Bent polyynes: ring geometry studied by Raman and IR spectroscopy
Article first published online: 8 JUL 2011
Copyright © 2011 John Wiley & Sons, Ltd.
Journal of Raman Spectroscopy
Volume 43, Issue 1, pages 95–101, January 2012
How to Cite
Lucotti, A., Tommasini, M., Chalifoux, W. A., Fazzi, D., Zerbi, G. and Tykwinski, R. R. (2012), Bent polyynes: ring geometry studied by Raman and IR spectroscopy. J. Raman Spectrosc., 43: 95–101. doi: 10.1002/jrs.2992
- Issue published online: 27 JAN 2012
- Article first published online: 8 JUL 2011
- Manuscript Accepted: 18 APR 2011
- Manuscript Received: 24 MAR 2011
- Raman spectroscopy;
- IR spectroscopy;
- ring strain;
- density functional theory calculations
Infrared (IR) and Raman spectroscopy have been used to examine the vibrational characteristics of a series of three macrocyclic tetraynes in comparison with an acyclic analog. By changing the length of the alkyl tether of the macrocycles, varying degrees of bending of the tetrayne moiety can be achieved, and the joint use of IR and Raman spectroscopies provides an avenue to probe the impact of bending on the sp-chain. The spectroscopic data show a general trend toward decreasing activation of Raman bands in the IR spectra, and vice versa, as bending of the polyyne chain is decreased. Density functional theory calculations provide a detailed rationalization of the experimental observations. Copyright © 2011 John Wiley & Sons, Ltd.