ボトムアップ型「多核クラスター錯体」の創製とレドックス・多電子移動機能

高い分子設計性と優れた光・電子機能を持つ遷移金属錯体を分子ブロックと見立て、それらを合理的に並べ、つなげ、積み上げる戦略により、巨大な分子サイズとユニークな化学特性を示す多核クラスター錯体を創出することを目指しています。より具体的には、ルテニウム多核錯体を基本コアとした「大環状クラスター」および「ワイヤー状クラスター」の合成と構造決定、多電子移動能と長距離レドックスコミュニケーションの評価、ポルフィリン骨格を組み込んだ「巨大カプセル分子」の合成、さらには次世代分子エレクトロニクスを志向した新規な分子材料開発を進めています。

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【この研究テーマに関連する主要な論文】

  • “A Heterometallic Protocol for Turn-On Fluorescence. Synthesis, Structure, and Luminescence Behavior of Diruthenium(III)-Magnesium(II) Complex Decorated with Four Pyrenecarboxylates”

Atsushi Ikegami, Masaaki Abe, and Yoshio Hisaeda
  Chem. Lett., 201443, 456-458.

  DOI: 10.1246/cl.131093

  • “Oxo-Centered Trimetallic Clusters Supported by Electron-Withdrawing Carboxylates: Highly Inert Character in Ligand Exchange Kinetics of Dichloroacetate-bridged Complex [Ru3(μ3-O)(μ-CHCl2COO)6(pyridine)3]”

Atsushi Inatomi, Masaaki Abe, and Yoshio Hisaeda
Aust. J. Chem., 2012, 65, 1599–1607

DOI: org/10.1071/CH12378

  • Electroactive chain-like compounds constructed from trimetallic clusters and 4,4’-bipyridine spacers: one-pot synthesis, characterization and surface binding

Masaaki Abe, Atsushi Inatomi, and Yoshio Hisaeda
   Dalton Trans., 201140, 2289-2298

   DOI: 10.1039/C0DT01237H

New Talent Asia

  • “Synthetic Design of Heterometallic Cluster Compounds with Site-Selective and Stepwise Substitution of Bridging Carboxylates”

Atsushi Ikegami, Masaaki Abe, Atsushi Inatomi, Yoshio Hisaeda
Chem. Eur. J., 2010, 16, 4438-4441.

   DOI: 10.1002/chem.201000387

  • “Carboxylato-Modified New Oxo-Centred Triruthenium Cluster Compounds with CO and Solvent Ligands. The X-Ray Structure of [Ru3O(C2H5CO2)6(CO)(THF)2]”

Atsushi Inatomi, Masaaki Abe, and Yoshio Hisaeda

Eur. J. Inorg. Chem., 2009, 4830–4836

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HP用(池上).pptx

 

 

以上の研究を支えるこれまでの研究

単結晶電極表面への多核クラスター錯体の分子集積化と固液界面における機能発現 —「表面クラスター錯体化学」の創製—

 

精緻にデザインされた機能性分子を固体電極表面に固定化・配列化・積層化することにより所望の界面機能を発現させる研究は、分子素子開発などの観点から重要性を持ち、近年急速な発展を遂げています。この研究では、一分子中にπ(パイ)共役性の発達したルテニウム(Ru)三核クラスターを単結晶Au(111)電極表面へ固定化する戦略により、可逆な多電子移動能を示す金属錯体単分子膜や多積層膜の作製に成功しました。具体的には、Ru三核クラスターの自己組織化単分子膜(Self-assembled Monolayer; SAM)の構築と電子移動・配位子置換特性、光誘起CO解離反応、COとNOの可逆的センシング特性、多積層膜のlayer-by-layer構築など、画期的な新成果を発表しています。さらに、電気化学走査型トンネル顕微鏡(EC-STM)を用いることにより、金属錯体のレドックス反応を一分子レベルで「その場観察」するなど実験難度の高い研究にもチャレンジし、前人未到の成果を挙げています。

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 【この研究テーマに関連する主要な論文】

  • “Electrochemical and Infrared Spectroscopic Study of the Self-Assembled Monolayer of a Cyano-Bridged Dimeric Triruthenium Complex on Gold Surface”

Hua-Xin Zhang, Yoichi Sasaki, Masaaki Abe, Yi Zhang, Shen Ye, Masatoshi Osawa, and Kohei Uosaki
J.Electroanal. Chem., 2014, 714–715, 51-55

DOI: org/10.1016/j.jelechem.2013.12.012

  • “Proton-Coupled Electron Transfer and Lewis Acid Recognition at Self-Assembled Monolayers of an Oxo-Bridged Diruthenium(III) Complex Functionalized with Two Disulfide Anchors”

Hua-Xin Zhang, Masaaki Abe, Yi Zhang, Guofang Li, Shen Ye, Masatoshi Osawa, and Yoichi Sasaki
Langmuir, 2013, 29, 10110-10119

DOI: org/10.1021/la401736f

  • “Fabrication of Photochemical Pattern on a Self-Assembled Monolayer (SAM) of a Ruthenium Cluster under Electrochemical Control”

Yi Zhang, Yujin Tong, Masaaki Abe, Kohei Uosaki, Masatoshi Osawa, Yoichi Sasaki, and Shen Ye
J.Mater. Chem., 2009, 19, 261-267

DOI: 10.1039/B815571B

  • “In Situ Scanning Tunneling Microscopy Observation of Metal–Cluster Redox Interconversion and CO Dissociation Reactions at a Solution/Au(111) Interface”

Hiroyuki Noda, Hiromitsu Uehara, Masaaki Abe, Takayuki Michi, Masatoshi Osawa, Kohei Uosaki, and Yoichi Sasaki
Bull. Chem. Soc. Jpn., 2009, 82, 1227-1231

DOI: 10.1246/bcsj.82.1227

BCSJ Award Article

  • “Multicomponent Molecular Layers That Exhibit Electrochemical Potential Flip on Au(111) by Use of Proton-Coupled Electron-Transfer Reactions”

Hiromitsu Uehara, Tomohiko Inomata, Masaaki Abe, Kohei Uosaki, and Yoichi Sasaki
Chem. Lett., 2008, 37, 684-685

DOI: 10.1246/cl.2008.684

  • “Surface Coordination of Nitric Oxide to a Self-Assembled Monolayer of a Triruthenium Cluster: An In Situ Infrared Spectroscopic Study”

Wei Zhou, Yi Zhang, Masaaki Abe, Kohei Uosaki, Masatoshi Osawa, Yoichi Sasaki, and Shen Ye
Langmuir, 2008, 24, 8027-8035

DOI: 10.1021/la800374s

  • “Effects of Electrolytes on the Redox Potential and the Rate of the CO Dissociation Reaction of Trinuclear Ruthenium Monocarbonyl Complexes Self-Assembled on an Au(111) Electrode Surface”

Takayuki Michi, Masaaki Abe, Junzo Matsuno, Kohei Uosaki, and Yoichi Sasaki
Bull. Chem. Soc. Jpn., 2007, 80, 1368-1376

DOI: 10.1246/bcsj.80.1368

Selected Paper

  • “Immobilization of a Binuclear Ruthenium(III) Complex on a Gold(111) Surface: Observations of Proton-Coupled Electron Transfer and Electrochemical Durability in Aqueous Media”

Hiromitsu Uehara, Masaaki Abe, Yoshio Hisaeda, Kohei Uosaki, and Yoichi Sasaki
Chem. Lett., 2006, 35, 1178-1179

DOI: 10.1246/cl.2006.1178

  • “Oxidation States and CO Ligand Exchange Kinetics in a Self-Assembled Monolayer of a Triruthenium Cluster Studied by In Situ Infrared Spectroscopy”

Wei Zhou, Shen Ye, Masaaki Abe, Takuma Nishida, Kohei Uosaki, Masatoshi Osawa, and Yoichi Sasaki
Chem. Eur. J., 2005, 11, 5040-5054

DOI: 10.1002/chem.200401340

  • “Photoconversion of a Redox-Active Self-Assembled Monolayer: In Situ Probing of Photoinduced CO Dissociation from a Triruthenium Cluster Center on Gold”

Masaaki Abe, Takuya Masuda, Toshihiro Kondo, Kohei Uosaki, and Yoichi Sasaki
Angew. Chem. Int. Ed., 2005, 44, 416-419

DOI: 10.1002/anie.200460651

  • “Electrochemical Control of CO/NO Ligand Exchange in a Triruthenium Cluster Monolayer Assembled on a Gold Electrode Surface”

Shen Ye, Wei Zhou, Masaaki Abe, Takuma Nishida, Longfei Cui, Kohei Uosaki, Masatoshi Osawa, and Yoichi Sasaki
J.Am. Chem. Soc., 2004, 126, 7434-7435

DOI: 10.1021/ja049478j

  • “Electrochemically Controlled Layer-by-Layer Deposition of Metal Cluster Molecular Multilayers on Gold”

Masaaki Abe, Takayuki Michi, Akira Sato, Toshihiro Kondo, Wei Zhou, Shen Ye, Kohei Uosaki, and Yoichi Sasaki
Angew. Chem. Int. Ed., 2003, 42, 2912-2915

DOI: 10.1002/anie.200351334

Very Important Papers

  • “A Ligand Substitution Reaction of Oxo-Centred Triruthenium Complexes Assembled as Monolayers on Gold Electrodes”

Akira Sato, Masaaki Abe, Tomohiko Inomata, Toshihiro Kondo, Shen Ye, Kohei Uosaki, and Yoichi Sasaki
Phys. Chem. Chem. Phys., 2001, 3, 3420-3426

DOI: 10.1039/b101561n