A High-Spin and Durable Polyradical:  Poly(4-diphenylaminium-1,2-phenylenevinylene)

A purely organic, high-spin, and durable polyradical molecule was synthesized:  It is based on the non-Kekulé- and non-disjoint design of a π-conjugated poly(1,2-phenylenevinylene) backbone pendantly 4-substituted with multiple robust arylaminium radicals. 4-N,N-Bis(4-methoxy- and -tert-butylphenyl)...

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Bibliographic Details
Published in:Journal of organic chemistry 2004-02, Vol.69 (3), p.631-638
Main Authors: Murata, Hidenori, Takahashi, Masahiro, Namba, Kazuaki, Takahashi, Naoki, Nishide, Hiroyuki
Format: Article
Language:English
Subjects:
Chemistry
Exact sciences and technology
Free radicals chemistry
Organic chemistry
Reactivity and mechanisms
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Summary:A purely organic, high-spin, and durable polyradical molecule was synthesized:  It is based on the non-Kekulé- and non-disjoint design of a π-conjugated poly(1,2-phenylenevinylene) backbone pendantly 4-substituted with multiple robust arylaminium radicals. 4-N,N-Bis(4-methoxy- and -tert-butylphenyl)amino-2-bromostyrene 5 were synthesized and polymerized with a palladium−phosphine catalyst to afford the head-to-tail-linked polyradical precursors (1). Oxidation of 1 with the nitrosonium ion solubilized with a crown ether gave the aminium polyradicals (1 + ) which were durable (half-life > 1 month) at room temperature in air. A high-spin ground state with an average S = (4.5)/2 for 1a + was proved even at room temperature by magnetic susceptibility, magnetization, ESR, and NMR measurements.
ISSN:0022-3263
1520-6904
DOI:10.1021/jo0302758