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Photoexcited States in the Diimine Platinum(II) Metal Complex and the Stacking Interaction

Research Project

Project/Area Number 13640558
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Inorganic chemistry
Research InstitutionOsaka University

Principal Investigator

IKEDA Noriaki  Osaka University, Graduate School of Science, Associate Processor, 大学院・理学研究科, 助教授 (70176098)

Project Period (FY) 2001 – 2002
Project Status Completed (Fiscal Year 2002)
Budget Amount *help
¥1,100,000 (Direct Cost: ¥1,100,000)
Fiscal Year 2002: ¥1,100,000 (Direct Cost: ¥1,100,000)
KeywordsMetal Complex / Platinum(II) / Crystal Structure / Luminescence / Excimer / Polymorphism / Stacking / MO Calculation
Research Abstract

Emission behavior and polymorphism of Ipt(II)(dpphen)CN_2l (dpphen= 4,7-diphenyl-pheuanthroline) in the crystal has been studied. Two kinds of crystals (needle and plate types) of this compound were obtained by recrystallization from N,N-dimethylformamide (DMF), and show different emission behavior Needle crystal (Ipt(dpphen)(CN)_2l0.5H_2O). Shows triplet ligand centered (^3LC) emission around 500 nm, but plate crystal (Ipt(dpphen)(CN)_2l 0.5DMF) shows very broad red emission around 820 nm which is similar with excimer-like emission as observed in concentrated solution. Their X-ray crystal structures have been determined. In both crystal, the molecular planes are in stacking structure with a space-distance of 3.3-3.5A, which are close Pt-phen ring or phen-CN group overlapping sites, but there is no Pt-Pt interaction site. In the plate type crystal, there is no intermolecular phenanthrolines-overlapping site that seems to cause excimer interaction due to aromatic-ring overlap.
In order t … More o clarify a main interaction factor that brings excimer-like association in solution and in crystal, .the electronic structure calculation of the compound by the density functional theory (DFT) method also performed. The optimized strtrcture obtained by calculation was is good agreement with the crystal structure. The lowest excited state of the eomplex is the mixed state of ^3MLCT and ^3LC, and is complicated, because there are so many states with different contribution in ^3LC nature within narrow energy. To consider how the state energy changes with an environment or association/stacking, quantum-chemical calculation was performed by changing the dielectric constant of the surroundings of the compound. The interesting result that a contribution of ^3MCT in the lowest. Excited state become remarkable is the case of surrounding with lower dielectric constant have been obtained. This suggests the increase of CT structure accompanied by association ar stacking in the crystal, and is considered that the clue explaining an excimer-like emission. However, slight possibility of an impurity cannot be excluded. Less

Report

(3 results)
  • 2002 Annual Research Report   Final Research Report Summary
  • 2001 Annual Research Report
  • Research Products

    (14 results)

All Other

All Publications (14 results)

  • [Publications] H.Yonehara et al.: "Controlled Fabrication of Molecular-aligned Solid Films of Oxotitanium(IV)-phthalocyanine by Conventional Vacuum-deposition and Their Spectroscopic Behavior"Chem. Materials. 13. 1015-1022 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] H.D.Hossain et al.: "Syntheses, Spectroelectrochemistry and Photoinduced Electron-transfer Processes of Novel Ru and Os Dyad and Triad Complexes with Functionalized Diimide"Collect. Czech. Chem. Commun.. 66. 307-337 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Tsushima et al.: "Excitons and a Charge-Separated Pair in Thin Crystals of Oxotitanium(IV) phthalocyanine as Revealed by Femtosecond Time-Resolved Absorption and ・・・"J. Phys. Chem. A. 106. 2256-2264 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Tsushima et al.: "A Charge-Separated Pair in Thin Crystals of Oxotitanium(IV) phthalocyanine as Revealed by Femtosecond Time-Resolved Absorption"Coord Chem. Rev.. 229. 3-8 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] H.Yonehara, H.Etori, M.K.Engel, M.Tsushima, N.Ikeda, T. Ohno, and C.Pac: "Controlled Fabrication of Molecular-aligned solid Filmes of oxotitanium(IV)-phthalocyanine by Conventional Vacuum-depositioa and Their Spectroscopic Behavior."Chem. Materials. 13. 1015-1022 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Md. D. Hossain, M.Haga, B.Gholamkhass, K.Nozaki, M.Tsushima, N.Ikeda, and T.Ohno: "Syntheses, Spectroelectrochemistry and Photoindused Electron-transfer Processes of Novel Ru and Os Dyad and Triad Complexes with Functionalied Diirmde"Collect. Czech. Chem. Commun.. 66(2). 307-337 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Tsushima, Y.Motojima, N.Ikeda, H.Yonehara, H.Etori, C.Pac, and, T.Ohno: "Excitons and a Charge-Separated Pair in Thin Crystals of Oxotitanium(IV) phthaloyanine as Revesled by Femtosecond Time-Resolved Absorption and and Time-Correlated Single Photon Counting."J. Phys. Chem. A. 106(10). 2256-2264 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Tsushima, N.Ikeda, H.Yonehara, H.Etori, C.Pac, and T Ohno: "A Charge-Separated Pair in Thin Crystals of Oxotitanium(IV) phthalocyanine as Revealed by Femtosecond Time-Resolved Absorption."Coord. Chem. Rev.. 229(1-2). 3-8 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Tsushima et al.: "Excitons and a Charge-Separated Pair in Thin Crystals of Oxotitanium(IV) phthalocyanine as Revealed by Femotsecond Time-Resolved Absorption and ・・・"J. Phys. Chem. A. 106・10. 2256-2264 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] M.Tsushima et al.: "A Charge-Separated Pair in Thin Crystals of Oxotitanium(IV) phthalocyanine as Revealed by Femtosecond Time-Resolved Absorption"Coord. Chem. Rev.. 229・1-2. 3-8 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] H.Yonehara et al.: "Controlled Fabrication of Molecular-aligned Solid Films of Oxotitanium(IV)-phthalocyanine by Conventional Vacuum-deposition and Their Spectroscopic Behavior"Chem. Materials. 13・3. 1015-1022 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] H.D.Hossain et al.: "Syntheses, Spectroelectrochemistry and Photoinduced Electron-transfer Processe of Novel Ru and Os Dyad and Triad Complexes with Functionalized Diimide"Collect. Czech. Chem. Commun.. 66・2. 307-337 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] M.Tsushima et al.: "Excitons and a Charge-Separated Pair in Thin Crystals of Oxotitanium(IV)phthalocyanine as Revealed by Femtosecond Time-Resolved Absorption and …"J. Phys. Chem. A. 106・10. 2256-2264 (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] M.Tsushima et al.: "A Charge-Separated Pair in Thin Crystals of Oxotitanium(IV)phthalocyanine as Revealed by Femtosecond Time-Resolved Absorption"Coord. Chem. Rev.. (in press). (2002)

    • Related Report
      2001 Annual Research Report

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Published: 2002-04-01   Modified: 2016-04-21  

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