Regioregular polythiophenl with pendant phenoxyl radicals

A new high-spin organic polymer

Makoto Miyasaka, Tomoko Yamazaki, Eishun Tsuchida, Hiroyuki Nishide

Research output: Contribution to journalArticle

49 Citations (Scopus)

Abstract

Poly[3-(3', 5'-di-tert-butyl-4'-acetoxyphenyl)thiophene] (la) was regioselectively synthesized via simple oxidative polymerization of 3-(3', 5'-di-ferf-butyl-4'-acetoxyphenyl)thiophene (2a) with ferric chloride. Head-to-tail content of la with a molecular weight of > 104 reached 96% by modulating both the polymerization conditions and the purification procedure of the polymer. Visible absorption and fluorescence maxima were bathochromically shifted for both la and poly[3-(3', 5'-di-tert-butyl-4'hydroxyphenyl)thiophene] (Ib), which suggests an extended, -r-conjugation, i.e., a regioregular structure. Redox of the phenolate and of the thiophene residue of Ib was observed reversibly and independently under alkaline conditions. The polyphenoxyl 1 derived from the oxidation of Ib showed an electrical conductivity of 10-5 S cm-1. The polyradical 1 satisfies both an alternant but non-Kekulé-type π-conjugation and ferromagnetic connectivity of the unpaired electrons of the pendant phenoxyls. 1 with a spin concentration of 0.3 spin/unit displayed a spin quantum number (S) value of 2/2 to %, indicating a highspin ground state and an intramolecular ferromagnetic spin coupling through the polythiophene backbone.

Original languageEnglish
Pages (from-to)8211-8217
Number of pages7
JournalMacromolecules
Volume33
Issue number22
Publication statusPublished - 2000

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Thiophenes
Organic polymers
Thiophene
Polymerization
Polymers
Ground state
Purification
Fluorescence
Molecular weight
Oxidation
phenoxy radical
Electrons

ASJC Scopus subject areas

  • Materials Chemistry

Cite this

Regioregular polythiophenl with pendant phenoxyl radicals : A new high-spin organic polymer. / Miyasaka, Makoto; Yamazaki, Tomoko; Tsuchida, Eishun; Nishide, Hiroyuki.

In: Macromolecules, Vol. 33, No. 22, 2000, p. 8211-8217.

Research output: Contribution to journalArticle

Miyasaka, M, Yamazaki, T, Tsuchida, E & Nishide, H 2000, 'Regioregular polythiophenl with pendant phenoxyl radicals: A new high-spin organic polymer', Macromolecules, vol. 33, no. 22, pp. 8211-8217.
Miyasaka, Makoto ; Yamazaki, Tomoko ; Tsuchida, Eishun ; Nishide, Hiroyuki. / Regioregular polythiophenl with pendant phenoxyl radicals : A new high-spin organic polymer. In: Macromolecules. 2000 ; Vol. 33, No. 22. pp. 8211-8217.
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