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THERMAL GENERATION OF ELECTRONICALLY EXCITED STATES BY α‐PEROXYLACTONES: ACTIVATION PARAMETERS AND EXCITATION YIELDS AS A FUNCTION OF α‐DEUTERATION*
Author(s) -
Adam Waldemar,
Yany Faris
Publication year - 1980
Publication title -
photochemistry and photobiology
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.818
H-Index - 131
eISSN - 1751-1097
pISSN - 0031-8655
DOI - 10.1111/j.1751-1097.1980.tb03716.x
Subject(s) - diradical , excited state , quantum yield , chemistry , chemiluminescence , photochemistry , yield (engineering) , singlet state , fluorescence , kinetic isotope effect , excitation , kinetics , molecule , ground state , atomic physics , materials science , organic chemistry , physics , quantum mechanics , deuterium , metallurgy
Abstract— The kinetics and the direct, the 9,10‐dibromo‐ (DBA) and the 9,10‐diphenylanthracene‐ (DPA) enhanced chemiluminescence of tert‐butyl α‐peroxylactone 1, with and without α‐deuteration, was investigated in order to probe the mechanism of direct chemiexcitation by these hyperenergetic molecules. The small secondary isotope effect on the rates and activation parameters suggests that a diradical mechanism is obtained. The partitioning of the diradical intermediate into excited vs ground state product and the yield of triplet excited product are moderately (ca. 5‐fold) increased by α‐deuteration, but the singlet yield is unaffected. A convenient and useful chemiluminescence method for the determination of fluorescence quantum yields has been developed.