A high-spin and helical organic polymer: Poly{[4-(dianisylaminium)phenyl] acetylene}

Hidenori Murata, Daisuke Miyajima, Hiroyuki Nishide

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Abstract

A high-spin polyradical, poly{[4-(dianisylaminium)phenyl]acetylene}1 +, was synthesized as a π-conjugated polymer with an excess of the one-handed helical structure bearing stable aminium cation radicals. [4-(Dianisylamino)phenyl]acetylene (3) was synthesized and polymerized using [Rh(norbornadiene)Cl]2 in (R)-l-phenylethylamine, (S)-1-phenylethylamine, or triethylamine to produce the corresponding poly{[4-(dianisy-lamino)phenyl]acetylene} 1 (1(R)-PEA, 1 (R)-PEA, and ITEA. The positive and negative Cotton effects were observed at 270-450 nm for the polymers 1(R)-PEA and 1(S)-PEA, indicating that an excess of the one-handed helical polyacetylene backbone was induced by the polymerization using chiral solvents despite the achiral monomer. The oxidation of 1 with NOPF6 gave the corresponding aminium polyradicals 1+, and the circular dichroism (CD) spectrum was observed even after the oxidation of the helical polyradical 1(R)-PEA +. The SQUID and NMR shift measurements indicated a high-spin state of the polyradical at room temperature and a contribution of the well-regulated helical structure to the through-space interaction between the aminium cation radicals.

Original languageEnglish
Pages (from-to)6331-6335
Number of pages5
JournalMacromolecules
Volume39
Issue number19
DOIs
Publication statusPublished - 2006 Sep 19

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ASJC Scopus subject areas

  • Materials Chemistry

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