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Novel Photochromism Using Thin Films of Ion-Pair Charce-Transfer Complexes

Research Project

Project/Area Number 01550629
Research Category

Grant-in-Aid for General Scientific Research (C)

Allocation TypeSingle-year Grants
Research Field 工業物理化学
Research InstitutionShizuoka University (1990)
Kyushu University (1989)

Principal Investigator

NAGAMURA Toshihiko  Shizuoka University, Research Institute of Electronics, Professor, 電子工学研究所, 教授 (90117200)

Project Period (FY) 1989 – 1990
Project Status Completed (Fiscal Year 1990)
Budget Amount *help
¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 1990: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1989: ¥1,500,000 (Direct Cost: ¥1,500,000)
KeywordsIon-Pair Charce-Transfer Complex / Polymer Films / Photochromism / Photoinduced Electron Transfer Reaction / Optical Memory / Langmuir-Blodgett Films / Polarized Absorption Spectrum / Optical Waveguide / 光レモリ- / 電荷移動錯体
Research Abstract

The following results were obtained from the present research on novel photochromism based on the photoinduced electron transfer and thermal reverse reactions.
1) Synthesis of ion-pair charge-transfer complexes
4, 4'-Bipyridinium ions with symmetrical and asymmetrical substituents at 1, 1'-positions and polymers containing 4, 4'-bipyridinium ions as part of the main chain were synthesized. High bulk and chemically stable tetrakis [3,5-bis (trifluoromethyl) phenly] borate was used to form salts with 4, 4'-b-bipyridinium ions, which showed specific ion-pair charge-transfer (CT) absorption.
2) Preparation of Langmuir-Blodgett films and polymer cast films
Monolayer properties of 4, 4'-bipyridinium ions with symmetrical and asymmetrical substituents were studied in mixtures with arachidic acid. Y-type Langmuir-Blodgett (LB) films with good quality were deposited. Very thin transparent polymer films were prepared by a casting method.
3) Novel photochromism upon excitation of ion-pair charge-trans … More fer band
Upon CT excitation of LB and polymer films in vacuo resulted in colour changes from pale yellow to blue due to the formation of 4, 4'-bipyridinium radical cations. The blue colour disappeared in dark reversibly with lifetimes depending on temperature and microenvironment, tau _<1/e> =4 h in LB and 72 h in polymer films at 20^゚C. The colour change was repeated for many times.
4) Molecular control of the orientation of 4, 4'-bipyridinium radical cations
Polarized absorption spectra were measured before and after irradiation of LB films. From polarization and incident angle dependences, it was demonstrated for the first time that the molecular orientation of 4, 4'-bipyridinium radical cations was controlled by the substituents.
5) Highly sensitive detection of colour changes by optical waveguide technique
About 150-fold increase of sensitivity was achieved by this technique using a He-Ne laser. Colour changes in ultra thin films (about 20 nm) cast on a glass optical waveguide were successfully observed.
6) Optical recording by cast films of polymeric 4, 4'-bipyridinium salts
The lifetime of blue state in polymer films were considerably longer than in LB films. It was demonstrated that the optically written state was kept without decay below 0^゚C and was erased at higher temperatures. Less

Report

(3 results)
  • 1990 Annual Research Report   Final Research Report Summary
  • 1989 Annual Research Report
  • Research Products

    (21 results)

All Other

All Publications (21 results)

  • [Publications] Toshihiko Nagamura: "Photoinduced electrochromism in monolayer assemblies of ionーpair chargeーtransfer complexes of 4,4'ーbipyridinium ions" Thin Solid Films. 179. 375-380 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Toshihiko Nagamura: "Persistent and reversible photoreduction of 4,4'ーbipyridinium ions via excitation of their chargeーtransfer complexes with tetrakisー【3,5ーbis(trifluoromethyl)phenyl】borate in the crystalline state" Berichte der BunsenーGesellschaft fur physikalische Chemie. 93. 1432-1436 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Toshihiko Nagamura: "Control of molecular orientation of 4,4'ーbipyridinium cation radicals in novel photochromic monolayer assemblies" Journal of Chemical Society,Chemical Communications. 703-704 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] 長村 利彦: "機能制御のデザインー単分子累積膜系の光機能とクロモフォアの配列制御" 機能物質科学研究所報告. 3. 217-227 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Toshihiko Nagamura: "Novel photochromic polymer films containing ionーpair chargeーtransfer complexes of 4,4'ーbipyridinium ions for optical recording" Journal of Chemical Society,Chemical Communications. 72-74 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Toshihiko Nagamura: "Optical data storage by novel photoelectrochromic polymer" Polymer International.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Toshihiko Nagamura: "Photoinduced electrochromism in monolayer assemblies of charge-transfer complexes of 4, 4'-bipyridinium ions" Thin Solid Films. 179. 375-380 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Toshihiko Nagamura: "Persistent and reversible photoreduction of 4, 4'-bipyridinium ions via excitation of their charge-transfer complexes with tetrakis [3, 5-bis (trifluoromethyl) phenyl] borate in the crystalline state" Berichte der Bunsen-Gesellschaft fur physikalische Chemie. 93. 1432-1436 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Toshihiko Nagamura: "Control of molecular orientation of 4, 4'-bipyridinium cation radicals in novel potochromic monolayer assemblies" Journal of Chemical Society, Chemical Communications. 703-704 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Toshihiko Nagamura: "Molecular design for controlling functionality-photochemical properties of ordered chromophores in monolayer assemblies" The Reports of Institute of Advanced Material Study Kyushu University. 3. 217-227 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Toshihiko Nagamura: "Novel photochromic polymer films containing ion-pair charge-transfer complexes of 4, 4'-bipyridinium ions for optical recording" Journal of Chemical Society, Chemical Communications. 72-74 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Toshihiko Nagamura: "Optical data storage by novel photoelectrochromic polymer" Polymer International.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Toshihiko Nagamura: "Photoinduced electrochromism in monolayer assemblies of ionーpair chargeーtransfer complexes of 4,4'ーbipyridinium ions" Thin Solid Films. 179. 375-380 (1989)

    • Related Report
      1990 Annual Research Report
  • [Publications] Toshihiko Nagamura: "Persistent and reversible photoreduction of 4,4'ーbipyridinium ions via excitation of their chargeーtransfer complexes with tetrakisー[3,5ーbis(trifluoromethyl)phenyl]borate in the crystalline state" Berichte der BunsenーGesellschaft fu^^‥r physikalische Chemie. 93. 1432-1436 (1989)

    • Related Report
      1990 Annual Research Report
  • [Publications] Toshihiko Nagamura: "Control of molecular orientation 4,4'ーbipyridinium cation radicals in novel photochromic monolayer assemblies" Journal of Chemical Society,Chemical Communications. 703-704 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] 長村 利彦: "機能制御のデザインー単分子累積膜系の光機能とクロモフォアの配列制御" 機能物質科学研究所報告. 3. 217-227 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] Toshihiko Nagamura: "Novel photochromic polymer films containing ionーpair chargeーtransfer complexes of 4,4'ーbipyridinium ions for optical recording" Journal of Chemical Society,Chemical Communications. 72-74 (1991)

    • Related Report
      1990 Annual Research Report
  • [Publications] Toshihiko Nagamura: "Optical data storage by novel photoelectrochromic polymer" Polymer International.

    • Related Report
      1990 Annual Research Report
  • [Publications] Toshihiko Nagamura: "Control of Molecular orientation of 4,4'-bipyridinium cation radicals in novel photochromic monolayer assemblies" Journal of Chemical Society,Chemical Communications.

    • Related Report
      1989 Annual Research Report
  • [Publications] Toshihiko Nagamura: "Persistent and reversible photoreduction of 4,4'-bipyridinium ions via excitation of their charge-transfer complexes with tetrakis[3,5-bis(trifluoromethyl)phenyl]borate in the crystalline state" Berichte der Bunsen-Gesellscahft fur physikalische Chemie. 93. 1432-1436 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] Toshihiko Nagamura: "Photoinduced electrochromism in monolayer assemblies of ion-pair charge-transfer complexes of 4,4'-bipyridinium ions" Thin Solid Films. 179. 375-380 (1989)

    • Related Report
      1989 Annual Research Report

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Published: 1989-04-01   Modified: 2016-04-21  

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