The interplay between conformation and absolute configuration in chiral electron dynamics of small diols
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...
| Main Authors: | , , , , |
|---|---|
| Format: | Article |
| Published: |
Wiley-VCH Verlag
2016
|
| Online Access: | https://eprints.nottingham.ac.uk/34135/ |
| _version_ | 1848794781439754240 |
|---|---|
| author | Daly, Stephen Tia, Maurice Garcia, Gustavo A. Nahon, Laurent Powis, Ivan |
| author_facet | Daly, Stephen Tia, Maurice Garcia, Gustavo A. Nahon, Laurent Powis, Ivan |
| author_sort | Daly, Stephen |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | 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 modelling of this chiroptical effect. A surprising prediction is that a conformationally produced pseudoenantiomerism in 1,3-butanediol generates a chiral response in the frontier electron dynamics that effectively 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. |
| first_indexed | 2025-11-14T19:21:39Z |
| format | Article |
| id | nottingham-34135 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| last_indexed | 2025-11-14T19:21:39Z |
| publishDate | 2016 |
| publisher | Wiley-VCH Verlag |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | nottingham-341352020-05-04T18:00:00Z https://eprints.nottingham.ac.uk/34135/ The interplay between conformation and absolute configuration in chiral electron dynamics of small diols Daly, Stephen Tia, Maurice Garcia, Gustavo A. Nahon, Laurent Powis, Ivan 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 modelling of this chiroptical effect. A surprising prediction is that a conformationally produced pseudoenantiomerism in 1,3-butanediol generates a chiral response in the frontier electron dynamics that effectively 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. Wiley-VCH Verlag 2016-07-22 Article PeerReviewed Daly, Stephen, Tia, Maurice, Garcia, Gustavo A., Nahon, Laurent and Powis, Ivan (2016) The interplay between conformation and absolute configuration in chiral electron dynamics of small diols. Angewandte Chemie International Edition . ISSN 1433-7851 http://onlinelibrary.wiley.com/doi/10.1002/anie.201603771/abstract doi:10.1002/anie.201603771 doi:10.1002/anie.201603771 |
| spellingShingle | Daly, Stephen Tia, Maurice Garcia, Gustavo A. Nahon, Laurent Powis, Ivan The interplay between conformation and absolute configuration in chiral electron dynamics of small diols |
| title | The interplay between conformation and absolute configuration in chiral electron dynamics of small diols |
| title_full | The interplay between conformation and absolute configuration in chiral electron dynamics of small diols |
| title_fullStr | The interplay between conformation and absolute configuration in chiral electron dynamics of small diols |
| title_full_unstemmed | The interplay between conformation and absolute configuration in chiral electron dynamics of small diols |
| title_short | The interplay between conformation and absolute configuration in chiral electron dynamics of small diols |
| title_sort | interplay between conformation and absolute configuration in chiral electron dynamics of small diols |
| url | https://eprints.nottingham.ac.uk/34135/ https://eprints.nottingham.ac.uk/34135/ https://eprints.nottingham.ac.uk/34135/ |