Bottom-up synthesis and chemical functions of heterostructures of metal-cluster complexes

• Project/Area Number: 16550048
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Inorganic chemistry
• Research Institution: Kyushu University (2005-2007); Hokkaido University (2004)
• Principal Investigator: ABE Masaaki Kyushu University, Graduate School of Engineering, Associate Professor (90260033)
• Project Period (FY): 2004 – 2007
• Project Status: Completed (Fiscal Year 2007)
• Budget Amount: ¥3,710,000 (Direct Cost: ¥3,500,000、Indirect Cost: ¥210,000); Fiscal Year 2007: ¥910,000 (Direct Cost: ¥700,000、Indirect Cost: ¥210,000); Fiscal Year 2006: ¥700,000 (Direct Cost: ¥700,000); Fiscal Year 2005: ¥800,000 (Direct Cost: ¥800,000); Fiscal Year 2004: ¥1,300,000 (Direct Cost: ¥1,300,000)
• Keywords: Ruthenium / Surface / Layered structures / Proton-coupled electron transfer / Dinuclear complexes / Trinuclear complexes / Porphyrin / Corrin complexes / 自己集合化単分子層 / 固液界面 / ルイス酸 / ポテンシャル勾配 / 多核錯体 / 金属クラスター / ボトムアップ / 配位子置換 / 酸化還元 / ポルフィリン配位子 / レニウム錯体 / 金電極 / 自己組織化 / 単分子膜 / 多層膜 / 光誘起反応

Research Abstract

This project has explored synthesis and characterizations of new potential-gradient molecular architectures where multiple units of redox-active moieties (including multinuclear complexes and organic ligands)are built up on Au electrode surfaces in a well-defined sequence. Here we have focused on the construction of molecular systems in which two different metal-cluster units are linked by a bridging ligand on a surface of Au(111) electrode. The hetero-molecular layers have been prepared by immersing an Au (111) electrode covered with the H_2O-terminated triruthenium SAM into a CH_2Cl_2 solution of a new ruthenium dimer. Here, the Ru_3 unit(bottom layer)and the Ru_2 unit (upper layer) are linked with 4,4'-bpy. Owing to the nature of proton-coupled electron transfer reaction in the ruthenium dimer, it was demonstrated that the potential gradient of molecular wire was controlled by pH of the electrolyte media in a reversible manner. Direct and facile immobilization of a solvent-terminated new diruthenium complex onto organic SAM was also demonstrated. For the triruthenium complex SAM, we examined electrolyte anion effects in redox potentials, reactivity of Ru_3 SAM with gaseous molecules such as CO and NO,^3 and photoreactivity. Another achievement in this project was a successful synthetic incorporation of a series of terapyrrol ligands and their metal complexes into the triruthenium complex.

Research Products

• [Journal Article] Spontaneous Rapid Growth of Triruthenium Cluster Multilayers on Gold Surface.Cyclic Voltammetric in situ Monitoring and AFM Characterization (2008)
  • Author(s): Takayuki Michi, et. al.
  • Journal Title: Chem.Lett 37・6 Pages: 576-577
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Multicomponent Molecular Layers that Exhibit Electrochemical Potential Flip on Au(111)by Use of Proton-coupled Electron Transfer Reactions (2008)
  • Author(s): Hiromitsu Uehara, et. al.
  • Journal Title: Chem.Lett (印刷中)
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Surface Coordination of Nitric Oxide to a Self-Assembled Monolayer of a Triruthenium Cluster:An in situ Infrared Spectroscopic Study (2008)
  • Author(s): Shen Ye, et. al.
  • Journal Title: Langmuir (印刷中)
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Spontaneous Rapid Growth of Triruthenium Cluster Multilayers on Gold Surface.Cyclic Voltammetric in situ Monitoring and AFM Characterization (2008)
  • Author(s): Takayuki, Michi, Masaaki, Abe, Satoru, Takakusagi, Masako, Kato, Kohei, Uosaki, Yoichi, Sasaki
  • Journal Title: Chem.Lett. 37(6) Pages: 576-577
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Spontaneous Rapid Growth of Triruthenium Cluster Multilayers on Gold Surface. Cyclic Voltammetric In Situ Monitoring and AFM Characterization (2008)
  • Author(s): Takayuki Michi, et. al.
  • Journal Title: Chem. Lett. 37(in press)
  • Peer Reviewed
• [Journal Article] Mixed Re^<VII>-Fe^<VII>-Cu^<II>Complexes Prepared by the Use of the Complex Ligand [Re(O)_3(tpenH-κ^<3>N,N'',N''')]^<2+>(tpen = N,N,N',N'-Tetrakis(2-pyridylmethyl)ethylenediamine) (2007)
  • Author(s): Toshihiro Tabeya, et. al.
  • Journal Title: Bull.Chem.Soc.Jpn 80・1 Pages: 192-194
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Remarkable Stabilization of a Ligand-Based Mixed-Valence State in the Metal-Based Mixed Valent Ru_2^<II>M^<II>(μ_3-O)(M=Co,Ni) Trinuclear Cluster Complexes (2007)
  • Author(s): Maiko Tanaka, et. al.
  • Journal Title: Bull.Chem.Soc.Jpn 80・1 Pages: 192-194
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] 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 (2007)
  • Author(s): Takayuki Michi, et. al.
  • Journal Title: Bull.Chem.Soc.Jpn 80・7 Pages: 1368-1376
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Remarkable Stabilization of a Ligand-Based Mixed-Valence State in the Metal-Based Mixed Valent Ru2II,IIIMII(μ3-O)(M=Co,Ni)Trinuclear Cluster Complexes (2007)
  • Author(s): Maiko, Tanaka, Nobuko, Kariya, Masaaki, Abe, Yoichi, Sasaki
  • Journal Title: Bull.Chem.Soc.Jpn. 80(1) Pages: 192-194
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] 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 (2007)
  • Author(s): Takayuki, Michi, Masaaki, Abe, Junzo, Matsuno, Kohei, Uosaki, Yoichi, Sasaki
  • Journal Title: Bull Chem.Soc.Jpn. 80(7) Pages: 1368-1376
  • NAID: 10019527726
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Remarkable Stabilization of a Ligand-Based Mixed-Valence State in the Metal-Based Mixed Valent Ru_2^<II,III>M^<II>(μ_3-O)(M=Co,Ni)Trinuclear Cluster Complexes (2007)
  • Author(s): Maiko Tanaka, et. al.
  • Journal Title: Bull. Chem. Soc. Jpn. 80 Pages: 192-194
  • Peer Reviewed
• [Journal Article] Effects of Electrolytes on the Redox Potential and the Rate of the CO Dissociati on Reaction of Trinuclear Ruthenium Monocarbonyl Complexes Self-assembled on an Au(111)Electrode Surface (2007)
  • Author(s): Takayuki Michi, et. al.
  • Journal Title: Bull. Chem. Soc. Jpn. 80 Pages: 1368-1376
  • Peer Reviewed
• [Journal Article] Remarkable Stabilization of a Ligand-Based Mixed-Valence State in the Metal-Based Mixed Valent Ru_2^<II,III>Mu^<II>(μ_3O)(M=Co, Ni) Trinuclear Cluster Complexes (2007)
  • Author(s): Makio Tanaka et al.
  • Journal Title: Bull. Chem, Soc. Jpn. 80・1 Pages: 192-194
• [Journal Article] Immobilization of a Binuclear Ruthenium(III) Complex on a Gold (111)Surface:Observations of Proton-coupled Electron Transfer and Electrochemical Durability in Aqueous Media (2006)
  • Author(s): Hiromitsu Uehara, et. al.
  • Journal Title: Chem.Lett 35・10 Pages: 1178-1179
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Disproportionation Reaction of Seven-coordinate [Re^<V>O(tpen)]^<3+> into [Re^<IV>O(tpen)]^<2+> and [Re^<VII>(O)_3(tpenH-κ^<3>N,N'',N''')]^<2+> where tpen is N,N,N',N'-Tetrakis(2-pyridylmethyl)ethylenediamine (2006)
  • Author(s): Toshihiro Tabeya, et. al.
  • Journal Title: Chem.Lett 35・9 Pages: 1066-1067
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Immobilization of a Binuclear Ruthenium(III)Complex on a Gold (111) Surface : Observations of Proton-coupled Electron Transfer and Electrochemical Durability in Aqueous Media (2006)
  • Author(s): Hiromitsu, Uehara, Masaaki, Abe, Yoshio, Hisaeda, Kohei, Uosaki, Yoichi, Sasaki
  • Journal Title: Chem.Lett. 35(10) Pages: 1178-1179
  • NAID: 10018323533
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Disproportionation Reaction of Seven-coordinate [ReVO(tpen)]3+into[ReIVO(tpen)]2+and[ReVII(O)3(tpenH-κ3N,N'',N''')]2+where tpen is N,N,N',N'-Tetrakis(2-pyridylmethyl)ethylenediamine (2006)
  • Author(s): Toshihiro, Tabeya, Masaaki, Abe, Yoichi, Sasaki
  • Journal Title: Chem.Lett. 35(9) Pages: 1066-1067
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Mixed ReVII-FeIII and ReVII-CuII Complexes Prepared by the Use of the Complex Ligand[Re(O)3(tpenH-κ3N,N'',N''')]2+(tpen=N,N,N',N'-Tetrakis(2-pyridylmethyl)ethylenediamine) (2006)
  • Author(s): Toshihiro, Tabeya, Masaaki, Abe, Yoichi, Sasaki
  • Journal Title: Bull.Chem.Soc.Jpn. 79(9) Pages: 1398-1403
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Immobilization of a Binuclear Ruthenium(III) Complex on a Gold(111) Surface : Observations of Proton-coupled Electron Transfer and Electrochemical Durability in Aqueous Media. (2006)
  • Author(s): Hiromitsu Uehara et al.
  • Journal Title: Chem. Lett. 35・10 Pages: 1178-1179
• [Journal Article] Disproportionation Reaction of Seven-coordinate [Re^vO(tpen)]-<3+> into [Re^<IV>O(tpen)]^<2+> and [Re^<VII>(O)_3(tpenH-k^3N,N",N"')]^<2+> where tpen is N,N,N',N'-Terakis(2-pyridylmethyl)ethylenediamine (2006)
  • Author(s): Toshihiro Tabeya et al.
  • Journal Title: Chem. Lett. 35・9 Pages: 1066-1067
• [Journal Article] Mixed Re^<VII>-Fe^<III> and Re^<VII>-Cu^<II> Complex Prepared by the Use of the Complex Ligand [Re(O)_3(tpenH-k^3N,N",N"')]^<2+> (tpen N,N,N",N2-Tetrakis(2-pyridymethyl)ethylenediamine) (2006)
  • Author(s): Toshihiro Tabeya et al.
  • Journal Title: Bull. Chem. Soc. Jpn. 79・9 Pages: 1398-1403
• [Journal Article] Photoconversion of a Redox-Active Self-Assembled Monolayer:In Situ Probing of Photoinduce CO Dissociation from a Triruthenium Cluster Center on Gold (2005)
  • Author(s): Masaaki Abe, et. al.
  • Journal Title: Angew.Chem.Int.Ed. 44・3 Pages: 416-419
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Oxidation States and CO Ligand Exchange Kinetics in a Self-Assembled Monolayer of a Trirutenium Cluster Studied by in situ Infrared Spectroscopy (2005)
  • Author(s): Wei Zhou, et. al.
  • Journal Title: Chem.Eur.J. 11・17 Pages: 5040-5054
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] X-ray Structure and Electrochemical Properties of a Tpen-Bridged Hetero-Binuclear Complex fac,fac-[Re^<VII>O_3(μ-tpen)Re^<I>(CO)_3](PF_6)_2 where Tpen Is N,N,N',N'-Tetrakis(2-pyridylmethyl)ethylenediamine (2005)
  • Author(s): Toshihiro Tabeya, et. al.
  • Journal Title: J.Nucl.Radiochem.Sci. 6・3 Pages: 157-159
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Interfacial Electron-Transfer and Ligand-Dissociation Characteristics of Layer-by-Layer Nanoarchitectures Constructed from Ruthenium Cluster Molecules (2005)
  • Author(s): Michi, et. al.
  • Journal Title: ECS Proceedings Volume, Electrode Processes VII Pages: 116-131
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Photoconversion of a Redox-Active Self-Assembled Monolayer : In Situ Probing of Photoinduced CO Dissociation from a Triruthenium Cluster Center on Gold (2005)
  • Author(s): Masaaki, Abe, Takuya, Masuda, Toshihiro, Kondo, Kohei, Uosaki, Yoichi, Sasaki
  • Journal Title: Angew.Chem.Int.Ed. 44(3) Pages: 416-419
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Oxidation States and CO Ligand Exchange Kinetics in a Self-Assembled Monolayer of a Triruthenium Cluster Studied by in situ Infrared Spectroscopy (2005)
  • Author(s): Wei, Zhou, Shen, Ye, Masaaki, Abe, Takuma, Nishida, Kohei, Uosaki, Masatoshi, Osawa, Yoichi, Sasaki
  • Journal Title: Chem.Eur.J. 11(17) Pages: 5040-5054
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Interfacial Electron-Transfer and Ligand-Dissociation Characteristics of Layer-by-Layer Nanoarchitectures Constructed from Ruthenium Cluster Molecules (2005)
  • Author(s): Takayuki, Michi, Masaaki, Abe, Shen, Ye, Masatoshi, Osawa, Toshihiro, Kondo, Kohei, Uosaki, Yoichi, Sasaki
  • Journal Title: ECS Proceedings Volume, Electrode Processes VII Pages: 116-131
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] X-ray Structure and Electrochemical Properties of a Tpen-Bridged Hetero-Binuclear Complex fac-,fac-[ReVIIO3(μ-tpen)ReI(CO)3](PF6)2 where Tpen Is N,N,N',N'-T etrakis(2-pyridylmethyl)ethylenediamine (2005)
  • Author(s): Toshihiro, Tabeya, Masaaki, Abe, Ayako, Mitani, Kiyoshi, Tsuge, Yoichi, Sasaki
  • Journal Title: J.Nucl.Radiochem.Sci. 6(3) Pages: 157-159
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Photoconversion of a Redox-Active Self-Assembled Monolayer : In Situ Probing of Photoinduced CO Dissociation from a Triruthenium Cluster Center on Gold (2005)
  • Author(s): Masaaki Abe et al.
  • Journal Title: Angew.Chem.Int.Ed. 44・3 Pages: 416-416
• [Journal Article] Interfacial Electron-Transfer and Ligand-Dissociation Characteristics of Layer-by-Layer Nanoarchitectures Constructed from Ruthenium Cluster Molecules (2005)
  • Author(s): Takayuki Michi et al.
  • Journal Title: ECS Proceedings Volume, Electrode Processes VII Pages: 116-116
• [Journal Article] Oxidation States and CO Ligand Exchange Kinetics in a Self-Assembled Monolayer of a Triruthenium Cluster Studied by in situ Infrared Spectroscopy (2005)
  • Author(s): Wei Zhou et al.
  • Journal Title: Chem.Eur.J 11・17 Pages: 5040-5040
• [Journal Article] X-ray Structure and Electrochemical Properties of a Tpen-Bridged Hetero-Binuclear Complex fac-fac0[Re^<VII>O_3(μ-tpen)Re^I(CO)_3](PF_6)_2 where Tpen Is N,N,N',N'-Tetrakis(2-pyridylmethyl)ethylenediamine (2005)
  • Author(s): Toshihiro Tabeya et al.
  • Journal Title: J.Nucl.Radiochem.Sci 6・3 Pages: 157-157
• [Journal Article] Photoconversion of a Redox-Active Self-Assembled Monolayer : In Situ Probing of Photoinduced CO Dissociation from a Triruthenium Cluster Center on Gold (2005)
  • Author(s): Masaaki Abe
  • Journal Title: Angew.Chem.Int.Ed. 44巻3号 Pages: 416-419
• [Journal Article] Syntheses, Structures, and Redox Properties of Dimeric Triruthenium Cluster Bridged by Bis(diphenylphosphino)acetylene and -ethylene (2004)
  • Author(s): Jing-Lin Chen
  • Journal Title: Inorg.Chem. 43巻4号 Pages: 1481-1490
• [Journal Article] A Pair of Seven-Coordinate Oxorhenium Complexes : [Re^<IV>O(tpen)]^<2+> and [Re^vO(tpen)]^<3+>(tpen=N,N,N'N'-Tetrakis(2-pyridylmethyl)ethylenediamine) (2004)
  • Author(s): Hai-Ying Jin
  • Journal Title: Bull.Chem.Soc.Jpn. 77巻6号 Pages: 1139-1146
• [Journal Article] Electrochemical Control of CO/NO Ligand Exchange in a Triruthenium Cluster Monolayer Assembled on a Gold Electrode Surface (2004)
  • Author(s): Shen Ye
  • Journal Title: J.Am.Chem.Soc. 126巻24号 Pages: 7434-7435
• [Journal Article] Photodissociation of CO from [Ru_3(μ_3-O)(μ-OOCCH_3)_6(CO)L_2] in Acetonitrile, where L=Pyridine, 4-Cyanopyridine and Methanol (2004)
  • Author(s): Daisuke Akashi
  • Journal Title: Dalton Trans 18号 Pages: 2883-2889
• [Journal Article] Ligand-Ligand Redox Interactions through Some Metal-Cluster Units (2004)
  • Author(s): Yoichi Sasaki
  • Journal Title: Chem.Record 4巻5号 Pages: 279-290
• [Journal Article] Multicomponent Molecular Layers that Exhibit Electrochemical Potential Flip on Au(111) by Use of Proton-coupled Electron Transfer Reactions
  • Author(s): Hiromitsu, Uehara, Tomohiko, Inomata, Masaaki, Abe, Kohei, Uosaki, Yoichi, Sasaki
  • Journal Title: Chem.Lett. (in press)
  • NAID: 10021081818
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Surface Coordination of Nitric Oxide to a Self-Assembled Monolayer of a Triruthenium Cluster : An in situ Infrared Spectroscopic Study
  • Author(s): Shen, Ye, Wei, Zhou, Yi, Zhang, Masaaki, Abe, Kohei, Uosaki, Masatoshi, Osawa, Yoichi, Sasaki
  • Journal Title: Langmuir (in press)
  • Description: 「研究成果報告書概要(欧文)」より
• [Presentation] Interfacial Control of Chemical Function in Surface-Integrated Coordination Space Based on Redox-Active Coordination Compounds (2007)
  • Author(s): Masaaki Abe, et. al.
  • Organizer: 第三回「配位空間の化学」国際会議(ISCCS 2007)
  • Place of Presentation: 淡路夢舞台国際会議場(淡路市)
• [Book] Inorganic Chromotropism
  • Author(s): 佐々木 陽一, 阿部 正明
  • Publisher: 講談社サイエンティフィック(印刷中)
  • Description: 「研究成果報告書概要(和文)」より
• [Patent(Industrial Property Rights)] クロミックな近赤外線吸収特性を有する有機重合体組成物および成形体 (2008)
  • Inventor(s): 森原 靖、大木 弘之、大竹 富明、阿部 正明、久枝 良雄、冨安 佑騎
  • Industrial Property Rights Holder: 森原 靖、大木 弘之、大竹 富明、阿部 正明、久枝 良雄、冨安 佑騎
  • Industrial Property Number: 2008-053677
  • Filing Date: 2008-03-04