Isotopic and steric perturbations of 2E-chromium(III) excited state behavior in fluid solution: Evidence for a solvent mediated, strongly coupled quenching channel
✍ Scribed by John F. Endicott; R. Tamilarasan; Ronald B. Lessard
- Publisher
- Elsevier Science
- Year
- 1984
- Tongue
- English
- Weight
- 505 KB
- Volume
- 112
- Category
- Article
- ISSN
- 0009-2614
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✦ Synopsis
The lifetimes of the IOH es&energy excited state designated 'E, of chromium(II1) complexes in fluid solution decrease markedly with increasing temperatures near ambient conditions, but become nearly temperature independent at lower temperatures. The details of the temperature dependence are dependent on the medium and the solvent is implicated as a participant in the quenching process. Perdeuteration of coordinated amine (or a mmine) Jigands in Cr( [ 141 aneN4,) (CN): ([14] aneN = 1,4,8,11-tetraazacyclodecane) and Cr(NH&' results in increased lifetimes in ah the temperature re&res investigated. This implicates a substantial nuclear reorganizational barrier for the quenching process in fhrid solutions_ The most likely quenching channel in fluid solutions involves an adiabatic crossing from the excited state potential energy surface of a ground state reaction intermediate.