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Synthesis and Property of Dichroic Photochromism of Bipyridinium Bis(phosphonate)s

Research Project

Project/Area Number 12650696
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Structural/Functional materials
Research InstitutionUniversity of Yamanashi

Principal Investigator

NANASAWA Masato  University of Yamanashi, Faculty of Engineering, Professor, 工学部, 教授 (70020451)

Co-Investigator(Kenkyū-buntansha) KUWABARA Tetsuo  University of Yamanashi, Faculty of Engineering, Research Associate, 工学部, 助手 (70273034)
HIRAI Michiko  University of Yamanashi, Faculty of Engineering, Research Associate, 工学部, 助手 (00303397)
Project Period (FY) 2000 – 2002
Project Status Completed (Fiscal Year 2002)
Budget Amount *help
¥1,900,000 (Direct Cost: ¥1,900,000)
Fiscal Year 2002: ¥300,000 (Direct Cost: ¥300,000)
Fiscal Year 2001: ¥300,000 (Direct Cost: ¥300,000)
Fiscal Year 2000: ¥1,300,000 (Direct Cost: ¥1,300,000)
KeywordsViologene / Photo-reductive coloration / Photochromism / Dichroism / Alkanephosphonic acid / 光還元 / サーモクロミズム
Research Abstract

The viologens, bis-quaternary salts of 4,4'-bipyridine turn to intensive blue radical cations by one-electron by photochemical reaction. With the intention to evaluate the reversible photo-reduction(photochromism), the synthesis and dichroism of viologens with alkanephophonate anions which possess relatively good nucleophilicity and anisotrophic character was investigated. N,N'-dialkyl-4,4'-bipyridinium dihalides were prepared by two steps of Menshutkin reactions with different alkyl halides and their counter ions were exchanged with alkanephosphonates using an anion-exchange resin. ^1H-NMR and elemental analyses indicated that the viologens consist of two phosphonate anions, and protons at pyridinium rings are shifted to higher field, presumably due to low electrostatic interaction with bulky bivalent phophonate anions. This causes that the phosphonate salts are thermally unstable and decompose at relative low temperature without melting.
The radical formation by near-UV irradiation is small in organic solvents possessing high ionization potential. The photo-reduction in high-diluted solvents possessing electron-donating property (low IP) mainly proceeds by the ET-reaction from surrounding solvent molecules. The radical cations in glass sandwiched PVC-films were observed by steady state UV-irradiation, and the color of the radical cations persisted for several days. IR-spectra indicate that the photo-induced reduction of solid phosphonate salts proceeds from counter anion within a viologen molecule. When films were prepared by gradually cooling the melted viologen-bisphosphonate with alkanephosphonic acids, the absorption at 530 nm corresponds to the dimeric radical cation increased compared with rapidly cooling ones. While the absorption difference was small, the films of viologen-bisphosphonate salt showed dichroism by the orientation of viologen molecules in anisotropically organized alkanephosphonic acids.

Report

(4 results)
  • 2002 Annual Research Report   Final Research Report Summary
  • 2001 Annual Research Report
  • 2000 Annual Research Report

Research Products

(12 results)

All Other

All Publications (12 results)

  • [Publications] M.Hirai, T.Yuzawa, Y.Haramoto, M.Nanasawa: "Synthesis and photochromic behavior of methylmethacrylate copolymers having anils as pendant"Reactive and Functional Polymers. 45. 175-181 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Nanasawa, T.Tomoda, M.Hirai: "Syntheses and photochromic behavior of biquinolinium salts"Mol. Cryst. Liq. Cryst.. 344. 163-168 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Kuwabara, M.Sugiyama, M.Nanasawa: "Photochromism of viologens included crown ether cavity"Photochem. Photobiol.. 73. 469-472 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] 七澤真人: "ビオロゲン集合体の光還元発色"色材協会誌. 74. 298-302 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Nanasawa, N.Kosaki, T.Kaneko, M.Hirai: "Synthesis and Photo-induced Reduction of N, N'-Dialkylbipyridium Bis(alkanephosphonates)"Heterocyclic Commn. 9. 57-60 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M. Hirai, T. Yuzawa, Y. Haramoto, and M. Nanasawa: "Synthesis and Photochromic Behavior of Methylmethacrylate Copolymers Having Anils as Pendant"Reactive and Functional Polymers. 45. 175-181 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M. Nanasawa, T. Tomoda, and M. Hirai: "Syntheses and Photochromic Behavior of Biquinolinium Salts"Mol. Cryst. Liq. Cryst.. 344. 163-168 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T. Kuwabara, M. Sugiyama, M. Nanasawa: "Photochromism of Viologens Included Crown Ether Cavity"Photochem. Photobiol.. 73. 469-472 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M. Nanasawa: "Photoreductive Coloration of Viologen Assembly"J. Jpn. Colour Material. 74. 298-302 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M. Nanasawa, N. Kosaki, T. Kaneko, and M. Hirai: "Synthesis and Photo-induced Reduction of N,N'-Dialkylbipyridium Bis(alkanephosphonate)s"Heterocyclic Commn.. 9. 57-60 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Nanasawa et al.: "Synthesis and Photo-induced Reduction of N, N^1-Dialkylbipyridium Bis (alkanephosphonates)"Heterocyelic Commn.. (in press).

    • Related Report
      2002 Annual Research Report
  • [Publications] 七澤 真人: "ビオロゲン集合体の光還元発色"色材協会誌. 74(6). 298-302 (2001)

    • Related Report
      2001 Annual Research Report

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Published: 2000-03-31   Modified: 2016-04-21  

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