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The Interplay Between Conformation and Absolute Configuration in Chiral Electron Dynamics of Small Diols
Steven Daly1,2,3, Maurice Tia2,4, Gustavo A Garcia2
1School of Chemistry, University Park, University of Nottingham, Nottingham, NG7 2RD, UK.
Abstract:
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.
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