Faculty Profiles - MATSUDA Ryotaro

Papers - MATSUDA Ryotaro

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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

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

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

Web of Science

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

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

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

Web of Science

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

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

Web of Science

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

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

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

Web of Science

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

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

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

Web of Science

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

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

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

Web of Science

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

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

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

Web of Science

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

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

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

Web of Science

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

Language：English Publishing type：Research paper (scientific journal) Publisher：NATURE PUBLISHING GROUP

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

Web of Science

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

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

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

Web of Science

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

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

Web of Science

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

Language：English Publishing type：Research paper (scientific journal) Publisher：CHEMICAL SOC JAPAN

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

Web of Science

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

Language：English Publishing type：Research paper (scientific journal) Publisher：ELSEVIER SCIENCE BV

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

Web of Science

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

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

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

Web of Science

MATERIALS CHEMISTRY Selectivity from flexibility Reviewed

Ryotaro Matsuda

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

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

Language：English Publishing type：Research paper (scientific journal) Publisher：AMER ASSOC ADVANCEMENT SCIENCE

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.

DOI： 10.1126/science.1246423

Web of Science

PubMed

Functional Hybrid Porous Coordination Polymers Reviewed

Maw Lin Foo, Ryotaro Matsuda, Susumu Kitagawa

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

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

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

Web of Science

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

Language：English Publishing type：Research paper (scientific journal) Publisher：ROYAL SOC CHEMISTRY

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

Web of Science

PubMed

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

Language：English Publishing type：Research paper (scientific journal) Publisher：ROYAL SOC CHEMISTRY

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

Web of Science

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

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

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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Papers - MATSUDA Ryotaro