A High-Spin and Durable Polyradical

Poly(4-diphenylaminium-1,2-phenylenevinylene)

Hidenori Murata, Masahiro Takahashi, Kazuaki Namba, Naoki Takahashi, Hiroyuki Nishide

Research output: Contribution to journalArticle

46 Citations (Scopus)

Abstract

A purely organic, high-spin, and durable polyradical molecule was synthesized: It is based on the non-Kekulé- and non-disjoint design of a φ-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.

Original languageEnglish
Pages (from-to)631-638
Number of pages8
JournalJournal of Organic Chemistry
Volume69
Issue number3
DOIs
Publication statusPublished - 2004 Feb 6

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phosphine
Crown Ethers
Palladium
Magnetic susceptibility
Ground state
Paramagnetic resonance
Magnetization
Nuclear magnetic resonance
Oxidation
Temperature
Catalysts
Molecules
Air
nitrosonium ion

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

A High-Spin and Durable Polyradical : Poly(4-diphenylaminium-1,2-phenylenevinylene). / Murata, Hidenori; Takahashi, Masahiro; Namba, Kazuaki; Takahashi, Naoki; Nishide, Hiroyuki.

In: Journal of Organic Chemistry, Vol. 69, No. 3, 06.02.2004, p. 631-638.

Research output: Contribution to journalArticle

Murata, Hidenori ; Takahashi, Masahiro ; Namba, Kazuaki ; Takahashi, Naoki ; Nishide, Hiroyuki. / A High-Spin and Durable Polyradical : Poly(4-diphenylaminium-1,2-phenylenevinylene). In: Journal of Organic Chemistry. 2004 ; Vol. 69, No. 3. pp. 631-638.
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