Faculty Profiles - MATSUDA Ryotaro

Papers - MATSUDA Ryotaro

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

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

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

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

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

DOI： 10.1021/ic4020477

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

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

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

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

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

DOI： 10.1021/ic401924d

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

Ryotaro Matsuda

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

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

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

DOI： 10.1246/bcsj.20130157

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

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

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

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

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

DOI： 10.7566/JPSJ.82.084703

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

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

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

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

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

DOI： 10.1039/c2cc36153a

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

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

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

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

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

DOI： 10.1021/ic300695v

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

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

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

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

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

DOI： 10.1016/j.micromeso.2012.01.015

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

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

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

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

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

DOI： 10.1021/ja2115713

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

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

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

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

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

DOI： 10.1039/c2dt11891b

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

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

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

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

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

DOI： 10.1039/c2sc20443f

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

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

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

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

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

DOI： 10.1039/c2cc31083j

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

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

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

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

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

DOI： 10.1039/c2ce06701c

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

Hirotoshi Sakamoto, Ryotaro Matsuda, Susumu Kitagawa

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

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

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

DOI： 10.1039/c2dt12012g

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

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

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

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

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

DOI： 10.1038/NMAT3104

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

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

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

Language：English Publishing type：Research paper (scientific journal) Publisher：WILEY-BLACKWELL

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

DOI： 10.1002/adma.201101356

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

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

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

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

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

DOI： 10.1021/ja201484s

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

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

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

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

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

DOI： 10.1002/chem.201003734

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

Satoru Shimomura, Nobuhiro Yanai, Ryotaro Matsuda, Susumu Kitagawa

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

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

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

DOI： 10.1021/ic1015498

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

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

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

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

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

DOI： 10.1039/c1cc11416f

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

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

Nat. Mater. page： . 2011

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