Homoconjugation vs. Exciton Coupling in Chiral α,β-Unsaturated Bicyclo[3.3.1]nonane Dinitrile and Carboxylic Acids

Molecules

Gintautas Bagdžiūnas¹  Eugenijus Butkus¹ 

[1] Department of Organic Chemistry, Vilnius University, Naugarduko 24, 03225 Vilnius, Lithuania; E-Mails:

关键词: circular dichroism;    conformational analysis;    TD-DFT calculations;    transannular interactions;    homoconjugation;   

DOI  :  10.3390/molecules19079893

来源: mdpi

【 摘 要 】

The chiroptical properties of enantiomerically pure bicyclo[3.3.1]nona-2,6-diene-2,6-dicarbonitrile and related acids were studied by circular dichroism spectroscopy and theoretical computations. A consideration of the molecular structure of the synthesized difunctional compounds revealed that chromophores are predisposed to transannular through-space interaction due to a favourable conformation of the bicyclic skeleton and a rather small interchromophoric distance. Evidence for non-exciton-type coupling between the two acrylonitrile and acrylate moieties in 3 and 4, respectively, was obtained by chiroptical spectroscopy and DFT calculations.

【 授权许可】

CC BY   
© 2014 by the authors; licensee MDPI, Basel, Switzerland.