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2001 Fiscal Year Final Research Report Summary

Creation of multi-dimensional structures of functional molecules by metal complexation reactions

Research Project

Project/Area Number 11309003
Research Category

Grant-in-Aid for Scientific Research (A)

Allocation TypeSingle-year Grants
Section一般
Research Field 広領域
Research InstitutionThe University of Tokyo

Principal Investigator

NISHIHARA Hiroshi  The University of Tokyo, Graduate School of Science, Professor, 大学院・理学系研究科, 教授 (70156090)

Co-Investigator(Kenkyū-buntansha) KURIHARA Masato  The University of Tokyo, Graduate School of Science, Assistant, 大学院・理学系研究科, 助手 (50292826)
KUBO Kenya  The University of Tokyo, Graduate School of Science, Assistant, 大学院・理学系研究科, 助手 (60214988)
Project Period (FY) 1999 – 2001
Keywordsmetal nanoparticles / azo-coningated comolexes / photochromic complexes / donor-acceptor interaction / quinone / ferrocene / redox / intramolecular electron transfer
Research Abstract

To construct new multi-dimensional functional molecular systems by utilizing complex reactions of transition metal complexes has been investigated in this research project. The molecular systems that have been focused are 1) azo-conjugated metal complexes with photo-functions, 2) donor-acceptor conjugated complexes with an ability of proton-coupled intramolecular electron-transfer reactions, and 3) metal nanoparticles modified with redox- and photo-functional complexes. The summary of the results is as follows.
The trans-to-cis isomerization of azoferrocene proceeds not only by the photoexcitation of the π-π^* transition band but also by photoexcitation of the MLCT (d-π^* transition) band. The trans/cis ratio of the azobenzene-attached bipyridine ligands in their cobalt complex is reversibly altered by a combination of photoirradiation with a single UV light source and the reversible redox change between Co(II) and Co(III). A newly synthesized Ni, Pd and Pt tolylazophenylenedithiolato c … More omplexes 2-4 show reversible trans-to-cis photoisomerization, proto-chromism, and novel proton-coupled cis-to-trans isomerization.
The protonation to carbonyl groups of the anthraquinone moiety in 1 -ferrocenylethynylanthraquinone causes intramolecular electron transfer leading to a novel structural change into a η^6-fulvene-cumulene Fe(II) complex. A 2:1 donor-acceptor complex, l,5-bis(ferrocenylethynyl)anthraquinone undergoes a two-step proton response, and the doubly protonated species involves a η^6-fulvene-Fe(II) complex-cumulene structure, and a novel spin-separated form of a ferrocenium (Fe(III)) ion and a semiquinone radical in the solution. Furthermore, the complex is in a thermal equilibrium between the valence tautomers of a donor-acceptor system in the solid state.
Synthesis and electrochemical deposition behavior of biferrocene and anthraquinone derivative-modified Au and Pd clusters have been investigated. It is also possible to fabricate hetero structures by alternative electrodeposition of Bfc-modified gold and palladium nanoparticles. Less

  • Research Products

    (64 results)

All Other

All Publications (64 results)

  • [Publications] H.Nishihara, T.Horikoshi: "Intervalence-Transfer Bands for Mixed-Valence Oligo(1, 1'-dihexylferrocenylene)s"Synth. Metals. 101(1-3). 1523 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.Nishihara, M.Kurashina, K.Aramaki, K.Kubo: "Near-IR Photoconductivity of Poly(1, 1'-dihexylferrocenylene)-TCNE CT Complex"Synth. Metals. 101(1-3). 457-458 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] I.Matsuoka, H.Yoshikawa, M.Kurihara, H.Nishihara: "Synthesis and Redox Properties of Poly (cobaltacyclopentadienylene thienylene)"Synth. Metals. 102(1-2). 1519-1520 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Kurihara, M.Kurosawa, T.Matsuda, H.Nishihara: "Synthesis and Physical Properties of Azo-ferrocene Oligomers and Polymers"Synth. Metals. 102(1-3). 1517-1518 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Horikoshi, M.Itoh, M.Kurihara, K.Kubo, H.Nishihara: "Synthesis, Redox Behaviors and Electrodeposition of Biferrocene-modified Gold Clusters"J. Electroanal. Chem.. 473(1-2). 113-116 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.N.Jayaprakash, P.C.Ray, I.Matsuoka, M.M.Bhadbhade, V.G.Puranik, P.K.Das, H.Nishihara, A.Sarkar: "Ferrocene in Conjugation with a Fischer Carbene : Synthesis NLO and Electrochemical Behavior of a Novel Organometallic Push-Pull system"Organometallics. 18(19). 3851-3858 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Horikoshi, K.Kubo, H.Nishihara: "Dependence of intervalence-transfer bands for mixed-valence oligo(1, 1'-dihexylferrocenylene)s on the oxidation number and the number of ferrocene units from two to six"J. Chem. Soc., Dalton Trans.. (19). 3355-3360 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Kurosawa, T.Nankawa, T.Matsuda, K.Kubo, M.Kurihara, H.Nishihara: "Synthesis of Azo-bridged Ferrocene Oligomers and a Polymer and Electrochemical and Optical Analysis of Internuclear Electronic Interactions in Their Mixed-Valence States"Inorg. Chem.. 38(22). 5113-5123 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Kubo, H.Kondow, H.Nishihara: "Oxidative-Decomposition and Electron-Transfer Kinetics of Self-Assembled Monolayers of Biferrocene-Terminated Alkanethiol on Gold"Electrochemistry. 67(12). 1229-1131 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Yamada, K.Kubo, H.Nishihara: "Electroreductive Deposition of Au Clusters Modified with an Anthraquinone Derivative"Chem. Lett. (12). 1335-1336 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Yutaka, M.Kurihara, K.Kubo, H.Nishihara: "Novel Photoisomerization Behavior of Rh Binuclear Complexes Involving an Azobenzene-bridged Bis(terpyridine) Ligand -Strong Effects of Counterion and Solvent and the Induction of Redox Potential Shift"Inorg. Chem.. 39(16). 3438-3439 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Yutaka, M.Kurihara, H.Nishihara: "Synthesis and Physical Properties of a a-Conjugated Ruthenium(II) Dinuclear Complex Involving an Azobenzene-Bridged Bis(terpyridine) Ligand"Mol. Cryst. Liq. Cryst. 343. 193-198 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Kurihara, K.Kubo, T.Horikoshi, M.Kurosawa, T.Nankawa, T.Matsuda, H.Nishihara: "Electron Transfer of Conjugated Polymeric Ferrocenes"Macromol. Symp.. 156. 21-27 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Murata, T.Fujita, M.Yamada, M.Kurihara, H.Nishihara: "Novel Protonation-Induced Structural Conversion of an Ethynylene-bridged Ferrocene-Anthraquinone Complex"Chem. Lett. 1328-1329 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Kurihara, T.Matsuda, A.Hirooka, T.Yutaka, H.Nishihara: "Novel Photo-isomerization of Azoferrocene with a Low-energy MLCT Band and Significant Change of the Redox Behavior between the Cis and Trans Isomers"J. Am. Chem. Soc. 122(49). 12373-12374 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Murata, T.Hoshi, I.Matsuoka, T.Nankawa, M.Kurihara, H.Nishihara: "Synthesis and Redox Properties of a π-Conjugated Cyclobutadienecobalt Polymer Containing Ferrocenyl Groups"J. Inorg. Organomet. Polym.. 10(4). 209-219 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Kurihara, H.Sano, M.Murata, H.Nishihara: "Synthesis of a Vinylene-Bridged Ferrocene-Hydroquinone Complex and Its Unusual Structural Change Originated by Proton-Coupled Electron Transfer"Inorg. Chem. 40(1). 4-5 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.Nishihara: "Redox and Optical Properties of Conjugated Ferrocene Oligomers"Bull. Chem. Soc. Jpn (Accounts). 74(1). 19-29 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Yamada, T.Tadera, K.Kubo, H.Nishihara: "Electroreductive Deposition of Anthraquinone Derivative Attached Au Clusters : Optical Properties and Scanning Tunneling Microscopy Observation of the Electrodeposited Cluster Film"Langmuir. 17(8). 2363-2370 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Yamada, I.Quiros, J.Mizutani, K.Kubo, H.Nishihara: "Preparation of palladium nanoparticles functionalized with biferrocene thiol derivatives and their electro-oxidative deposition"Phys. Chem. Chem. Phys.. 3. 3377-3381 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y.Men, K.Kubo, M.Kurihara, H.Nishihara: "Syntheses of biferrocene dithiol and disulfide derivatives and their redox behavior in SAM with and without gold clusters on the gold substrate"Phys. Chem. Chem. Phys.. 3. 3427-3430 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.Kume, M.Kurihara, Hiroshi Nishihara: "Reversible trans-cis photoisomerization of azobenzene-attached bipyridine ligands coordinated to cobalt using a single UV light source and the Co(III)/Co(II) redox change"Chem. Commun.. 17. 1656-1657 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Yutaka, I.Mori, M.Kurihara, J.Mizutani, K.Kubo, S.Furusho, K.Matsumura, N.Tamai, H.Nishihara: "Synthesis, Characterization, and Photochemical Properties of Azobenzene-Conjugated Rh and Ru Bis(terpyridine) Complexes"Inorg. Chem.. 40(19). 4986-4995 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Nihei, M.Kurihara, J.Mizutani, H.Nishihara: "Photo-and Proton-coupled Isomerization of Novel Azo-conjugated Platinadithiolene Complex"Chem. Lett. 9. 852-853 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y.Yamada, J.Mizutani, M.Kurihara, H.Nishihara: "Synthesis of a New Bis(ferrocenyl)ruthenacyclopentatriene Compound with a Significant Inter-metal Electronic Communication"J. Organometal. Chem. 637-639. 80-83 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Yamada, A.Kuzume, M.Kurihara, K.Kubo, H.Nishihara: "Formation of a novel porphyrin -gold nanoparticle network film induced by infrared light irradiation"Chem. Commun. 2476-2477 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Murata, M.Yamada, T.Fujita, K.Kojima, M.Kurihara, K.Kubo, Y.Kobayashi, H.Nishihara: "Structural Conversion and Spin Separation in Bis(ferrocenylethynyl)anthraquinones Triggered by Proton-Coupled Intramolecular Electron Transfer"J. Am. Chem. Soc. 123(51). 12903-12904 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Nishiyama, A.Kubo, I.Taniguchi, M.Yamada, H.Nishihara: "Effects of Alkyl Chain as a Spacer on Electrochemical Reaction and SEIRA Spectra for Self-assembled Monolayers' Having Anthraquinone Redox Center"Electrochemistry. 69(12). 980-983 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] I.Quiros, M.Yamada, K.Kubo, J.Mizutani, M.Kurihara, H.Nishihara: "Preparation of Alkyl Thiolate-Protected Palladium Nanoparticles and Their Size Dependence on Synthetic Conditions"Langmuir. (in press).

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 西原 寛: "機能性金属錯体への期待"化学と教育. 49. 28-31 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 西原 寛, 栗原正人: "金属錯体系のレドックス共役ナノ分子材料"化学工業. 52(8). 615-621 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Kurihara, H.Nishihara: "Azo-and quinone-conjugated redox complexes -photo-and proton-coupled intramolecular reactions based on d-π interaction"Coord. Chem. Rev.. (in press).

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 西原 寛: "「相性」,異なる物質間の相性"東京大学出版会. 249-270 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.Nishihara: "Adv. Inorg. Chem."Redox Chemistry and Functionalities of Conjugated Ferrocene Systems(in press).

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M. Yamada, I. Quiros, J. Mizutani, K. Kubo, H. Nishihara: "Preparation of palladium nanoparticles functionalized with biferrocene thiol derivatives and their electro-oxidative deposition"Phys. Chem. Chem. Phys.. 3. 3377-3381 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H.Nishihara, T.Horikoshi: "Intervalence-Transfer Bands for Mixed-Valence Oligo(1, 1'-dihexylferrocenylene)s"Synth. Metals. 102(1-3). 1523 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H.Nishihara, M.Kurashina, K.Aramaki, K.Kubo: "Near-IR Photoconductivity of Poly(1, 1'-dihexylferrocenylene)-TCNE CT Complex"Synth. Metals. 101(1-3). 1523 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M. Kurihara, M. Kurosawa, T. Matsuda, H. Nishihara: "Synthesis and Physical Properties of Azo-ferrocene Oligomers and Polymers"Synth. Metals. 102(1-3). 1517-1518 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T. Horikoshi, M. Itoh, M. Kurihara, K. Kubo, H. Nishihara: "Synthesis, Redox Behaviors and Electrodeposition of Biferrocene-modified Gold Clusters"J. Electroanal. Chem.. 473(1-2). 113-116 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. N. Jayaprakash, P. C. Ray, I. Matsuoka, M. M. Bhadbhade, V. G. Puranik, P. K. Das, H. Nishihara, A. Sarkar: "Ferrocene in Conjugation with a Fischer Carbene: Synthesis, NLO and Electrochemical Behavior of a Novel Organometallic Push-Pull system"Organometallics. 18(19). 3851-3858 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T. Horikoshi, K. Kubo, H. Nishihara: "Dependence of intervalence-transfer bands for mixed-valence oligo(1, 1 '-dihexylferrocenylene)s on the oxidation number and the number of ferrocene units from two to six"J. Chem. Soc., Dalton Trans.. (19). 3355-3360 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M. Kurosawa, T. Nankawa, T. Matsuda, K. Kubo, M. Kurihara, H. Nishihara: "Synthesis ofAzo-bridged Ferrocene Oligomers and a Polymer and Electrochemical and Optical Analysis of Internuclear Electronic Interactions in Their Mixed-Valence States"Inorg. Chem.. 38(22). 5113-5123 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Kubo, H. Kondow, H. Nishihara: "Oxidative-Decomposition and Electron-Transfer Kinetics of Self-Assembled Monolayers of Biferrocene-Terminated Alkanethiol on Gold"Electrochemistry. 67(12). 1129-1131 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M. Yamada, K. Kubo, H. Nishihara: "Electroreductive Deposition of Au Clusters Modified with an Anthraquinone Derivative"Chem. Lett. (12). 1335-1336 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T. Yutaka, M. Kurihara, K. Kubo, H. Nishihara: "Novel Photoisomerization Behavior of Rh Binuclear Complexes Involving an Azobenzene-bridged Bis(terpyridine) Ligand - Strong Effects ofCounterion and Solvent and the Induction of Redox Potential Shift"Inorg. Chem.. 39(16). 3438-3439 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T. Yutaka, M. Kurihara, H. Nishihara: "Synthesis and Physical Properties of a π-Conjugated Ruthenium(II) Dinuclear Complex Involving an Azobenzene-Bridged Bis(terpyridine) Ligand"Mol. Cryst. Liq. Cryst.. 343. 193-198 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M. Kurihara, K. Kubo, T. Horikoshi, M. Kurosawa, T. Nankawa, T. Matsuda, H. Nishihara: "Electron Transfer of Conjugated Polymeric Ferrocenes"Macromol. Symp.. 156. 21-27 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M. Murata, T. Fujita, M. Yamada, M. Kurihara, H. Nishihara: "Novel Protonation-Induced Structural Conversion of an Ethynylene-bridged Ferrocene-Anthraquinone Complex"Chem. Lett.. 1328-1329 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M. Kurihara, T. Matsuda, A. Hirooka, T. Yutaka, H. Nishihara: "Novel Photo-isomerization of Azoferrocene with a Low-energy MLCT Band and Significant Change of the Redox Behavior between the Cis and Trans Isomers"J. Am. Chem. Soc. 122(49). 12373-12374 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M. Murata, T. Hoshi, I. Matsuoka, T. Nankawa, M. Kurihara, H. Nishihara: "Synthesis and Redox Properties of a π-Conjugated Cyclobutadienecobalt Polymer Containing Ferrocenyl Groups"J. Inorg. Organoment. Polym.. 10(4). 209-219 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M. Kurihara, H. Sano, M. Murata, H. Nishihara: "Synthesis of a Vinylene-Bridged Ferrocene-Hydroquinone Complex and Its Unusual Structural Change Originated by Proton-Coupled Electron Transfer"Inorg. Chem.. 40(1). 4-5 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H. Nishihara: "Redox and Optical Properties of Conjugated Ferrocene Oligomers"Bull. Chem. Soc. Jpn. (Accounts). 74(1). 19-29 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M. Yamada, T. Tadera, K. Kubo, H. Nishihara: "Electroreductive Deposition of Anthraquinone Derivative-Attached Au Clusters: Optical Properties and STM Observation of the Electrodeposited Cluster Film"Langmuir. 17(8). 2363-2370 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y. Men, K. Kubo, M. Kurihara, H. Nishihara: "Syntheses of biferrocene dithiol and disulfide derivatives and their redox behavior in SAM with and without gold clusters on the gold substrate"Phys. Chem. Chem. Phys.. 3. 3427-3430 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S. Kume, M. Kurihara, H. Nishihara: "Reversible trans-cis photoisomerization of azobenzene-attached bipyridine ligands coordinated to cobalt using a single UV light source and the Co(III)/Co(II) redox change"Chem. Commun.. 2001(17). 1656-1657

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T. Yutaka, I. Mori, M. Kurihara, J. Mizutani, K. Kubo, S. Furusho, K. Matsumura, N. Tamai, H. Nishihara: "Synthesis, Characterization, and Photochemical Properties of Azobenzene- Conjugated Rh and Ru Bis(terpyridine) Complexes"Inorg. Chem.. 40(19). 4986-4995 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M. Nihei, M. Kurihara, J. Mizutani, H. Nishihara: "Photo- and Proton-coupled Isomerization of Novel Azo-conjugated Platinadithiolene Complex"Chem. Lett.. 2001(9). 852-853

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y. Yamada, J. Mizutani, M. Kurihara, H. Nishihara: "Synthesis of a New Bis(ferrocenyl)ruthenacyclopentatriene Compound with a Significant Inter-metal Electronic Communication"J. Organometal. Chem.. 637-639. 80-83 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M. Yamada, A. Kuzume, M. Kurihara, K. Kubo H. Nishihara: "Formation of a novel porphyrin - gold nanoparticle network film induced by infrared light irradiation"Chem. Commun.. 2476-2477 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M. Murata, M. Yamada, T. Fujita, K. Kojima, M. Kurihara, K. Kubo, Y. Kobayashi, H. Nishihara: "Structural Conversion and Spin Separation in Bis(ferrocenylethynyl)anthraquinones Triggered by Proton-Coupled Intramolecular Electron Transfer"J. Am. Chem. Soc.. 123(51). 12903-12904 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Nishiyama, A. Kubo, I. Taniguchi, M. Yamada, H. Nishihara: "Effects of Alkyl Chain as a Spacer on Electrochemical Reaction and SEIRA Spectra for Self-assembled Monolayers Having Anthraquinone Redox Center"Electrochemistry. 69(12). 980-983 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] I. Quiros, M. Yamada, K. Kubo, J. Mizutani, M. Kurihara, H. Nishihara: "Preparation of Alkyl Thiolate-Protected Palladium Nanoparticles and Their Size Dependence on Synthetic Conditions"Langmuir. (In press).

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M. Kurihara, H. Nishihara: "Azo- and quinone-conjugated redox complexes photo- and proton-coupled intramolecular reactions based on d-π interaction"Coord. Chem. Rev.. (In press).

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H. Nishihara: "Redox Chemistry and Functionalities of Conjugated Ferrocene Systems"Adv. Inorg. Chem.. (In press).

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 2003-09-17  

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