期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 13, 期 34, 页码 9572-9581出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200701008
关键词
dendrons; helical structures; polymers; self-assembly; supramolecular chemistry
The first example of a self-assembling phenylpropyl ether based dendronized polymer has been reported and its preferred helical handedness has been determined. Dendronized polymer poly(10) and its nondendritic analogue poly(8) are high-cis-content polyphenylacetylenes (PPAs) prepared by using (Rh(nbd)Cl](2)/NEt3 (nbd: 2,5-norbornadiene). Both polymers possess a stereocenter in their side chain, which selects a preferred helical handedness. Based on negative exciton chirality observed in the CD spectra of poly(10), we have designated this molecule as a right-handed helical polymer, which persists over a wide temperature range. Poly(10) self-organizes into both Phi(io)(h) and Phi(h) lattices in bulk. The Phi(io)(h)-to-Phi(h) transition is associated with thermoreversible cis-cisoidal to cis-transoidal isomerization of the helical PPA, accompanied by a dramatic decrease in the column diameter and a decrease in the pi-stacking correlation length along the column. A model for the right-handed helical dendronized PPA has been proposed wherein dendrons from adjacent column strata interdigitate to effectively fill space.
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