Synthesis of poly(arylene cobaltacyclopentadienylene)s, a new class of organometallic π-conjugated polymers, by metallacycling polymerization and their physical properties

Tadashi Shimura, Akira Ohkubo, Nao Matsuda, Isao Matsuoka, Kunitsugu Aramaki, Hiroshi Nishihara

研究成果: Article査読

24 被引用数 (Scopus)

抄録

Reaction of Cp′Co(PPh3)2, where Cp′ = η5-cyclopentadienyl (Cp) or η5-n-hexylcyclopentadienyl (hexCp), with conjugated diacetylenes, RC≡C-A-C≡CR, where A = p-phenylene, p-fluorophenylene, p-2,5-difluorophenylene, or 4,4′-biphenylene and R = H or Me affords new organometallic polymers, [-C4R2{CoCp′(PPh3)}-A-]n (1-6) involving linearly π-conjugated chains. The polymers are insoluble when Cp′ = Cp but soluble in common organic solvents when Cp′ = hexCp. It is suggested by the results of reactions of (hexCp)Co(PPh3)2 with PhC≡CH and PhC≡CMe that stereoregularity favorable to π-conjugation, i.e., connection of cobaltacyclopentadienylene moieties at 2,5 position is higher when R = Me compared to when R = H. The cobaltacyclopentadiene polymers undergo quasi-reversible oxidation and irreversible reduction at low temperatures. The oxidation potential is not significantly changed, but the reduction potential shifts considerably in the positive direction for the polymers compared to monomeric cobaltacyclopentadienes. The polymers' bandgap energies (as estimated from visible spectra) are between 2.1 and 2.3 eV. Photoconductivity is observed for [-C4Me2{Co(hexCp)(PPh3)}-C6H 4-]n (6e).

本文言語English
ページ(範囲)1307-1315
ページ数9
ジャーナルChemistry of Materials
8
6
DOI
出版ステータスPublished - 1996 6月

ASJC Scopus subject areas

  • 化学一般
  • 化学工学一般
  • 材料化学

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