Journal
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 22, Issue 46, Pages 27280-27289Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/d0cp03608k
Keywords
-
Funding
- CONICET
- FONCyT
- SeCyT-UNC
- CNRS (INSIS)
- ANR Research Grant [ANR2010BLANC040501-ESPEM, ANR17CE05000502-Wsplit]
- Chiang Mai University, Campus France
- PHC SIAM exchange program
Ask authors/readers for more resources
We present a study of the photofragmentation of three protonated azaindole molecules - 7-azaindole, 6-azaindole, and 5-azaindole - consisting of fused pyrrole-pyridine bicyclic aromatic systems, in which the pyridinic (protonated) nitrogen heteroatom is located at the 7, 6, and 5 positions, respectively. Photofragmentation electronic spectra of the isolated aforementioned azaindolinium cations reveal that their photodynamics extends over timescales covering nine orders of magnitude and provide evidence about the resultant fragmentation pathways. Moreover, we show how the position of the heteroatom in the aromatic skeleton influences the excited state energetics, fragmentation pathways, and fragmentation timescales. Computed ab initio adiabatic transition energies are used to assist the assignation of the spectra, while geometry optimisation in the excited electronic states as well as ab initio calculations along the potential surfaces demonstrate the role of pi pi*/pi sigma* coupling and/or large geometry changes in the dynamics of these species. Evidence supporting the formation of Dewar valence isomers as intermediates involved in sub-picosecond relaxation processes is discussed.
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