC  

    A layered metal-organic framework (MOF) comprising extra-large nanographene sheets, (MOF)-M-HBC, was successfully synthesized using a dicarboxylic acid derivative of hexa-perihexab enzocoronene ((LH2)-L-HBC), and its structure was characterized by single-crystal X-ray diffraction analysis. The crystal structure shows that 2D layers composed of a dinuclear Zn2+ complex unit and L-HBC are located on top of each other through multiple weak interlayer bonds, affording (MOF)-M-HBC, having three dimensionally connected nanopores with large nanographene surfaces. The HBC-based nanographene sheets are anchored to the MOF framework via two zinc carboxylate linkages and therefore have an axial rotational freedom. The sorption isotherms of gaseous molecules such as carbon dioxide and hydrocarbons (acetylene, propane, propylene, benzene, and cyclohexane) on (MOF)-M-HBC all displayed a hysteretic profile with reversible structural changes, as observed by in situ powder X-ray diffraction studies.

    DOI: 10.1021/jacs.9b07732

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  16. 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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  17. Creation of MOFs with open metal sites by partial replacement of metal ions with different coordination numbers Reviewed International journal

    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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  18. 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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  19. Design and control of gas diffusion process in a nanoporous soft crystal. Reviewed International journal

    Cheng Gu, Nobuhiko Hosono, Jia-Jia Zheng, Yohei Sato, Shinpei Kusaka, Shigeyoshi Sakaki, Susumu Kitagawa

    Science (New York, N.Y.)   Vol. 363 ( 6425 ) page: 387 - +   2019.1

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    Design of the gas-diffusion process in a porous material is challenging because a contracted pore aperture is a prerequisite, whereas the channel traffic of guest molecules is regulated by the flexible and dynamic motions of nanochannels. Here, we present the rational design of a diffusion-regulatory system in a porous coordination polymer (PCP) in which flip-flop molecular motions within the framework structure provide kinetic gate functions that enable efficient gas separation and storage. The PCP shows substantial temperature-responsive adsorption in which the adsorbate molecules are differentiated by each gate-admission temperature, facilitating kinetics-based gas separations of oxygen/argon and ethylene/ethane with high selectivities of ~350 and ~75, respectively. Additionally, we demonstrate the long-lasting physical encapsulation of ethylene at ambient conditions, owing to strongly impeded diffusion in distinctive nanochannels.

    DOI: 10.1126/science.aar6833

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

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

    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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    Language:Japanese   Publishing type:Research paper (scientific journal)   Publisher:AMER CHEMICAL SOC  

    The gate-opening adsorption mechanism and sigmoidal adsorption isotherm were theoretically investigated taking CO, adsorption into porous coordination polymers, [Fe(ppt)(2)](n) (PCP-N, Hppt = 3-(2-pyrazinyl)-5-(4-pyridyl)-1,2,4-triazole) and [Fe(dpt)(2)](n) (PCP-C, Hdpt = 3-(2-pyridiny1)-5-(4-pyridy1)-1,2,4-triazole) as examples, where the hybrid method consisting of dispersion-corrected DFT or infinite PCP and a post-Hartree-Fock (SCS-MP2 and CCSD(T)) method for the cluster model was employed. PCP-N has site I (one-dimensional channel), site II (small aperture to site I), and site III (small pore) useful for CO2 adsorption. CO2 adsorption at site I occurs in a one by one manner with a Langmuir adsorption isotherm. CO2 adsorption at sites II and III occurs through a gate-opening adsorption mechanism, because the crystal deformation energy (EDEF) at these sites is induced largely by the first CO2 adsorption but induced much less by the subsequent CO2 adsorption. Interestingly, nine CO2 molecules are adsorbed simultaneously at these sites because a large EDEF cannot be overcome by adsorption of one CO2 molecule but can be by simultaneous adsorption of nine CO2 molecules. For such CO2 adsorption, the Langmuir-Freundlich sigmoidal adsorption isotherm was derived from the equilibrium equation for CO2 adsorption. A very complicated CO2 adsorption isotherm, experimentally observed, is reproduced by combination of the Langmuir and Langmuir Freundlich adsorption isotherms. In PCP-C, CO2 adsorption occurs only at site I with the Langmuir adsorption isotherm. Sites II and III of PCP-C cannot be used for CO2 adsorption because a very large EDEF cannot be overcome by simultaneous adsorption of nine CO2 molecules. Factors necessary for gate-opening adsorption mechanism are discussed on the basis of differences between PCP-N and PCP-C.

    DOI: 10.1021/jacs.8b09358

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  22. Switchable gate-opening effect in metal-organic polyhedra assemblies through solution processing Reviewed International journal

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

    CHEMICAL SCIENCE   Vol. 9 ( 31 ) page: 6463 - 6469   2018.8

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    DOI: 10.1039/c8sc02263a

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  23. Reversible Switching between Highly Porous and Nonporous Phases of an Interpenetrated Diamondoid Coordination Network That Exhibits Gate-Opening at Methane Storage Pressures. Reviewed International journal

    Qing-Yuan Yang, Prem Lama, Susan Sen, Matteo Lusi, Kai-Jie Chen, Wen-Yang Gao, Mohana Shivanna, Tony Pham, Nobuhiko Hosono, Shinpei Kusaka, John J Perry 4th, Shengqian Ma, Brian Space, Leonard J Barbour, Susumu Kitagawa, Michael J Zaworotko

    Angewandte Chemie (International ed. in English)   Vol. 57 ( 20 ) page: 5684 - 5689   2018.5

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    Herein, we report that a new flexible coordination network, NiL2 (L=4-(4-pyridyl)-biphenyl-4-carboxylic acid), with diamondoid topology switches between non-porous (closed) and several porous (open) phases at specific CO2 and CH4 pressures. These phases are manifested by multi-step low-pressure isotherms for CO2 or a single-step high-pressure isotherm for CH4 . The potential methane working capacity of NiL2 approaches that of compressed natural gas but at much lower pressures. The guest-induced phase transitions of NiL2 were studied by single-crystal XRD, in situ variable pressure powder XRD, synchrotron powder XRD, pressure-gradient differential scanning calorimetry (P-DSC), and molecular modeling. The detailed structural information provides insight into the extreme flexibility of NiL2 . Specifically, the extended linker ligand, L, undergoes ligand contortion and interactions between interpenetrated networks or sorbate-sorbent interactions enable the observed switching.

    DOI: 10.1002/anie.201800820

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

    Shinpei Kusaka, Ryotaro Matsuda, Susumu Kitagawa

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

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    Language:Japanese   Publishing type:Research paper (scientific journal)   Publisher:Royal Society of Chemistry  

    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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  25. Finely Controlled Stepwise Engineering of Pore Environments and Mechanistic Elucidation of Water-Stable, Flexible 2D Porous Coordination Polymers. Reviewed International journal

    Haijun Wang, Haifei Cao, Jia-Jia Zheng, Simon Mathew, Nobuhiko Hosono, Bihang Zhou, Hongliang Lyu, Shinpei Kusaka, Wanqin Jin, Susumu Kitagawa, Jingui Duan

    Chemistry (Weinheim an der Bergstrasse, Germany)   Vol. 24 ( 24 ) page: 6412 - 6417   2018.4

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    Two porous coordination polymers (PCPs) with different topologies (NTU-19: sql and NTU-20: dia) underwent finely controlled, stepwise crystal conversions to yield a common water-stable, flexible 2D framework (NTU-22: kgm). The crystal conversions occurred directly at higher temperature via the 3D intermediate (NTU-21: nbo), which could be observed at lower temperature. The successful isolation of the intermediate product of NTU-21, characterization with in situ PXRD and UV/Vis spectra were combined with DFT calculations to allow an understanding of the dynamic processes at the atomic level. Remarkably, breakthrough experiments demonstrate NTU-22 with integral structural properties allowed significant CO2 /CH4 mixture separation.

    DOI: 10.1002/chem.201705858

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  26. Readily accessible shape-memory effect in a porous interpenetrated coordination network. Reviewed International journal

    Mohana Shivanna, Qing-Yuan Yang, Alankriti Bajpai, Susan Sen, Nobuhiko Hosono, Shinpei Kusaka, Tony Pham, Katherine A Forrest, Brian Space, Susumu Kitagawa, Michael J Zaworotko

    Science advances   Vol. 4 ( 4 ) page: eaaq1636   2018.4

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    Shape-memory effects are quite well-studied in general, but there is only one reported example in the context of porous materials. We report the second example of a porous coordination network that exhibits a sorbate-induced shape-memory effect and the first in which multiple sorbates, N2, CO2 and CO promote this effect. The material, a new threefold interpenetrated pcu network, [Zn2(4,4'-biphenyldicarboxylate)2(1,4-bis(4-pyridyl)benzene)]n (X-pcu-3-Zn-3i), exhibits three distinct phases: the as-synthesized α phase; a denser-activated β phase; and a shape-memory γ phase, which is intermediate in density between the α and β phases. The γ phase is kinetically stable over multiple adsorption/desorption cycles and only reverts to the β phase when heated at >400 K under vacuum. The α phase can be regenerated by soaking the γ phase in N,N'-dimethylformamide. Single-crystal x-ray crystallography studies of all three phases provide insight into the shape-memory phenomenon by revealing the nature of interactions between interpenetrated networks. The β and γ phases were further investigated by in situ coincidence powder x-ray diffraction, and their sorption isotherms were replicated by density functional theory calculations. Analysis of the structural information concerning the three phases of X-pcu-3-Zn-3i enabled us to understand structure-function relationships and propose crystal engineering principles for the design of more examples of shape-memory porous materials.

    DOI: 10.1126/sciadv.aaq1636

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    PubMed

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

    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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    PubMed

  28. Development of a Porous Coordination Polymer with a High Gas Capacity Using a Thiophene-Based Bent Tetracarboxylate Ligand Reviewed International journal

    Fei Wang, Shinpei Kusaka, Yuh Hijikata, Nobuhiko Hosono, Susumu Kitagawa

    ACS APPLIED MATERIALS & INTERFACES   Vol. 9 ( 39 ) page: 33455 - 33460   2017.10

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    A new porous coordination polymer (PCP) based on a ligand with a unique bent angle bearing a thiophene-bridged bent carboxylate ligand and the Cu2+ ion was synthesized and structurally characterized. The structure has a pillared-layer framework based on a kagome-like layer with aromatic partition groups. It exhibits a high CO2 uptake of 180 mL(STP)/g at 1 bar, and 400 mL(STP)/g at 30 bar at 273 K. The uptakes of C2H2 and C2H4 reach 164 and 160 mL(STP)/g at 298 K and 1 bar, with good selectivity of C2H2 and C2H4 over CH4, both of which are among the highest levels of reported PCPs.

    DOI: 10.1021/acsami.7b01568

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    PubMed

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

    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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  30. Fine-tuning optimal porous coordination polymers using functional alkyl groups for CH4 purification Reviewed International journal

    Fujun Cheng, Qianqian Li, Jingui Duan, Nobuhiko Hosono, Shin-ichiro Noro, Rajamani Krishna, Hongliang Lyu, Shinpei Kusaka, Wanqin Jin, Susumu Kitagawa

    JOURNAL OF MATERIALS CHEMISTRY A   Vol. 5 ( 34 ) page: 17874 - 17880   2017.9

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    Nano-porous coordination polymers (nano-PCPs), as a new class of crystalline material, have become a lucrative topic in coordination chemistry due to the facile tunability of their functional pore environments. However, elucidating the pathways for the rational design and preparation of nano-PCPs with various integrated properties for feasible gas separation remains a great challenge. Here, we demonstrate a new route to achieve nano-PCPs with an integrated pore system and physical properties using a reticular chemistry strategy. By optimizing the position and length of the shortest two alkyl groups in the channels, unprecedented phenomena of improved surface area, gas uptake, gas selectivity, thermal stability and chemical stability were observed in the PCPs, especially in NTU-14, the structure with a pendant ethyl group. Furthermore, the high performance of adsorption-and membrane-based separation makes NTU-14 a promising medium for CH4 purification from a mixture at room temperature.

    DOI: 10.1039/c7ta02760e

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  31. Density Gradation of Open Metal Sites in the Mesospace of Porous Coordination Polymers Reviewed International journal

    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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    PubMed

  32. Photofunctionality in Porphyrin-Hybridized Bis(dipyrrinato)zinc(II) Complex Micro- and Nanosheets.

    Sakamoto R, Yagi T, Hoshiko K, Kusaka S, Matsuoka R, Maeda H, Liu Z, Liu Q, Wong WY, Nishihara H

    Angewandte Chemie (International ed. in English)   Vol. 56 ( 13 ) page: 3526 - 3530   2017.3

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    DOI: 10.1002/anie.201611785

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  33. Photofunctionality in Porphyrin-Hybridized Bis(dipyrrinato)zinc(II) Complex Micro- and Nanosheets Reviewed International journal

    Ryota Sakamoto, Toshiki Yagi, Ken Hoshiko, Shinpei Kusaka, Ryota Matsuoka, Hiroaki Maeda, Zheng Liu, Qian Liu, Wai-Yeung Wong, Hiroshi Nishihara

    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   Vol. 56 ( 13 ) page: 3526 - 3530   2017.3

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

    New bis(dipyrrinato) zinc(II) complex micro- and nanosheets containing zinc(II) porphyrin (N2) are synthesized. A liquid/liquid interface method between dipyrrin porphyrin ligand L2 and zinc acetate produces N2 with a large domain size. N2 can be layered quantitatively onto a flat substrate by a modified Langmuir-Schafer method. N2 deposited on a SnO2 electrode functions as a photoanode for a photoelectric conversion system. The photoresponse of N2 covers the whole visible wavelength range (400-650 nm), with a maximum quantum efficiency of more than twice that of a bis(dipyrrinato) zinc(II) complex nanosheet without porphyrin.

    DOI: 10.1002/ange.201611785

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MISC 25

  1. 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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  2. 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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  3. Reversible Switching between Highly Porous and Nonporous Phases of an Interpenetrated Diamondoid Coordination Network That Exhibits Gate-Opening at Methane Storage Pressures Reviewed

    Yang Qing-Yuan, Lama Prem, Sen Susan, Lusi Matteo, Chen Kai-Jie, Gao Wen-Yang, Shivanna Mohana, Pham Tony, Hosono Nobuhiko, Kusaka Shinpei, Perry John J., Ma Shengqian, Space Brian, Barbour Leonard J., Kitagawa Susumu, Zaworotko Michael J.

    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   Vol. 57 ( 20 ) page: 5684-5689   2018.5

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    DOI: 10.1002/anie.201800820

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

    Kusaka Shinpei, Matsuda Ryotaro, Kitagawa Susumu

    CHEMICAL COMMUNICATIONS   Vol. 54 ( 38 ) page: 4782-4785   2018.5

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    DOI: 10.1039/c8cc01837e

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  5. Finely Controlled Stepwise Engineering of Pore Environments and Mechanistic Elucidation of Water-Stable, Flexible 2D Porous Coordination Polymers Reviewed

    Wang Haijun, Cao Haifei, Zheng Jia-jia, Mathew Simon, Hosono Nobuhiko, Zhou Bihang, Lyu Hongliang, Kusaka Shinpei, Jin Wanqin, Kitagawa Susumu, Duan Jingui

    CHEMISTRY-A EUROPEAN JOURNAL   Vol. 24 ( 24 ) page: 6412-6417   2018.4

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    DOI: 10.1002/chem.201705858

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  6. Readily accessible shape-memory effect in a porous interpenetrated coordination network Reviewed

    Shivanna Mohana, Yang Qing-Yuan, Bajpai Alankriti, Sen Susan, Hosono Nobuhiko, Kusaka Shinpei, Pham Tony, Forrest Katherine A., Space Brian, Kitagawa Susumu, Zaworotko Michael J.

    SCIENCE ADVANCES   Vol. 4 ( 4 )   2018.4

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    DOI: 10.1126/sciadv.aaq1636

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  7. 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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  8. Development of a Porous Coordination Polymer with a High Gas Capacity Using a Thiophene-Based Bent Tetracarboxylate Ligand Reviewed

    Wang Fei, Kusaka Shinpei, Hijikata Yuh, Hosono Nobuhiko, Kitagawa Susumu

    ACS APPLIED MATERIALS & INTERFACES   Vol. 9 ( 39 ) page: 33455-33460   2017.10

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    DOI: 10.1021/acsami.7b01568

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  9. Fine-tuning optimal porous coordination polymers using functional alkyl groups for CH4 purification Reviewed

    Cheng Fujun, Li Qianqian, Duan Jingui, Hosono Nobuhiko, Noro Shin-ichiro, Krishna Rajamani, Lyu Hongliang, Kusaka Shinpei, Jin Wanqin, Kitagawa Susumu

    JOURNAL OF MATERIALS CHEMISTRY A   Vol. 5 ( 34 ) page: 17874-17880   2017.9

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    DOI: 10.1039/c7ta02760e

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  10. Photofunctionality in Porphyrin-Hybridized Bis(dipyrrinato)zinc(II) Complex Micro- and Nanosheets Reviewed

    Sakamoto Ryota, Yagi Toshiki, Hoshiko Ken, Kusaka Shinpei, Matsuoka Ryota, Maeda Hiroaki, Liu Zheng, Liu Qian, Wong Wai-Yeung, Nishihara Hiroshi

    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   Vol. 56 ( 13 ) page: 3526-3530   2017.3

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    DOI: 10.1002/anie.201611785

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  11. Dissymmetric Bis(dipyrrinato)zinc(II) Complexes: Rich Variety and Bright Red to Near-Infrared Luminescence with a Large Pseudo-Stokes Shift Reviewed

    Sakamoto Ryota, Iwashima Toshiki, Koegel Julius F., Kusaka Shinpei, Tsuchiya Mizuho, Kitagawa Yasutaka, Nishihara Hiroshi

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   Vol. 138 ( 17 ) page: 5666-5677   2016.5

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    DOI: 10.1021/jacs.6b02128

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  12. Heteroleptic [Bis(oxazoline)](dipyrrinato)zinc(II) Complexes: Bright and Circularly Polarized Luminescence from an Originally Achiral Dipyrrinato Ligand Reviewed

    Koegel Julius F., Kusaka Shinpei, Sakamoto Ryota, Iwashima Toshiki, Tsuchiya Mizuho, Toyoda Ryojun, Matsuoka Ryota, Tsukamoto Takamasa, Yuasa Junpei, Kitagawa Yasutaka, Kawai Tsuyoshi, Nishihara Hiroshi

    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   Vol. 55 ( 4 ) page: 1377-1381   2016.1

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    DOI: 10.1002/anie.201509411

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

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

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

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    DOI: 10.1021/jacs.5b09666

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  14. A photofunctional bottom-up bis(dipyrrinato)zinc(II) complex nanosheet Reviewed

    Sakamoto Ryota, Hoshiko Ken, Liu Qian, Yagi Toshiki, Nagayama Tatsuhiro, Kusaka Shinpei, Tsuchiya Mizuho, Kitagawa Yasutaka, Wong Wai-Yeung, Nishihara Hiroshi

    NATURE COMMUNICATIONS   Vol. 6   2015.4

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    DOI: 10.1038/ncomms7713

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  15. New aspects in bis and tris(dipyrrinato) metal complexes: bright luminescence, self-assembled nanoarchitectures, and materials applications Reviewed

    Sakamoto Ryota, Iwashima Toshiki, Tsuchiya Mizuho, Toyoda Ryojun, Matsuoka Ryota, Koegel Julius F., Kusaka Shinpei, Hoshiko Ken, Yagi Toshiki, Nagayama Tatsuhiro, Nishihara Hiroshi

    JOURNAL OF MATERIALS CHEMISTRY A   Vol. 3 ( 30 ) page: 15357-15371   2015

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    DOI: 10.1039/c5ta02040a

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  16. Luminescent Heteroleptic Tris(dipyrrinato)indium(III) Complexes Reviewed

    Kusaka Shinpei, Sakamoto Ryota, Nishihara Hiroshi

    INORGANIC CHEMISTRY   Vol. 53 ( 7 ) page: 3275-3277   2014.4

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    DOI: 10.1021/ic500326u

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  17. Asymmetric dinuclear bis(dipyrrinato)zinc(II) complexes: broad absorption and unidirectional quantitative exciton transmission Reviewed

    Tsuchiya Mizuho, Sakamoto Ryota, Kusaka Shinpei, Kitagawa Yasutaka, Okumura Mitsutaka, Nishihara Hiroshi

    CHEMICAL COMMUNICATIONS   Vol. 50 ( 44 ) page: 5881-5883   2014

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    DOI: 10.1039/c4cc01573h

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  18. Triarylamine-Conjugated Bis(dipyrrinato)zinc(II) Complexes: Impact of Triarylamine on Photochemical Property and Multi-Redox Reaction Reviewed

    Tsuchiya Mizuho, Sakamoto Ryota, Kusaka Shinpei, Kakinuma Junko, Nishihara Hiroshi

    ELECTROCHEMISTRY   Vol. 81 ( 5 ) page: 337-339   2013.5

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  19. Coordination Programming of Photofunctional Molecules Reviewed

    Sakamoto Ryota, Kusaka Shinpei, Hayashi Mikihiro, Nishikawa Michihiro, Nishihara Hiroshi

    MOLECULES   Vol. 18 ( 4 ) page: 4091-4119   2013.4

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  20. meso-Alkynyl BODIPYs: Structure, Photoproperties, -Extension, and Manipulation of Frontier Orbitals Reviewed

    Kusaka Shinpei, Sakamoto Ryota, Kitagawa Yasutaka, Okumura Mitsutaka, Nishihara Hiroshi

    CHEMISTRY-AN ASIAN JOURNAL   Vol. 8 ( 4 ) page: 723-727   2013.4

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    DOI: 10.1002/asia.201201176

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  21. An Extremely Bright Heteroleptic Bis(dipyrrinato)zinc(II) Complex Reviewed

    Kusaka Shinpei, Sakamoto Ryota, Kitagawa Yasutaka, Okumura Mitsutaka, Nishihara Hiroshi

    CHEMISTRY-AN ASIAN JOURNAL   Vol. 7 ( 5 ) page: 907-910   2012.5

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    DOI: 10.1002/asia.201200131

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  22. Fluorescent azadipyrrinato zinc(II) complex: hybridisation with a dipyrrinato ligand Reviewed

    Sakamoto Ryota, Kusaka Shinpei, Kitagawa Yasutaka, Kishida Masa-aki, Hayashi Mikihiro, Takara Yusuke, Tsuchiya Mizuho, Kakinuma Junko, Takeda Takuma, Hirata Keisuke, Ogino Tomoya, Kawahara Keisuke, Yagi Toshiki, Ikehira Shu, Nakamura Tomoya, Isomura Mayuko, Toyama Mikoto, Ichikawa Saki, Okumura Mitsutaka, Nishihara Hiroshi

    DALTON TRANSACTIONS   Vol. 41 ( 46 ) page: 14035-14037   2012

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    DOI: 10.1039/c2dt32039h

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  23. Elucidation of the Stereochemistry of Thiirane Formation from a 1 lambda(4),2-Dithietane Bearing Two Chiral Carbon Centers Reviewed

    Kusaka Shinpei, Kano Naokazu, Kawashima Takayuki

    HETEROATOM CHEMISTRY   Vol. 21 ( 6 ) page: 412-417   2010

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    DOI: 10.1002/hc.20630

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  24. Insertion of platinum and palladium into a sulfur(IV)-sulfur(II) bond of a sulfur-substituted sulfurane Reviewed

    Kano Naokazu, Kusaka Shinpei, Kawashima Takayuki

    DALTON TRANSACTIONS   Vol. 39 ( 2 ) page: 456-460   2010

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    DOI: 10.1039/b911566h

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  25. Structure and Properties of a Sulfur(IV)-Sulfur(II)-Bond Compound: Reversible Conversion of a Sulfur-Substituted Organosulfurane into a Thiol Reviewed

    Kano Naokazu, Itoh Yusuke, Watanabe Yuki, Kusaka Shinpei, Kawashima Takayuki

    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   Vol. 47 ( 49 ) page: 9430-9433   2008

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    DOI: 10.1002/anie.200803945

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KAKENHI (Grants-in-Aid for Scientific Research) 5

  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

    日本学術振興会  科学研究費助成事業  挑戦的研究(開拓)

    松田 亮太郎, 日下 心平

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    Authorship:Coinvestigator(s) 

    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。
    熱を特定の方向に流すことが可能な「熱スイッチ材料」は、熱制御において中核的な役割を果たすものである。しかし、熱伝導を能動的かつ任意に制御可能な材料はほとんど研究がない。本研究では、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。本研究では多孔性物質の一種である多孔性金属錯体(MOF)を熱制御材料として用いる。これまでのMOF研究のほとんどは、ガス吸着やガス分離に主眼がおかれている。その一方で、細孔への分子吸脱着によりMOF細孔内の密度が大きく変化するので、「吸着状態のMOF結晶」と、「脱着状態のMOF結晶」の熱物性は大きく異なっていると予想されるが、そのことに着目した研究はほとんど見当たらない。本研究課題では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し、外の環境温度や圧力の操作で、物質を変えることなく、熱良導体から熱不良導体へとスイッチ可能な全く新しい熱制御システムの開拓を行うことを目的としている。これをふまえ、当該年度は下記の実験を実施した。
    (1).熱スイッチ機能を志向した、MOF結晶の合成。
    (2).水および二酸化炭素を用いて、水および二酸化炭素を用いた、熱伝導度測定に影響すると想定される吸着熱の直接観察。
    (3).熱伝導度測定装置の立ち上げ
    その結果、(1)に関しては6種類の剛直および柔軟な構造特性を有するMOFの合成に成功した。また、(2)に関しては吸着熱の観察システムの高度化を達成し、精密に吸着熱を測定することが可能にした。これを用いて、吸着熱測定を(1)で合成したMOFに対して実施し、それぞれの吸着熱の挙動を明らかにした。
    本研究課題を実現するために必須の下記A、B、Cの課題を設定し、計画的に取り組んでいる。
    課題A:MOFへの気体分子の吸脱着を基盤とした熱スイッチ材料の開発
    課題B:高速熱伝導材料を志向した高速分子拡散が可能なMOFの開発
    課題C:超高速熱拡散率を有するMOFの構築
    当該年度は課題Aを中心に研究を実施した。その結果予定より多くのMOF結晶の合成に成功し、また吸着の際の熱の直接観察にも成功した。本成果は現在論文としてまとめており、本年度中に投稿できる段階にある。また、当初課題Bは2年度以降に実施することを考えていたが、計画を前倒しして、吸着熱測定とともに吸着速度測定を実施することができ、従来の物質よりも吸着速度が高速であるものを見出した。
    上述したように、本研究課題を実現するために必須の下記A、B、Cの課題を設定し、計画的に取り組んでいる。
    課題A:MOFへの気体分子の吸脱着を基盤とした熱スイッチ材料の開発
    課題B:高速熱伝導材料を志向した高速分子拡散が可能なMOFの開発
    課題C:超高速熱拡散率を有するMOFの構築
    今年度は課題Bを中心に推進し、昨年度に合成を実施したMOFの熱伝導に関する基本的知見を得るとともに、吸着下での熱物性と分子拡散特性についての検討を行っていく。

  2. Chemistry of Adaptable Space

    Grant number:18H05262  2018.6 - 2023.3

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (S)

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    Authorship:Coinvestigator(s) 

  3. Development of Gas Separative Membrane Reactor with Coordination Nanochannels

    Grant number:18H02072  2018.4 - 2021.3

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

    Hosono Nobuhiko

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    Authorship:Coinvestigator(s) 

    Gas separation membrane is one of indispensable materials for our daily life. In order to improve the performance of gas separation membranes, we developed new synthetic approach of gas separation membranes by using metal-organic frameworks (MOFs) and metal-organic cages (MOCs) as nano-space channels for sorting gas molecules. As a result, we succeeded in developing new technologies to synthesize hybrid materials of MOCs and organic polymers that can be formed into gas separation membranes by simple thermal and solution processes. In addition, we developed a new MOF that exhibit ultra-high performance gas separation ability and a MOF with catalytic activity that convert carbon dioxide into industrially useful organic materials.

  4. Development of a gating gas separation membrane fabricated by stacked nanosheets

    Grant number:18K14043  2018.4 - 2020.3

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research Grant-in-Aid for Early-Career Scientists  Grant-in-Aid for Early-Career Scientists

    Kusaka Shinpei

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    Authorship:Principal investigator 

    Grant amount:\4160000 ( Direct Cost: \3200000 、 Indirect Cost:\960000 )

    A thin film formed by a porous coordination polymer (PCP), which is a crystal with molecular-sized pores, with a thickness of 1 micron or less without gaps, is actively studied because it can be used for separation of a mixture of substances. Until now, PCP membrane had a random orientation of PCP. In this study, the PCP and the holes were aligned in one direction by peeling the PCP into nanosheets and re-stacking them into a membrane. Furthermore, it was clarified that the PCP, which changes the size of the pores depending on the environment, retains its properties by this film formation method.

  5. 空間融合による機能化学の新機軸

    Grant number:18H03928  2018.4 - 2019.3

    日本学術振興会  科学研究費助成事業 基盤研究(A)  基盤研究(A)

    北川 進

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    Authorship:Coinvestigator(s) 

    生物は細胞や膜といったように、機能をコンパートメントに分け、それらを有機的に連携させることで複雑な機能を生み出している。これは、例えば分子シグナルの授受や細胞膜内外の物質移動といったナノレベルの多重な機能を協同的に連携作用させて応答を行う「流れ(flow)」の確立にある。その実現には「ナノ空間の化学」が重要な役割をしている。
    本課題では、生物の受容、検出、移送、変換などの基本操作を材料化学的な空間素子として設計し、それらを連携させた空間を有機的に結合・融合させる「空間融合法」の開発を目指す。具体的には、機能開拓の舞台として動的なナノ空間機能を有する多孔性配位高分子(PCP)を主として用いる。異なる機能を有するPCPを「融合(fusion)」させる界面の化学を深化させ、例えば外部刺激・環境変化といったシグナルを増幅・伝搬するflowの創出に繋がる基盤技術の確立を目的とする。
    本年度は「空間融合」の学理の土台構築のために不可欠なPCP結晶の界面について理解を深めるため、PCP結晶表面の直接観察手法について検討した。PCPの結晶表面・界面は、その動的変形を最初に映し出すため、極めて重要な研究対象である。また、PCP結晶を融合・接合する上で、界面の理解は最も重要である。結果、原子間力顕微鏡を用い、PCP結晶表面を安定的に長時間観察するための条件の一部を決定することができた。基盤研究(S)の採択により、本課題は2018年6月11日付で廃止となった。
    平成30年度が最終年度であるため、記入しない。
    平成30年度が最終年度であるため、記入しない。