Updated on 2026/03/10

写真a

 
KAWANO MASAKI
 
Organization
School of Science Professor
Title
Professor
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News & Topics

Degree

  • 理学(博士) ( 早稲田大学 )

Research Interests

  • 配位高分子、結晶化学

  • 結晶化学

  • 錯体化学

  • 超分子化学

  • 配位高分子

Research Areas

  • Nanotechnology/Materials / Inorganic/coordination chemistry  / 超分子化学・配位高分子化学・結晶化学

Education

  • Waseda University   School of Science and Engineering

    1990.3

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  • Waseda University   School of Science and Engineering

    1998.3

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  • Waseda University

    1993.3

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Research History

  • Institute of Science Tokyo   School of Science, Department of Chemistry   Professor

    2024.10

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  • Tokyo Institute of Technology   School of Science   Professor

    2015.9 - 2024.9

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  • Pohnag University of science and Technology,   Division of Advanced Materials Science   Professor

    2009.3 - 2015.9

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  • 東京大学大学院   工学系研究科   助教授(改組により准教授)

    2004.7 - 2009.2

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  • 東京大学大学院   工学系研究科   特任講師

    2003.7 - 2004.7

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  • 科学技術振興団   博士研究員

    1997.4 - 2003.7

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  • University of Wisconsin

    1994.4 - 1997.3

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  • Waseda University   School of Science and Engineering

    1992.4 - 1994.3

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Professional Memberships

  • THE JAPANESE SOCIETY FOR SYNCHROTRON RADIATION RESEARCH

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  • JAPAN SOCIETY OF COORDINATION CHEMISTRY

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  • THE CRYSTALLOGRAPHIC SOCIETY OF JAPAN

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  • THE CHEMICAL SOCIETY OF JAPAN

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Papers

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MISC

  • Porus coordination network with unique CO2 adsorption capability using isolated spaces

    嶋田光将, USOV Pavel M, 和田雄貴, 松本隆也, 松本隆也, 大津博義, 河野正規

    錯体化学会討論会講演要旨集   71st (CD-ROM)   2021

  • カチオン-アニオン分離集積型構造をもつCoIII2AuI4六核錯体の結晶状態における水分子の吸脱着挙動

    吉成信人, 板井拓真, 小島達弘, 河野正規, 桑村直人, 今野巧, 今野巧

    日本化学会講演予稿集   95th ( 2 )   2015

  • 自己集合性錯体の電子受容性と光応答

    中林耕二, 河野正規, 藤田誠

    日本化学会講演予稿集   87th ( 1 )   572   2007.3

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    Language:Japanese  

    J-GLOBAL

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  • 自己組織化中空錯体を利用したスピン間相互作用の発現と制御

    中林耕二, 河野正規, 藤田誠

    錯体化学討論会講演要旨集   56th   76   2006.9

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    J-GLOBAL

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  • Photo‐response of donor molecules within self‐assembled coordination cages

    中林耕二, 河野正規, 藤田誠

    日本化学会講演予稿集   86th ( 1 )   326   2006.3

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    J-GLOBAL

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  • Control of a molecular array of organic molecular magnets by a self-assembled coordination cages

    河野正規, 中林耕二, 吉沢道人, 藤田誠

    日本化学会講演予稿集   84th ( 1 )   168   2004.3

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    J-GLOBAL

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  • High-nuclearity palladium carbonyl trimethylphosphine clusters containing unprecedented face-condensed icosahedral-based transition-metal core geometries: proposed growth patterns from a centered Pd-13 icosahedron

    NT Tran, M Kawano, LF Dahl

    JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS   ( 19 )   2731 - 2748   2001.10

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    Language:English   Publishing type:Book review, literature introduction, etc.  

    DOI: 10.1039/b103547a

    Web of Science

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  • X-Ray diffraction and spectroscopic studies of the light-induced metastable state of an ethylenediamine nitrosyl ruthenium complex

    KAWANO M, ISHIKAWA A, MORIOKA Y, TOMIZAWA H, MIKI E, OHASHI Y

    J. Chem. Soc.,   ( 14 )   2425 - 2431   2000

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  • Recent advances in high-nuclearity monometallic/bimetallic/trimetallic clusters containing platinum, palladium, and/or nickel in close-packed or infinite-chain metal cores.

    M Kawano, JM Bemis, NT Tran, PD Mlynek, JW Bacon, M Kozee, LF Dahl

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   215   U830 - U830   1998.4

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  • REVOLUTIONARY ADVANCES IN CRYSTALLOGRAPHIC ANALYSES OF HIGH-NUCLEARITY TRANSITION METAL CLUSTERS: FROM POINT-DETECTOR TO CCD AREA-DETECTOR SYSTEMS.

    Lawrence F. Dahl, Masaki Kawano, Jeffrey W. Bacon, John M. Bemis, Peter D. Mlynek, Nguyet T. Tran, Charles F. Campana

    ACTA CRYSTALLOGRAPHICA A-FOUNDATION AND ADVANCES   52   C286 - C286   1996

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    DOI: 10.1107/S0108767396088095

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  • FACILE C-H ACTIVATION OF DIETHYL-ETHER UTILIZING COORDINATED SULFUR LIGAND IN A SULFUR-BRIDGED RUTHENIUM COMPOUND

    M KAWANO, K MATSUMOTO

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   206   344 - INOR   1993.8

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    Web of Science

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Presentations

  • Atomic-resolution structure analysis inside an adaptable porous framework

    Masaki Kawano

    The 36 th Synchrotron Radiation Users' Workshop & KOSUA Meeting  2024.11 

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    Event date: 2024.11

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  • Design of amphiphilic porous coordination networks for structure determination of bioactive medium-sized molecules

    Masaki Kawano

    ICPAC Kota Kinabalu 2022  2022.11 

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    Event date: 2022.11

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  • Isolated Voids Having “Magic Doors” in a Coordination Network - Long Time CO2 Storage at Ambient Condition

    Masaki Kawano

    AsCA2022  2022.10 

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    Event date: 2022.10 - 2022.11

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  • 結晶性細孔を利用した反応のその場観察

    河野 正規

    日本化学会第98春季年会(船橋)  2018.3 

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  • 刺激応答システムの設計と構造―物性の相関の解 Invited

    河野 正規

    分子研研究会(岡崎)  2018.3 

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  • 細孔性配位高分子の速度論的合成 Invited

    河野 正規

    27th Annual Meeting of MRS-J 2017  2017.12 

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  • 非平衡系を利用した結晶空間の設計 Invited

    河野 正規

    日本結晶学会(広島)  2017.11 

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  • Kinetic Assembly Of Porous Coordination Networks Invited International conference

    KAWANO Masaki

    ACCC6(Melbourne)  2017.7 

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  • Ion conduction system based on multi-interactive molecules Invited International conference

    KAWANO Masaki

    Korea-Japan Joint Symposium on Hydrogen in Materials (Gachon Univ.)  2016.11 

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  • Kinetic Assembly of Porous Coordination Networks Invited International conference

    KAWANO Masaki

    ICCC2018(sendai)  2018.8 

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  • Direct Observation of Photoreactions in a Coordination Space Invited International conference

    KAWANO Masaki

    1st Symposium of Cutting Edge Organic Chemistry in Asia  2006.10 

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  • In situ observation of photochemical reactions in a self-assemble nano-cage by X-ray crystallographyI Invited International conference

    Masaki Kawano, Kanji Takaoka, Yasuhiro Kobayashi

    Pacifichem  2005.12 

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  • In Situ Crystallographic Observation of Photochemical Reactions in a Confined Cavity Invited International conference

    KAWANO Masaki

    Sino-Japanese Symposium on Organic Chemistry for Young Scientists  2005.10 

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  • Direct Observation of Photo-chemical Reactions by X-ray Crystallography – Supramolecular Approach Invited International conference

    Masaki Kawano Kobayashi, Kanji Takaoka, Makoto Fujita

    20th International Union of Crystallography Congress  2005.8 

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  • In situ observation of unstable species by X-ray crystallography – Supramolecular approach Invited International conference

    Masaki Kawano, Yasuhiro Kobayashi, Michito Yoshizawa, Makoto Fujita

    ICCC36 (XXXVIth International Conference on Coordination Chemistry)  2004.8 

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  • In situ observation of photo-induced reactive open-shell species by X-ray crystallography Invited International conference

    KAWANO Masaki

    TITECH International Symposium  2003.12 

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  • Structure Determination of Photo-Induced Triplet Diphenylcarbenes by X-ray Crystallography − How Do Substituents Contribute to their Stability? Invited International conference

    Masaki Kawano, Katsuyuki Hirai, Hideo Tomioka, Yuji Ohashi

    International Conference on Photochemistry  2003.8 

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  • X線回折による不安定中間体のその場観察” 日本化学会第82回-第17回若い世代の特別講演会 Invited

    河野 正規

    日本化学会第82回-第17回若い世代の特別講演会(  2002.9 

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  • Structure Analysis of Photo-induced Reactive Intermediate in a Crystal” 19th International Union of Crystallography Congress Invited International conference

    KAWANO Masaki

    19th International Union of Crystallography Congress  2002.8 

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  • The First Structure Analysis of a Transient Triplet Carbene Trapped in a Crystal Invited International conference

    M. Kawano, K. Hirai, H. Tomioka

    International Symposium on Reactive Intermediates and Unusual Molecules  2001.9 

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  • In situ observation of molecular swapping in a crystal by x-ray crystallography Invited International conference

    M. Kawano, Y. Ohashi

    Pacifichem  2000.12 

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  • THE FIRST IN SITU DIRECT OBSERVATION OF LIGHT-INDUCED RADICAL PAIR FROM HABI DERIVATIVE BY X-RAY CRYSTALLOGRAPHY Invited International conference

    M. Kawano, Y. Ohashi, T. Sano, J. Abe

    18th International Union of Crystallography Congress  1999.8 

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  • New-Generation Area Detector X-ray Systems: Their Use in Crystallographic Analyses of Giant-Sized Metal Clusters Invited International conference

    M. Kawano, J. W. Bacon, N. T. Tran, C. F. Campana, L. F. Dahl

    Pacifichem  1995.12 

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  • Globalization in Asia --- Life is unpredictable Invited International conference

    KAWANO Masaki

    Chemistry Innovation GCOE Symposium 

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  • ネットワーク錯体の瞬間合成

    河野 正規

    Nagoya Conference  2010.1 

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  • Instant synthesis of porous networks and ab initio powder diffraction structure analysis Invited International conference

    KAWANO Masaki

    2009.12 

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  • ネットワーク錯体の瞬間合成と粉末X線構造解析 Invited

    河野 正規

    2009.12 

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  • 結晶空間設計に基づく不安定種のX線その場観察 Invited

    KAWANO Masaki

    RIKEN seminar  2009.10 

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  • Direct observation of unstable species in porous networks by X-ray crystallography Invited International conference

    KAWANO Masaki

    KCS meeting  2009.10 

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  • A new world opened up by Synchrotron X-rays: in situ chemical crystallography Invited International conference

    KAWANO Masaki

    2009.10 

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  • Synchrotron Analysis of Supramolecules and In Situ Generated Unstable Species in a Crystal Invited International conference

    KAWANO Masaki

    Workshop on POSTECH‐RIKEN Joint Research Program  2009.10 

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  • X-ray Observation of Transient Species Trapped in Suplramolecules Invited International conference

    KAWANO Masaki

    ISAC  2009.9 

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  • In situ X-ray observation of reactive intermediates via supramolecular approach Invited International conference

    KAWANO Masaki

    2009.9 

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  • In situ observation of reactive intermediates by X-ray crystallography Invited International conference

    KAWANO Masaki

    The 2009 Summer Inorganic Chemistry Symposium, Cheonan  2009.8 

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  • 結晶空間設計に基づく反応仮定や不安定種のX線直接観察, Invited

    河野 正規

    日本化学会第89春季年会  2009.3 

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  • 結晶空間設計に基づく不安定種のX線その場観察 Invited

    河野 正規

    分析化学会第9回関東支部懇話会  2009.3 

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  • 新規ネットワーク錯体材料の開発と粉末X線構造解析 Invited

    河野 正規

    PF研究会「第4回粉末回折法討論会:粉末法の新しい技術と応用,高エネルギー加速器研究機構  2008.12 

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  • 配位空間を利用したX線回折による化学反応の直接観察 Invited

    河野 正規

    第14回錯体化学若手の会 中部・東海支部  2008.11 

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  • 結晶空間設計に基づく不安定種のその場観察 Invited

    河野 正規

    ナノ構造触媒研究の現状と展望の研究会  2008.11 

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  • Crystallographic direct observation of chemical reactions in a pore Invited International conference

    KAWANO Masaki

    The XXI Congress and General Assembly of the International Union of Crystallography  2008.8 

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  • Reactions in a pore _ The in situ observation by X-ray crystallography Invited International conference

    KAWANO Masaki

    2008.3 

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  • Encapsulation Approach for Direct Observation of Chemical Reactions Invited International conference

    KAWANO Masaki

    Third International Symposium on Chemistry of Coordination Space(ISCCS)  2007.12 

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  • 自己集合性ネットワーク錯体のab initio粉末・放射光構造解析 Invited

    河野 正規

    第5回有機・粉末結晶構造解析研究会  2007.10 

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  • X線回折による不安定種の直接観察 Invited

    河野 正規

    第68回分析化学討論会,「次世代の分析・計測-若手研究者の挑戦-」  2007.5 

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  • X線回折による包接錯体を用いた不安定種の直接観察 Invited

    河野 正規

    第57回錯体化学討論会シンポジウム 「錯体化学で展開される結晶構造解析研究の最先端」  2007 

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  • PHOTOCHEMICAL REACTIONS OF DIAZO-COMPOUNDS ENCAPSULATED IN COORDINATION SPACES Invited International conference

    KAWANO Masaki

    Second International Symposium on Chemistry of Coordination Space -ISCCS 2006-  2006.12 

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  • Kinetic assembly of porous coordination networks Invited International conference

    KAWANO Masaki

    2013 CONFERENCE (the 7th International Conference on Materials for Advanced Technologies, Suntec Singapore International Conventio)  2013.8 

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  • X線が切り拓くネットワーク錯体の新展開 Invited

    河野 正規

    化学科セミナー (岐阜大学)  2013.7 

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  • X線が切り拓くネットワーク錯体の新展開 Invited

    河野 正規

    化学科セミナー(筑波大学)  2013.1 

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  • Unstable Species Chemistry Explored by Powder Structure Analysis Invited International conference

    KAWANO Masaki

    Crystallographic Society of Japan annual meeting (Sendai)  2012.10 

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  • Kinetic Assembly of Coordination Networks and Ab Initio Powder Structure Determination Invited International conference

    KAWANO Masaki

    SMARTER 3 (Structure elucidation by coMbining mAgnetic Resonance, compuTation modEling and diffRactions, Univ. of VERSAILLES SAINT-QUENTIN-EN-YVELINES)  2012.10 

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  • What can SR do for Chemistry? International conference

    KAWANO Masaki

    AOFSRR 2012 (the 6th Asia Oceania Forum for Synchrotron Radiation Research, BangKok)  2012.8 

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  • Dynamic Self-Assembly of Porous Coordination Networks Invited International conference

    KAWANO Masaki

    Chemistry Department seminar ( Suranaree University of Technology)  2012.8 

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  • Dynamic Self-Assembly of Porous Coordination Networks Invited International conference

    KAWANO Masaki

    The 6th Waseda GCOE International Symposium (Waseda University)  2011.12 

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  • Kinetic assembly of porous coordination networks Invited International conference

    KAWANO Masaki

    3rd Asian Conference on Coordination Chemistry(New Delhi)  2011.10 

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  • Kinetic assembly of porous coordination networks Invited International conference

    KAWANO Masaki

    Global COE “Integrated Materials Science” Special Seminar (Kyoto Univ.)  2011.9 

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  • Kinetic trapping of metastable sulfur into a porous coordination network Invited International conference

    KAWANO Masaki

    The 63rd Divisional Meeting on Colloid and Interface Chemistry (Kyoto Univ.)  2011.9 

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  • Kinetic assembly of porous coordination networks and ab initio powder structure determination Invited International conference

    KAWANO Masaki

    IUCr2011 (Madrid)  2011.8 

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  • Kinetic assembly of porous coordination networks Invited International conference

    KAWANO Masaki

    The 829th IMS Colloquium (Okazaki)  2011.6 

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  • Frontier of Porous Coordination Networks Invited International conference

    KAWANO Masaki

    The 2nd international conference on New & Renewable Energy 2011 (ICNRE, Daegu)  2011.4 

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  • Frontier of Porous Coordination Networks Invited International conference

    KAWANO Masaki

    Current status of natural sciences: promise and challenge  2011.1 

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  • Kinetic Synthesis of a Porous Coordination Network and Ab Initio Powder Structure Analysis Invited International conference

    KAWANO Masaki

    Pacifichem  2010.12 

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  • その場観察X線解析による構造変化・化学反応の追跡 Invited

    河野 正規

    日本結晶学会60 周年記念シンポジウム  2010.12 

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  • Kinetic Syntheses of Coordination Networks and Ab initio Powder Structure Analysis Invited International conference

    KAWANO Masaki

    AsCA2010  2010.11 

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  • Kinetic synthesis of coordination networks and ab initio powder structure Invited International conference

    KAWANO Masaki

    60TH ANNIVERSARY CONFERENCE ON COORDINATION CHEMISTRY  2010.9 

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  • Formation of a Thermally Stable, Porous Coordination Network via Crystalline-to-Amorphous-to-Crystalline Phase Transitions International conference

    KAWANO Masaki

    2nd AMS Workshop  2010.3 

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  • 非経験的粉末構造解析が切り拓く新しいネットワーク錯体の科学

    河野 正規

    リガクセミナー  2010.3 

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  • 非経験的粉末構造解析によるネットワーク錯体の新展開 Invited

    河野 正規

    分子間反応機構の解明分科会シンポジウム  2010.1 

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  • REDOX-ACTIVE COORDINATION NETWORKS Invited International conference

    KAWANO Masaki

    International Workshop on Porous Coordination Compounds (IWPCC) 2016, (Altay, Russia)  2016.9 

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  • X-Ray Snapshot of Chemical Processes in Interactive Porous Networks Invited International conference

    KAWANO Masaki

    the 2016 Dynamic Structural Science Workshop(Abingdon)  2016.4 

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  • Ab initio Powder Structure Determination Opening Up New Research Fields Invited International conference

    KAWANO Masaki

    PITTCON(Atlanta)  2016.3 

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  • X-ray Snapshots of Labile Species in Interactive Pores Invited International conference

    KAWANO Masaki

    AsCA2015(Kolkata)  2015.12 

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  • Kinetic Assembly Leads to Chirality? International conference

    KAWANO Masaki

    he 15th International Conference on Chiroptical Spectroscopy (CD2015, Sapporo)  2015.9 

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  • Direct Observation of Chemical Reactions in an Interactive Pore by X-rays Invited International conference

    KAWANO Masaki

    ICCOSS XXII JAPAN (Niigata)  2015.8 

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  • Kinetic Assembly of Porous Coordination Networks Invited International conference

    KAWANO Masaki

    1st international conference on microstructure and property of materials(Hangzhou)  2015.5 

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  • Kinetic Assembly of Porous Coordination Network Invited International conference

    KAWANO Masaki

    2014 Workshop on New Frontiers in Namoporous Materials Science and Technology(POSTECH)  2014.10 

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  • Kinetic Control of Porous Network Formation Invited International conference

    KAWANO Masaki

    MOF 2014(Kobe)  2014.9 

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  • Reactive Species Unveiled by Ab Initio Powder Structure Analysis Invited International conference

    KAWANO Masaki

    IUCr2014 (Montreal)  2014.8 

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  • Kinetic Control of Porous Network Formation Invited International conference

    KAWANO Masaki

    Joint Congress of ACTS-2014 and CGOM11 (Nara)  2014.6 

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  • Kinetic Assembly of Porous Coordination Networks Invited International conference

    KAWANO Masaki

    AsCA2013 (The 12th Conference of the Asian Crystallographic Association, Hong Kong)  2013.12 

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  • Kinetic Assembly of Porous Coordination Networks Invited International conference

    KAWANO Masaki

    ACCC4 (the 4th Asian Conference on Coordination Chemistry, Jeju)  2013.11 

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  • MOFs beyond MOFs

    Masaki Kawano

    AsCA 2024  2024.12 

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  • Atomic-resolution structure analysis inside an adaptable porous framework Invited

    Masaki Kawano

    PACCON2025  2025.2 

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Industrial property rights

  • 可変抵抗デバイスおよびその製造方法

    河野正規

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    Applicant:国立大学法人東京工業大学

    Application no:特願特願2019-96797  Date applied:2019.5

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  • ジエン・オレフィンの分離材および分離方法

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    Application no:特願特願2021-i249 

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  • ピリジン配位子の合成法

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    Application no:特願2023-0205 

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  • 二酸化炭素の捕捉材

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    Application no:特願2021-0098 

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  • ネットワーク錯体結晶

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    Application no:特願2022-0081 

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  • ネットワーク錯体、および、それを用いた中分子の構造解析法

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    Application no:特願特願2020-0020 

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Awards

  • Nagase Foundation Award 2016

    2016  

    KAWANO Masaki

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  • Yamada Foundation Award 2015

    2015  

    KAWANO Masaki

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  • NRF Veteran Research Funding(韓国)

    2014  

    KAWANO Masaki

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  • NRF Korea-Japan Joint Research Funding(韓国)

    2013  

    KAWANO Masaki

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  • POSTECH Rising Star Award

    2011.8   浦項工科大学  

    河野 正規

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  • The CSJ Award for Creative Work

    2009.3   X-ray direct observation of reactions and labile species on the basis of crystal design

    KAWANO Masaki

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  • Chemistry Innovation UT GCOE Lectureship award

    2008.9  

    KAWANO Masaki

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  • 日英ナノテクノロジー若手研究者交流プログラム

    2005.9  

    河野 正規

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  • Young Scholar Lectures of CSJ

    2002.9  

    KAWANO Masaki

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Research Projects

  • Q-bitを目指したスピンを可視化する基盤としてのMOF創生とスピンデバイス応用

    Grant number:25K01784  2025.4 - 2029.3

    日本学術振興会  科学研究費助成事業  基盤研究(B)

    河野 正規

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    Grant amount:\18720000 ( Direct Cost: \14400000 、 Indirect Cost:\4320000 )

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  • Controlling guest orientation in the pore by external perturbation

    Grant number:24K21780  2024.6 - 2026.3

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

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    Authorship:Principal investigator 

    Grant amount:\6500000 ( Direct Cost: \5000000 、 Indirect Cost:\1500000 )

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  • メゾメカノ機能材料

    Grant number:23H04878  2023.4 - 2028.3

    日本学術振興会  科学研究費助成事業  学術変革領域研究(A)

    相良 剛光, 河野 正規, 阿部 二朗

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    Authorship:Coinvestigator(s) 

    Grant amount:\138840000 ( Direct Cost: \106800000 、 Indirect Cost:\32040000 )

    本学術変革領域では、分子がメゾスコピック領域で階層的に集合したメゾヒエラルキー材料を開発することが一つの主眼となっている。本A03-2班は、メゾヒエラルキー構造の特異な階層性を利用したメカノ機能性材料を開拓することを目指している。1分子の幅しか持たないメカノクロミック蛍光ファイバーに、メゾヒエラルキーの概念を導入し、力に応答して蛍光特性の可逆線形変化、蛍光特性の多段階変化、光応答性等を示すメゾメカノ機能材料を創製する。また、空孔錯体を用いた構造解析法により、分子集合構造変化と蛍光特性変化との相関関係を解明する。さらに新規フォトクロミック化合物を導入することにより機能性を拡張することを最終目標としている。その一方で、領域内で開発されるメゾヒエラルキー物質が生み出す力を可視化するための超分子メカノフォアを領域内に幅広く提供することも併せて目指す。
    初年度では、領域内共同研究により、ダンベル状の両親媒性分子が形成する1次元状の超分子ファイバーが示すメカノクロミック蛍光特性を解明した。両親媒性分子の疎水性蛍光団に導入したテトラエチレングリコール鎖の有無で、外部刺激に対する応答性が劇的に変化することが明らかとなり、その原因も明らかにすることができた。一方で、空孔錯体を用いた構造解析法を用いて、A01班で開発されたバルビツール酸誘導体が形成する分子集合構造の解明にも成功した。さらに、新規フォトクロミック機能に関しては、液晶散逸構造の研究基盤となる高速逆フォトクロミック分子の開発を推し進めた。これまでの逆フォトクロミック分子では数分程度要していた熱戻り反応を数秒まで高速化した新規キラル逆フォトクロミック分子の開発に成功した。

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  • 外部摂動を利用した異方的MOFの創製

    Grant number:21K18976  2021.7 - 2023.3

    日本学術振興会  科学研究費助成事業  挑戦的研究(萌芽)

    河野 正規

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    Grant amount:\6500000 ( Direct Cost: \5000000 、 Indirect Cost:\1500000 )

    磁場・電場による小分子の配向制御は熱エネルギーに打ち勝てないために極めて難しいが、分子間相互作用により集合体を形成する特異な配位子と金属イオンを組み合わせることにより自己集合の過程を磁場・電場により制御し初期段階で生成する微小な核の配向を制御することで、通常結晶成長が難しい準安定な異方的細孔性ネットワーク錯体(MOF)を創製することを目的とする。例えば、分子間相互作用により集合体を形成する配位子と比較的磁気的異方性が大きな金属イオンを組み合わせることにより自己集合の過程を磁場により制御することを検討する。さらに、様々な金属イオンと組み合わせることにより電場を利用することによって異方的なMOFの構築を検討する。タンパク質や有機物などの反磁性体の場合、粒子の磁気的異方性は、「分子そのものの構造」や「分子の集合体(結晶・繊維など)としての構造」の異方性に基づくものと、粒子の「形状」の異方性に基づくものに分類される。ベンゼンのような芳香環は、コイルのように振る舞い、磁場をかけることにより誘導電流が発生し、磁場を打ち消しあう方向に磁化しようとする。結果的に芳香環平面はエネルギー的に一番安定な状態、つまり磁場をかけた方向に対して平行に配向しようとする。ただし、今回の結晶化ターゲットであるMOFの配位子のような小分子1分子では熱エネルギーに打ち勝つことができないため、まず集合体を形成する必要がある。今回分子間相互作用により集合体を形成するカルボン酸基を有する配位子を新規に合成し様々な金属イオンと組み合わせることにより自己集合の過程を磁場により制御することを検討した。条件検討の段階で新規MOFの合成に成功しているが、現在のところ室温で錯形成自体を制御することが難しい状況であるため磁場の影響を評価できる状況に至っていない。

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  • 発光性ネットワーク錯体の励起構造の解明

    Grant number:20H04662  2020.4 - 2022.3

    日本学術振興会  科学研究費助成事業  新学術領域研究(研究領域提案型)

    河野 正規

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    Grant amount:\5070000 ( Direct Cost: \3900000 、 Indirect Cost:\1170000 )

    1. はじめに
    速度論的に得られるネットワーク錯体は準安定なソフトクリスタルであり、機械的刺激や加熱などの外部刺激に応じて柔軟な構造変化を示す。本研究では、その場観察X線回折法により光定常状態の発光性ネットワーク錯体の構造を決定し、過渡吸収分光法および理論計算と組み合わせることにより強い発光の起源を解明することを目的とする。その場観察X線回折実験のための分光学的基礎物性の精査および単結晶・粉末結晶を用いて光定常状態・過渡状態のX線回折実験を行った。
    2. 研究成果
    臭化銅四核錯体と4座ピリジン配位子(TPPM)をDMSO中で速度論的に自己集合することにより臭化銅二核錯体Cu2Br2をコネクターとする準安定な細孔性ネットワーク錯体を合成し、真空中で加熱すると強く発光する結晶性粉末錯体(Br体)が得られる。Cl体も合成し、これらの光物性を精査した。光物性評価(UV-vis、発光スペクトル、発光量子収率)を結晶構造に基づいてTD-DFT計算により電子遷移に対するゲストの寄与について調べた。光物性評価は吸収・発光・及び発光量子収率の測定をすべて固体で行った。Br体では発光量子収率13.2 %と高発光が観測された。また、Br体とCl体は同じネットワーク骨格を有しているにもかかわらず吸収スペクトルの極大波長とバンド幅が違っていたことから、ゲストが遷移に影響を及ぼしている可能性が示唆された。また、TD-DFT計算からも振動子強度の大きい遷移の中にゲスト上の軌道の寄与も見られ、空間を介したゲスト―ホスト電荷移動の存在が明らかになり、発光の起源はゲストからホストへの電荷移動(TSCT)およびホスト内の電荷移動(MLCT)によるりん光であった。特にゲストからホストへの電荷移動励起はネットワーク錯体固有のものである。以上の成果をInorg.Chem.で発表した。

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  • The Preparation of Anisotropic-Pressure-Reactive Mechanochemical Materials

    Grant number:15H06357  2015.8 - 2017.3

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Research Activity Start-up

    YAKIYAMA Yumi, SAKURAI Hidehiro, KAWANO Masaki

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    Grant amount:\2730000 ( Direct Cost: \2100000 、 Indirect Cost:\630000 )

    We have established the synthetic method for hetero-aromatic ring-introduced indanedione monomers and their dimers, such as 4-pyridyl, 2-pyradyl, 2-thienyl, 3-methyl-2-thienyl groups derivatives. In their crystal structures, the dissociative central C-C bond moieties were successfully aligned in a parallel manner. In addition, we confirmed C-C bond dissociation/re-association by heating/cooling in 4-pyridyl derivative. Furthermore, unexpectedly obtained porous structure in 4-pyridyl derivative showed high stability against heat and enabled us to reveal its crystal structure change induced by the removal of the solvents from the pores. This results may connect to the new project to investigate indandione dimers-based molecular networks as the molecular recognition/adsorption fields.

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  • Rational aggregation of thiolato metal clusters using structural deficiency

    Grant number:15K21127  2015.4 - 2018.3

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

    Yoshinari Nobuto, KONNO Takumi, IGASHIRA Asako, KUWAMURA Naoto, KAWANO Masaki, KOJIMA Tatsuhiro

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

    In this research project, new synthetic methodology for the structural conversion from stable coordination compounds that involve saturated atoms to reactive products that contain unsaturated atoms was developed using multinuclear metal complexes. As a result, a thermal-induced ligand-dissociation reaction on a luminescent digold(I) complex ([Au2(dppm)3]2+) and a ligand-induced rhodium atom abstraction reaction on an octanuclear complex cation ([Rh4Zn4(aet)12O]6+) were achieved.

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  • Programmed Molecular Self-assembly Utilizing Transition Metals : Synthesis and Function of Nano-scale Molecular Materials

    Grant number:14103014  2002 - 2006

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

    FUJITA Makoto, KAWANO Masaki, YOSHIZAWA Michito, SATO Sota

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    Grant amount:\113620000 ( Direct Cost: \87400000 、 Indirect Cost:\26220000 )

    In this project, we have focused on the synthesis and function of nano-scale molecular materials by programmed molecular self-assembly utilizing transition metals. Here we summarize our research results that are divided into the five topics. (1)Self-assembly of endo-functionalized molecular spheres : we succeeded in the formation of a liquid-like fluorous droplet, composed of 24 perfluoroalkyl chains confined in the interior of a 5-nanometer-sized, roughly spherical shell. The structures were spontaneously assembled in solution from 12 palladium ions and 24 bridging ligands. (2)Photo-switchable molecular catenate : We achieved a precise, clean molecular lock that operates by light. Since the inert Pt(II)-py bond is considerably labialized upon UV irradiation, we demonstrated the photo-switchable molecular lock by the one-way catenation of coordination rings. (3)Selective recognition and folding of oligopeptides by self-assembled hosts : We anticipated that the large hydrophobic cavity of self-assembled hosts could replace the protein scaffolds and stabilize the secondary structures of oligopeptides. (4)Unusual chemical reactions within self-assembled hosts : We found that an aqueous self-assembled cage induces highly unusual regioselectivity in the Diels-Alder reactions of anthracene and phthalimide molecules, promoting reaction at a terminal ring. (5)Direct crystallographic observation of unstable transition species within self-assembled hosts : We succeeded in the in situ crystallographic observation of a coordinatively unsaturated metal complex within a self-assembled coordination cage.

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  • 硫黄架橋ルテニウム複核錯体の合成とそれらの錯体を用いた窒素固定の研究

    Grant number:05740419  1993

    日本学術振興会  科学研究費助成事業  奨励研究(A)

    河野 正規

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    Grant amount:\900000 ( Direct Cost: \900000 )

    ジスルフィド架橋錯体[{RuCl(TMP)_2}_2(mu-Cl)_2(mu-S_2)](1)(TMP=P(OMe)_3)とnAg^+(n=1,2,4)を無水アセトニトリル(AN)中で反応させることによりClとANが置換し、さらに置換活性な錯体が生成することを単結晶X線構造解析とNMRにより明らかにした。特に注目すべき反応は4倍当量のAg^+と錯体1を反応させてエーテル拡散法により結晶化したとき、50℃では一電子還元された[{Ru(AN)_3(TMP)_2}_2(mu-S_2)]^<3+>(2)が生成するのに対して、0℃では架橋しているジスルフィド配位子にエーテル由来のCH_2CH_2CHOEtとCH_2CH_2CHOMeが結合した[{Ru(AN)_3(TMP)_2}_2(mu-S(H)CH_2CH_2CHO(mu-S)Me)]^<3+>と[{Ru(AN)_3(TMP)_2}_2(mu-S(H)CH_2CH_2CHO(mu-S)Me)]^<3+>が生成することをX線構造解析とNMRにより明らかにした。反応機構の詳細に関しては現在のところ明らかではないが、通常安定なエーテル分子の結合が非常に温和な条件下で活性化されたこと、活性化された分子が架橋している硫黄に結合したことが注目すべき結果である。また、錯体1に4AgCF_3SO_3をアセトニトリル中で反応させることにより[{Ru(AN)_3(TMP)_2}_2(mu-S_2)]^<4+>(3)が生成するが、エーテル拡散法により結晶化するとアセトニトリルが電子供与体として働き一電子還元された錯体2を与えることが明らかになった。この反応機構の詳細に関しては現在検討中である。

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