Premium
Effect of chlorine substitution on triplet state structure of thioxanthone: A time‐resolved resonance Raman study
Author(s) -
Pandey Rishikesh,
Rajkumar Nagappan,
Umapathy Siva
Publication year - 2013
Publication title -
journal of raman spectroscopy
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.748
H-Index - 110
eISSN - 1097-4555
pISSN - 0377-0486
DOI - 10.1002/jrs.4189
Subject(s) - thioxanthone , chemistry , triplet state , flash photolysis , reactivity (psychology) , resonance (particle physics) , excited state , raman spectroscopy , photochemistry , substitution (logic) , density functional theory , chlorine , computational chemistry , molecule , reaction rate constant , kinetics , atomic physics , organic chemistry , optics , medicine , physics , alternative medicine , pathology , quantum mechanics , computer science , photopolymer , polymerization , programming language , polymer
Substitution plays an important role in determining the triplet state reactivity. In this paper, we have studied the effect of chlorine substitution on the triplet state structure and the reactivity of thioxanthone (TX). We have employed time‐resolved resonance Raman technique to understand the structure of the lowest triplet excited state of 2‐chlorothioxanthone (CTX). The experimental findings have been corroborated with the computational results using density functional theory. Akin to the parent compound (TX), coexistence of two lowest triplet states has been observed in case of CTX, which has been substantiated using resonant probe wavelength dependence study. The relative contribution of 3 n–π* to 3 π–π* to the equilibrated triplet state has been found to be more for CTX compared to TX suggesting increase in the triplet state reactivity after the substitution. The above observation has been further supported by the flash photolysis experiments. Copyright © 2013 John Wiley & Sons, Ltd.