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Organometallic chemistry of carbon allotropes: extension to two-dimensional systems and applications to highly functionalized systems.

Research Project

Project/Area Number 15350032
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Inorganic chemistry
Research InstitutionTokyo Institute of Technology

Principal Investigator

AKITA Munetaka  Tokyo Institute of Technology, Chemical Resources Labo., professor, 資源化学研究所, 教授 (50167839)

Co-Investigator(Kenkyū-buntansha) TAKAO Akiko  Tokyo Institute of Technology, Chemical Resources Labo., research assosiate, 資源化学研究所, 助手 (00345357)
Project Period (FY) 2003 – 2006
Project Status Completed (Fiscal Year 2006)
Budget Amount *help
¥15,000,000 (Direct Cost: ¥15,000,000)
Fiscal Year 2006: ¥3,200,000 (Direct Cost: ¥3,200,000)
Fiscal Year 2005: ¥3,100,000 (Direct Cost: ¥3,100,000)
Fiscal Year 2004: ¥3,100,000 (Direct Cost: ¥3,100,000)
Fiscal Year 2003: ¥5,600,000 (Direct Cost: ¥5,600,000)
Keywordsmolecular wire / molecular switch / iron complex / disproportionation consatnt / redox / molecular circuit / 多核錯体 / intervalence charge transfer band / π共役系 / 二次元炭素骨格 / 三次元炭素骨格 / 情報伝達 / 炭素集合体 / ビニリデン中間体 / ポリエン / ポリイン / 均化定数 / Intervalence Charge Transferバンド
Research Abstract

We have been studying organometallic chemistry of polynuclear species containing carbon allotropes. In this study our research activity was focused on development of higher dimensional and highly functional molecular wires, which are indispensable components of "molecular circuit"
1.Synthetic study of higher dimensional molecular wires
As the two- and three-dimensional skeletons, ethylene and cyclophane were chosen and the redox-active iron fragments were attached to the organic cores. We established that, if the bulky organometallic fragments were separated enough, the desired polynuclea species were prepared successfully. The obtained compounds were characterized spectroscopically and crystallographically, and their performances as molecular wires was characterized by means of the electrochemical methods.
The above-mentioned synthetic study also provided dinuclear complexes with endiyne bridges. Their performance as molecular wires can be tuned by the introduction of substituents on the olefinic moiety and, in the case of the aryl derivatives, the performance was superior to that of the polyyneduyl complex, which was regarded as the most efficient organometallic molecular wire.
2.Introduction of switching function
Introduction of switching function was examined. The photochromic dithienylethene (DTE) bridge was employed and the desired compound was obtained by the synthetic method via a vinylidene intermediated and characterized spectroscopically and crystallographically. The DTE complex showed photochromic behavior analogous to the organic counterparts and the ON/OFF ratio of the Kc values was as large as 39 and much larger than the previously reported molecular switches. Molecules containing pH-sensitive functional groups were also studied.
The above-mentioned obtained results will contribute to the development of the molecular circuit.

Report

(5 results)
  • 2006 Annual Research Report   Final Research Report Summary
  • 2005 Annual Research Report
  • 2004 Annual Research Report
  • 2003 Annual Research Report
  • Research Products

    (34 results)

All 2007 2006 2005 2004 2003 Other

All Journal Article (25 results) Book (4 results) Publications (5 results)

  • [Journal Article] C-C Coupling of Permetallated Ethene, (μ4-C=C)Ru_2(FeCp^*)_2(CO)_<10>, with Alkynes, and Isolation of Labile MeCN Adduct, (μ4-C=C)Ru_2(FeCp^*)_2(CO)_8(NCMe)_22007

    • Author(s)
      G.Higashihara, M.Terada, A.Inagaki, M.Akita
    • Journal Title

      Organometallics 26

      Pages: 439-444

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] A photoswitchable molecular wire with the dithienylethene (DTE) linker, (dppe)(η^5-C_5Me_5)Fe-C≡C-DTE-C≡C-Fe(η^5-C_5Me_5)(dppe).2007

    • Author(s)
      Y.Tanaka, A.Inagaki, M.Akita
    • Journal Title

      Chem. Commun.

      Pages: 1169-1171

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Annual Research Report 2006 Final Research Report Summary
  • [Journal Article] C-C Coupling of Permetallated Ethene, (μ_4-C=C)Ru_2(FeCp^*)_2- (C0)_<10>, with Alkynes, and Isolation of Labile MeCN Adduct, (μ_4-C=C)Ru_2(FeCp^*)_2(CO)_8(NCMe)_22007

    • Author(s)
      G.Higashihara, M.Terada, A.Inagaki, M.Akita
    • Journal Title

      Organometallics 26

      Pages: 439-444

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] A photoswitchable molecular wire with the dithienylethene (DTE) linker, (dppe)(η^5-C_5Me_5)Fe-C=C-DTE-C-Fe(η^5-C_5Me_5)(dppe).2007

    • Author(s)
      Y.Tanaka, A.Inagaki, M.Akita
    • Journal Title

      Chem.Commun.

      Pages: 1169-1171

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Polynuclear Iron Compounds with Hydrocarbyl Ligands2007

    • Author(s)
      Munetaka Akita
    • Journal Title

      comprehensive Organometallic Chemistry(Elsevier) III, Vol.6.08

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] C-C Coupling of Permetallated Ethene, (μ_4-C=C)Ru_2(FeCp^*)_2(CO)_<10>, with Alkynes, and Isolation of Labile MeCN Adduct, (μ_4C=C)Ru_2(FeCp^*)_2(CO)_8(NCMe)_22007

    • Author(s)
      G.Higashihara, M.Terada, A.Inagaki, M.Akita
    • Journal Title

      Organometallics 26

      Pages: 439-444

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Synthesis of a Series of Diiron Complexes Based on Tetraethynylethene Skeleton and Related C_6-Endiyne Spacers, (dppe)Cp^*Fe-C≡C-C(R)=C(R)-C≡C-FeCp^*(dppe) : Tunable Molecular Wires.2006

    • Author(s)
      M.Akita, Y.Tanaka, C.Naitoh, T.Ozawa, N.Hayashi, M.Takeshita, A.Inagaki, M.-C.Chung
    • Journal Title

      Organometallics 25

      Pages: 5261-5275

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Annual Research Report 2006 Final Research Report Summary
  • [Journal Article] Redox-active Polyiron Complexes with Tetra(ethynylphenyl)ethene and [2,2]Paracyclophane Spacers Containing Ethynylphenyl Units : Extension to Higher Dimensional Molecular Wires.2006

    • Author(s)
      Y.Tanaka, T.Ozawa, A.Inagaki, M.Akita
    • Journal Title

      Dalton Trans

      Pages: 928-933

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Annual Research Report 2006 Final Research Report Summary
  • [Journal Article] Synthesis of a Series of Diiron Complexes Based on Tetraethynylethene Skeleton and Related C_6-Endiyne Spacers, (dppe)Cp^*Fe-C=C- C(R)=C(R)-C=C-FeCp^*(dppe) : Tunable Molecular Wires.2006

    • Author(s)
      M.Akita, Y.Tanaka, C.Naitoh, T.Ozawa, N.Hayashi, M.Takeshita, A.Inagaki, M.-C.Chung
    • Journal Title

      Organometallics 25

      Pages: 5261-5275

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Redox-active Polyiron Complexes with Tetra(ethynylphenyl)ethene and [2,2]Paracyclophane Spacers Containing Ethynylphenyl Units : Extension to Higher Dimensional Molecular Wires.2006

    • Author(s)
      Y.Tanaka, T.Ozawa, A.Inagaki, M.Akita
    • Journal Title

      Dalton Trans.

      Pages: 928-933

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Electronic Coupling in Dimetallic Complexes with π-Conjugated Bridge2006

    • Author(s)
      M.-C.Chung, H.-G.Ahn, C.-H.Kwak, M.Akita
    • Journal Title

      J. Nanosci. Nanotech. 6

      Pages: 3347-3350

    • Related Report
      2006 Annual Research Report
  • [Journal Article] A New Method for the Conversion of Allyl Alcohol into π-Allyl Species Promoted by Nucleophilic Interaction with a CO Ligand2006

    • Author(s)
      C.Dubs, T.Yamamoto, A.Inagaki, M.Akita
    • Journal Title

      Chemical Communications (印刷中)

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Synthesis of a Library of Ir-Containing Dinuclear Complexes with Bridging PNNN and PNNP Ligands (BL), [LM(μ-BL)M'L']BF_4, 1.2006

    • Author(s)
      C.Dubs, T.Yamamoto, A.Inagaki, M.Akita
    • Journal Title

      Organometallics 25

      Pages: 1359-1367

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Synthesis of a Library of Ir-Containing Dinuclear Complexes with Bridging PNNN and PNNP Ligands (BL), [LM(μ-BL)M'L']BF_4, 2.2006

    • Author(s)
      C.Dubs, T.Yamamoto, A.Inagaki, M.Akita
    • Journal Title

      Organometallics 25

      Pages: 1368-1358

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Xenophilic Complexes Bearing a Tp^R Ligand, Tp^RM-M'L_n : The Two Metal Centers are Held Together not by Covalent Interaction but by Electrostatic Attraction.2005

    • Author(s)
      K.Uehara, S.Hikichi, A.Inagaki, M.Akita
    • Journal Title

      Chem.A Eur.J. 11

      Pages: 2788-2809

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Photochromic Behavior and Diastereomeric Isomerism in [(η^6-Spirobenzopyran)RuCp^*]PF_62005

    • Author(s)
      A.Moriuchi, K.Uchida, A.Inagaki, M.Akita
    • Journal Title

      Organometallics 24

      Pages: 6382-6192

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Polynuclear Rhodium Complexes with Dinucleating PNNP Ligand : Dynamic and Diverse M…M Interactions in [(μ-X)Rh2(PNNP)(CO)2]^<n+> and [(μ4-X)Rh4(PNNP)2(CO)4]^<n+>2005

    • Author(s)
      S.Tanaka, C.Dubs, A.Inagaki, M.Akita
    • Journal Title

      Organometallics 24

      Pages: 163-184

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Xenophilic Complexes Bearing a Tp^κ Ligand, Tp^κM-M'L_n : The Two Metal Centers are Held Together not by Covalent Interaction but by Electrostatic Attraction2005

    • Author(s)
      K.Uehara, S.Hikichi, A.Inagaki, M.Akita
    • Journal Title

      Chem.A Eur.J (印刷中)

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Tetrakis(trimethylsilylbutadiynyl)ethene, C18(SiMe3)4 : An Extended Two-dimensional π-Conjugated System Consisting of Eighteen Carbon Atoms2004

    • Author(s)
      T.Ozawa, M.Akita
    • Journal Title

      Chem. Lett. 33

      Pages: 1180-1181

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Tetrakis(trimethylsilylbutadiyny1)- ethene, C_<18>(SiMe_3)_4 : An Extended Two-dimensional π- Conjugated System Consisting of Eighteen Carbon Atoms2004

    • Author(s)
      T.Ozawa, M.Akita
    • Journal Title

      Chem Lett. 33

      Pages: 1180-1181

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Tetrakis(trimethylsilylbutadiynyl)ethene, C18(SiMe3)4 : An Extended Two-dimensional π-Conjugated System Consisting of Eighteen Carbon Atoms2004

    • Author(s)
      T.Ozawa, M.Akita
    • Journal Title

      Chem.Lett. 33

      Pages: 1180-1181

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Tetranuclear Complexes Based on Dynamic Metal-metal Linkage, [(μ_4-X)Rh_4(CO)4(PNNP)2]^<n+>[X/n=R-C=C/1(Acetylide),C_2/0(Dicarbide)]2004

    • Author(s)
      S.Tanaka, C.Dubs, A.Inagaki, M.Akita
    • Journal Title

      Organometallics 23

      Pages: 317-319

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Selective synthesis of isomeric heterodinuclear complexes with switched metal arrangements : Proton-induced reversible metal migration on an iridium complex with a novel dinucleating PNNN ligand2004

    • Author(s)
      C.Dubs, A.Inagaki, M.Akita
    • Journal Title

      Chem.Commun.

      Pages: 2760-2761

    • Related Report
      2004 Annual Research Report
  • [Journal Article] μ4-Dicarbyne Complex with a Dimetallacyclobutatriene Core : A New Binding Mode of C2 Species2003

    • Author(s)
      M.Terada, G.Higashihara, A.Inagaki, M.Akita
    • Journal Title

      Chem. Commun.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] μ4- Dicarbyne Complex with a Dimetallacyclobutatriene Core : A New Binding Mode of C_2 Species2003

    • Author(s)
      M.Terada, G.Higashihara, A.Inagaki, M.Akita
    • Journal Title

      Chem.Commun.

      Pages: 2984-2985

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Book] Polynuclear Iron Compounds with Hydrocarbyl Ligands (Vol. 6.08) in"Comprehensive Organometallic Chemistry III"2007

    • Author(s)
      Munetaka Akita
    • Total Pages
      34
    • Publisher
      Elsevier
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Book] Polynuclear Iron Compounds without Hydrocarbyl Ligands (Vol. 6.07) in" Comprehensive Organometallic Chemistry III"2007

    • Author(s)
      Munetaka Akita
    • Total Pages
      34
    • Publisher
      Elsevier
    • Related Report
      2006 Annual Research Report
  • [Book] Polynuclear Iron Compounds with Hydrocarbyl Ligands (Vol. 6.08) in" Comprehensive Organometallic Chemistry III"2007

    • Author(s)
      Munetaka Akita
    • Total Pages
      14
    • Publisher
      Elsevier
    • Related Report
      2006 Annual Research Report
  • [Book] Comprehensive Organometallic Chemistry III.2006

    • Author(s)
      Munetaka Akita
    • Publisher
      Elsevier(印刷中)
    • Related Report
      2005 Annual Research Report
  • [Publications] Masako Terada: "μ_4-Dicarbyne Complex with a Dimetallacyclobutatriene Core : A New Binding Mode of C_2 Species"Chemical Communications. 2984-2985 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Masako Terada: "Formal Hydrogenation of a Permetalated Ethene, (μ_4-C=C)Fe_2Ru_2Cp^*_2(CO)_8(dppm), via Successive Protonation-Hydride Reduction Leading to C_2H_n Cluster Compounds"Organometallics. 22. 355-364 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Shukichi Tanaka: "Tetranuclear Complexes Based on Dynamic Metal-metal Linkage, [(μ_4^-X)Rh_4(CO)_4(PNNP)_2]^<n+>[X/n=R-C≡C/1(Acetylide), C_2/0(Dicarbide)]"Organometallics. 23. 317-319 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] Masato Kujime: "Interaction of Hydroperoxopalladium Complexes, (Tp^R)(py)Pd-OOH, with Hydroxonickel and -cobalt Complexes, [(μ-OH)(MTpR')]_2(M=Ni, Co), Leading to Oxidative Dehydrogenation of the Saturated Hydrocarbyl Moiety in the Ancillary Ligand (Tp^<iPr2>)."Dalton Transactions. 23. 3506-3515 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Masato Kujime: "Conversion of a Hydroperoxo Complex, (TpiPr_2)(py)Pd-OOH, into a Cyclic Alkylperoxo Complex Catalyzed by Cu(II) Species"Chemistry Letters. 486-487 (2003)

    • Related Report
      2003 Annual Research Report

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Published: 2003-04-01   Modified: 2016-04-21  

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