The Interplay Between Conformation and Absolute Configuration in Chiral Electron Dynamics of Small Diols

被引:13
作者
Daly, Steven [1 ,2 ,3 ]
Tia, Maurice [2 ,4 ]
Garcia, Gustavo A. [2 ]
Nahon, Laurent [2 ]
Powis, Ivan [1 ]
机构
[1] Univ Nottingham, Sch Chem, Univ Pk, Nottingham NG7 2RD, England
[2] Synchrotron SOLEIL, Orme Merisiers, St Aubin BP 48, F-91192 Gif Sur Yvette, France
[3] Univ Lyon 1, CNRS, Inst Lumiere Mat, UMR5306, F-69622 Villeurbanne, France
[4] Goethe Univ Frankfurt, Inst Kernphys, Max von Laue Str 1, D-60438 Frankfurt, Germany
关键词
absolute configuration; chirality; circular dichroism; 1; 3-propanediol; PHOTOELECTRON CIRCULAR-DICHROISM; SPECTROSCOPY; MOLECULES; RECOGNITION;
D O I
10.1002/anie.201603771
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A competition between chiral characteristics alternatively attributable to either conformation or to absolute configuration is identified. Circular dichroism associated with photoexcitation of the outer orbital of configurational enantiomers of 1,3- and 2,3-butanediols has been examined with a focus on the large changes in electron chiral asymmetry produced by different molecular conformations. Experimental gas-phase measurements offer support for the theoretical modeling of this chiroptical effect. A surprising prediction is that a conformationally produced pseudo-enantiomerism in 1,3-butanediol generates a chiral response in the frontier electron dynamics that outweighs the influence of the permanent configurational handedness established at the asymmetrically substituted carbon. Induced conformation, and specifically induced conformational chirality, may thus be a dominating factor in chiral molecular recognition in such systems.
引用
收藏
页码:11054 / 11058
页数:5
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