N,N-Bis(4-{5-[N,N-bis(4-methoxyphenyl)-N-yloammonio]-2-methylstyryl}phenyl)ammoniumyl Triradical

• Published in: Bulletin of the Chemical Society of Japan 2006-06, Vol.79 (6), p.953
• Main Authors: Fukuzaki, Eiji, Abe, Shigemoto, Nishide, Hiroyuki
• Format: Article
• Language: English
• ISSN: 0009-2673; 1348-0634

Hyperbranched poly[(4-methoxyphenyl-N-yloammonio)-1,2(or 4)-phenylenevinylene-1,2(or 4)-phenylene], obtained by the polycondensation of N-(4-methoxyphenyl)-N-(4-vinylphenyl)-3-bromo-4-vinylaniline and the subsequent oxidation, three-directionally satisfied the non-Kekulé-type π-conjugation and ferromagnetic connectivity of the unpaired electrons of triarylammoniumyl cationic radicals, and behaved as a high-spin organic polymer even at room temperature. The trimer model compound, N-(4-{5-[N,N-bis(4-methoxyphenyl)amino]-2-methylstyryl}-3-methylphenyl)-N-(4-{5-[N,N-bis(4-methoxyphenyl)amino]-2-methylstyryl}phenyl)-4-methoxyaniline, was synthesized from N-(4-methoxyphenyl)-N-(4-vinylphenyl)-3-methyl-4-vinylaniline. The corresponding ammoniumyl triradical displayed an average S (spin quantum number) value of 3/2, which supported the strong spin-coupling between the unpaired electrons of the ammoniumyl radicals through the π-conjugated and branched phenylenevinylene structure. Head-to-tail linkage and the branched structure of the polymer were also studied by a model reaction of N-(4-methoxyphenyl)-N-(4-vinylphenyl)-3-methyl-4-vinylaniline and bromobenzene.