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A Rational Design for the Directed Helicity Change of Polyacetylene Using Dynamic Rotaxane Mobility by Means of Through‐Space Chirality Transfer
Author(s) -
Ishiwari Fumitaka,
Fukasawa Keiichiro,
Sato Takashi,
Nakazono Kazuko,
Koyama Yasuhito,
Takata Toshikazu
Publication year - 2011
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201101727
Subject(s) - chirality (physics) , rotaxane , polyacetylene , helix (gastropod) , chemistry , monomer , stereochemistry , side chain , polymer chemistry , polymer , molecule , organic chemistry , ecology , supramolecular chemistry , physics , chiral symmetry breaking , quantum mechanics , snail , nambu–jona lasinio model , biology , quark
Directed helicity control of a polyacetylene dynamic helix was achieved by hybridization with a rotaxane skeleton placed on the side chain. Rotaxane‐tethering phenylacetylene monomers were synthesized in good yields by the ester end‐capping of pseudorotaxanes that consisted of optically active crown ethers and sec ‐ammonium salts with an ethynyl benzoic acid. The monomers were polymerized with [{RhCl(nbd)} 2 ] (nbd=norbornadiene) to give the corresponding polyacetylenes in high yields. Polymers with optically active wheel components that are far from the main chain show no Cotton effect, thereby indicating the formation of racemic helices. Our proposal that N‐acylative neutralization of the sec ‐ammonium moieties of the side‐chain rotaxane moieties enables asymmetric induction of a one‐handed helix as the wheel components approach the main chain is strongly supported by observation of the Cotton effect around the main‐chain absorption region. A polyacetylene with a side‐chain rotaxane that has a shorter axle component shows a Cotton effect despite the ammonium structure of the side‐chain rotaxane moiety, thereby suggesting the importance of proximity between the wheel and the main chain for the formation of a one‐handed helix. Through‐space chirality induction in the present systems proved to be as powerful as through‐bond chirality induction for formation of a one‐handed helix, as demonstrated in an experiment using non‐rotaxane‐based polyacetylene that had an optically active binaphthyl group. The present protocol for controlling the helical structure of polyacetylene therefore provides the basis for the rational design of one‐handed helical polyacetylenes.