Large solvation effect in the optical rotatory dispersion of norbornenone - PubMed (original) (raw)
. 2014 Jan 27;53(5):1386-9.
doi: 10.1002/anie.201306339. Epub 2013 Dec 16.
Affiliations
- PMID: 24375760
- DOI: 10.1002/anie.201306339
Large solvation effect in the optical rotatory dispersion of norbornenone
Priyanka Lahiri et al. Angew Chem Int Ed Engl. 2014.
Abstract
The anomalously large chiroptical response of (1R,4R)-norbornenone has been probed under complementary vapor-phase and solution-phase conditions to assess the putative roles of environmental perturbations. Measurements of the specific rotation for isolated (gas-phase) molecules could not be reproduced quantitatively by comprehensive quantum-chemical calculations based on density-functional or coupled-cluster levels of linear-response theory, which suggests that higher-order treatments may be needed to accurately predict such intrinsic behavior. A substantial, yet unexpected, dependence of the dispersive optical activity on the nature (phase) of the surrounding medium has been uncovered, with the venerable Lorentz local-field correction reproducing solvent-mediated trends in rotatory dispersion surprisingly well, whereas more modern polarizable continuum models for implicit solvation performed less satisfactorily.
Keywords: ab initio calculations; chirality; chiroptical spectroscopy; optical activity; solvent effects.
Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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