Faculty Profiles - MATSUDA Ryotaro

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

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

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 (< 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

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

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

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.

DOI： 10.1002/asia.200800112

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

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

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

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

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

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.

DOI： 10.1021/ja073505z

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

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

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).

DOI： 10.1021/ar600014m

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

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

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.

DOI： 10.1021/ja067374y

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

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

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.

DOI： 10.1038/nmat1827

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

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

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.

DOI： 10.1021/ja065254k

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

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

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

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

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

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

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

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

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

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

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.

DOI： 10.1021/jp054411j

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

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

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.

DOI： 10.1021/ja0561439

Flexible microporous coordination polymers Reviewed

K Uemura, R Matsuda, S Kitagawa

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

Language：English Publishing type：Research paper (scientific journal) Publisher：ACADEMIC PRESS INC ELSEVIER SCIENCE

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.

DOI： 10.1016/j.jssc.2005.05.036

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

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

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.

DOI： 10.1038/nature03852