PHOTOFRAGMENTATION IN LINKED DONOR-ACCEPTOR MOLECULES - INTRAMOLECULAR SINGLE-ELECTRON TRANSFER INDUCED CLEAVAGE OF A 1,2-DIAMINE

被引:27
作者
LEON, JW [1 ]
WHITTEN, DG [1 ]
机构
[1] UNIV ROCHESTER,DEPT CHEM,ROCHESTER,NY 14627
关键词
D O I
10.1021/ja00071a015
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Two intramolecular donor-acceptor molecules which fragment by a single electron transfer initiated cation radical carbon-carbon bond cleavage have been synthesized and their photoreactivity studied. The intramolecular ''diads'' consist of a 1,2- diamine linked via an ester bond to either an anthraquinone or a 9,10 dicyanoanthracene electron-acceptor chromophore. As the covalent linkage between the donor and acceptor chromophores prevents solvent separation of the photogenerated radical ion pair, these systems provide a ''clock'' to examine directly competition between fragmentation and back electron transfer. The linked anthraquinone molecule fragments efficiently, with quantum yields approaching 80%, despite the inability of the photoproduced radical ions to separate. These high yields may be attributed to a slow, spin-forbidden back electron transfer and a rapid fragmentation. In contrast, the quantum yields for the dicyanoanthracene diad (reactive singlet) are markedly lower, less than 0.001 in benzene. The reactivity of comparable intermolecular donor-acceptor combinations is also reported.
引用
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页码:8038 / 8043
页数:6
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