FREE-ENERGY AND ENTROPY CHANGES IN VERTICAL AND NONVERTICAL TRIPLET ENERGY-TRANSFER PROCESSES BETWEEN RIGID AND NONRIGID MOLECULES - A LASER PHOTOLYSIS STUDY

被引:11
作者
ZHANG, D [1 ]
CLOSS, GL [1 ]
CHUNG, DD [1 ]
NORRIS, JR [1 ]
机构
[1] ARGONNE NATL LAB,DIV CHEM,ARGONNE,IL 60439
关键词
D O I
10.1021/ja00062a036
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The free energy and entropy changes associated with intermolecular triplet energy transfer (TT) processes were determined by direct measurement of the equilibrium constant using a laser flash photolysis technique. 10,10-Dimethylanthrone and 9,9-dimethylfluorene were synthesized and used as a 'rigid' donor and acceptor, respectively, in comparison with 4-methylbenzophenone, a ''nonrigid'' donor, and 4-methylbiphenyl, a ''nonrigid'' acceptor, in the TT reactions. Both the nonrigid donor and the nonrigid acceptor lose entropy while going from the twisted ground state to the planar triplet state. The DELTAS values for 4-methylbenzophenone and 4-methylbiphenyl are 0.5-1.0 and 2.5-3.0 gibbs/mol, respectively.
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页码:3670 / 3673
页数:4
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