Remarkable effects of terminal groups and solvents on helical folding of o-phenylene oligomers.
Identifieur interne : 002238 ( Main/Merge ); précédent : 002237; suivant : 002239Remarkable effects of terminal groups and solvents on helical folding of o-phenylene oligomers.
Auteurs : Shinji Ando [Japon] ; Eisuke Ohta ; Atsuko Kosaka ; Daisuke Hashizume ; Hiroyuki Koshino ; Takanori Fukushima ; Takuzo AidaSource :
- Journal of the American Chemical Society [ 1520-5126 ] ; 2012.
Abstract
Although o-phenylene oligomers (OP(n)R) made of dimethoxyphenylene units are thought to be intrinsically dynamic due to π-electronic repulsion, we show that they fold into a regular helical geometry in CH(3)CN when they carry terminal groups such as CH(3), CH(2)OH, Br, CO(2)Bn, and NO(2). We evaluated their helical inversion kinetics via optical resolution of long-chain oligomers (e.g. 16- and 24-mers) by chiral HPLC. OP(24)Br at 298 K shows a half-life for the optical activity of 5.5 h in CH(3)OH/water (7/3 v/v) and requires 34 h for complete racemization. The perfectly folded helical conformers of OP(n)R, unlike their imperfectly folded ones, are devoid of extended π-conjugation and show a cyclic voltammogram featuring reversible multistep oxidation waves.
DOI: 10.1021/ja303117z
PubMed: 22709395
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We evaluated their helical inversion kinetics via optical resolution of long-chain oligomers (e.g. 16- and 24-mers) by chiral HPLC. OP(24)Br at 298 K shows a half-life for the optical activity of 5.5 h in CH(3)OH/water (7/3 v/v) and requires 34 h for complete racemization. The perfectly folded helical conformers of OP(n)R, unlike their imperfectly folded ones, are devoid of extended π-conjugation and show a cyclic voltammogram featuring reversible multistep oxidation waves.</div></front></TEI></record>Pour manipuler ce document sous Unix (Dilib)
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