PHOTOPHYSICS OF LINKED DONOR-ACCEPTOR SYSTEMS - THROUGH-SPACE AND THROUGH-BOND INTERACTIONS

被引:36
作者
DESCHRYVER, FC
DECLERCQ, D
DEPAEMELAERE, S
HERMANS, E
ONKELINX, A
VERHOEVEN, JW
GELAN, J
机构
[1] LIMBURGS UNIV CENTRUM,DEPT SBM,B-3590 DIEPENBEEK,BELGIUM
[2] UNIV AMSTERDAM,ORGAN CHEM LAB,1018 WS AMSTERDAM,NETHERLANDS
关键词
D O I
10.1016/1010-6030(94)02001-9
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Possible competition between through-sigma-bond and through-space interaction on the one hand and between through-sigma- and through-pi-bond interaction on the other has been studied in flexibly and rigidly linked donor-acceptor systems. In a first part, pyrenyl-substituted donor-acceptor compounds were studied, where a permethylated oligosilane chain acts as a flexible spacer. The possible involvement of a sigma delocalized oligosilane chain in the electron transfer process is studied. Intramolecular electron transfer was observed from a permethylated hexasilane chain towards pyrene in the excited state. Through-space ground-state interactions were observed for the donor-acceptor substituted hexamethyl trisilane chain. In order to study the electron transfer process via through-sigma- and through-pi-bond interactions, rigid trichromophoric compounds in an A1-D-A2 configuration were studied. One of the acceptors is directly bound to the donor moiety, while the other acceptor is separated from the donor by a rigid spacer of three sigma bonds. The study of these compounds by means of absorption, stationary and time-resolved emission spectroscopy reveals a competition between the two possible electron transfer directions in one of the trichromophoric compounds.
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页码:171 / 179
页数:9
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