Photoelectron spectra and electronic structures of highly substituted polyenes

被引:9
作者
Rademacher, P
Kowski, K
Hopf, H
Klein, D
Klein, O
Suhrada, C
机构
[1] Univ Essen Gesamthsch, Inst Organ Chem, D-45117 Essen, Germany
[2] Tech Univ Carolo Wilhelmina Braunschweig, Inst Organ Chem, D-38106 Braunschweig, Germany
关键词
electronic structure; photoelectron spectroscopy; UV-Vis spectroscopy; MO calculations; conformational analysis;
D O I
10.1016/S0022-2860(01)00530-0
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
The electronic structures of the alpha,alpha,omega,omega -tetra-t-butyl substituted conjugated polyenes 1-6 have been investigated by UV photoelectron spectroscopy and quantum chemical calculations. The all-trans-hexatriene (1), octatetraene (2), decapentaene (3), and the tetradecaheptaene (4) have essentially planar polyene chromophores and accordingly their pi MOs are spread by about 3-5 eV. On the other hand, interaction of the double bonds is Limited in the moderately twisted cis-hexatriene (5) and the highly distorted cis-3,4-dimethylhexatriene (6). The first U-Vis absorption of alpha,alpha,omega,omega -tetra-t-butyl-polyenes with three to thirteen conjugated C=C double bonds is linearly correlated with the PM3 calculated HOMO-LUMO energy gap. (C) 2001 Elsevier Science B.V. All rights reserved.
引用
收藏
页码:11 / 18
页数:8
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