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8244804 
Journal Article 
Exciplex photophysics. 7. Steric effects in exciplex photophysics 
Cheung, ST; Ware, WR 
1983 
Journal of Physical Chemistry
ISSN: 0022-3654 
87 
466-473 
English 
The influence of steric interference with sandwich-type exciplex formation has been investigated by using mono-and di-tert-butyl substitution of N,N-dimethylaniline (DMA). Pyrene was the electron acceptor and studies were carried out with both steady-state and fluorescence lifetime techniques in hexane and tetrahydrofuran (THF). All the rate constants of the classical exciplex mechanism were determined along with temperature coefficients. It was found that the most significant effect of tert-butyl substitution was a substantial decrease in the process (AQ)* → A* + Q. Solvent effects, exciplex thermodynamics, and activation parameters are discussed for the unsubstituted and tert-butyl-substituted systems. © 1983 American Chemical Society.