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 Title: Intrinsic optical activity and environmental perturbations: solvation effects in chiral building blocks Author(s): Lemler, Paul M. Contributor(s): Vaccaro, Patrick Subject(s): Conformers, isomers, chirality, stereochemistry Abstract: The non-resonant interaction of electromagnetic radiation with an isotropic ensemble of chiral molecules, which causes the incident state of linear polarization to undergo a signed rotation, long has served as a metric for gauging the enantiomeric purity of asymmetric syntheses. While the underlying phenomenon of circular birefringence (CB) typically is probed in the condensed phase, recent advances in ultrasensitive circular-differential detection schemes, as exemplified by the techniques of Cavity Ring-Down Polarimetry (CRDP), have permitted the first quantitative analyses of such processes to be performed in rarefied media. Efforts to extend vapor-phase investigations of CB to new families of chiral substrates will be discussed, with particular emphasis directed towards the elucidation of intrinsic (e.g., solvent-free) properties and their mediation by environmental perturbations (e.g., solvation). Specific species targeted by this work will include the stereoselective building blocks phenylpropylene oxide and $\alpha$-methylbenzyl amine, both of which exhibit pronounced solvent-dependent changes in measured optical activity. The nature of chiroptical response in different environments will be highlighted, with quantum-chemical calculations serving to unravel the structural and electronic provenance of observed behavior. Issue Date: 2016-06-20 Publisher: International Symposium on Molecular Spectroscopy Genre: Conference Paper/Presentation Type: Text Language: En URI: http://hdl.handle.net/2142/91453 Rights Information: Copyright 2016 by the authors Date Available in IDEALS: 2016-08-22
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