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 'neural soliton'.
|ジャーナル||Journal of macromolecular science. Chemistry|
|号||9 -11 pt 3|
|出版ステータス||Published - 1990 8|
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