Journal
JOURNAL OF PHYSICAL CHEMISTRY A
Volume 118, Issue 45, Pages 10433-10447Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp504174t
Keywords
-
Funding
- NSF [CHE-1057481]
- Ohio Supercomputer Center
- Department of Chemistry, University of Cincinnati
- Natural Sciences Research Council of Canada (NSERC)
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1057481] Funding Source: National Science Foundation
Ask authors/readers for more resources
The irradiation of trans-vinylketones 1a-c yields the corresponding cis isomers 2a-c. Laser flash photolysis of 1a and 1b with 308 and 355 nm lasers results in their triplet ketones (T-1K of 1), which rearrange to form triplet 1,2-biradicals 3a and 3b, respectively, whereas irradiation with a 266 nm laser produces their cis-isomers through singlet reactivity. Time-resolved IR spectroscopy of 1a with 266 nm irradiation confirmed that 2a is formed within the laser pulse. In comparison, laser flash photolysis of 1c with a 308 nm laser showed only the formation of 2c through singlet reactivity. At cryogenic temperatures, the irradiation of 1 also resulted in 2. DFT calculations were used to aid in the characterization of the excited states and biradicals involved in the cis-trans isomerization and to support the mechanism for the cis-trans isomerization on the triplet surface.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available