Magnetic properties of conjugated phenoxy polyradicals

Hiroyuki Nishide, Naoki Yoshioka, Eishun Tsuchida

研究成果: Article査読

4 被引用数 (Scopus)

抄録

Formation and magnetic properties of π-conjugated phenoxy radicals bearing a porphyrin macrocycle or a polyacetylenic backbone are described. Tetrakis(3,5-di-t-butyl-4-hydroxyphenyl)porphinatometals (7-M) [M = Zn(II), VO(II), and Cu(II)] were oxidized to give the corresponding stable monoradical and biradical. Magnetic properties of the radical species depend on the magnetic orbital of the central metal ion. ESR hfs structure reveals that the biradical for 7-Zn and - VO are in the triplet (S = 1) and quartet state (S = 3/2), respectively. Poly(3,5-di-t-butyl-4-hydroxyphenylacetylene) (8) and poly(p-ethynylphenylhydrogalvinoxyl) (9) with molecular weights of ~104 are characterized. ESR spectra with hyperfine structure for 8 indicate that the phenoxy radicals are conjugated with the polyacetylenic main chain over ~7 monomer units as a “neutral soliton.” Formed polyradicals for 8 and 9 are surprisingly stable, even in the solid state, due to resonance stabilization and/or steric effect of the conjugated main chain. An antiferromagnetic interaction is observed for oxidized 8 with a spin concentration above 10 mol%.

本文言語English
ページ(範囲)1261-1273
ページ数13
ジャーナルJournal of Macromolecular Science: Part A - Chemistry
27
9-11
DOI
出版ステータスPublished - 1990
外部発表はい

ASJC Scopus subject areas

  • 工学(全般)

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