PHOTOISOMERIZATION OF ARYLETHYLENES - EXPLORING THE SINGLET POTENTIAL-ENERGY SURFACE OF A PARTIALLY PLANAR, SPECIALLY STABILIZED COMPOUND

被引:7
作者
UDAYAKUMAR, BS
DEVADOSS, C
SCHUSTER, GB
机构
[1] Department of Chemistry, Roger Adams Laboratory, University of Illinois, Urbana
关键词
D O I
10.1021/j100136a011
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
A uniquely substituted tetraarylethylene was prepared and studied spectroscopically and photochemically. 9-Fluorenylidenetribenzocycloheptatriene (1) has a singlet lifetime of 4.1 ns at room temperature and fluorescence and transient absorption spectra that are independent of temperature and solvent. The fluorescence emission is assigned to the vertical (Franck-Condon) state. The relatively long lifetime of this state is a consequence of the barrier to planarization of the tribenzosuberenyl group. There are no photochemical reactions of 1 in cyclohexane, acetonitrile, or methanol solution. From the results it is clear that planarization of the groups on both ethylenic carbon atoms is required to facilitate rotation about this double bond. Further, the perpendicular excited state even in this highly stabilized example appears to be zwitterionic.
引用
收藏
页码:8713 / 8717
页数:5
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