Cis-Trans isomerisation of azobenzenes studied by laser-coupled NMR spectroscopy and DFT calculations

被引：44
|
作者：
Wazzan, Nuha A. [1 ]
Richardson, Patricia R. [1 ]
Jones, Anita C. [1 ]
机构：
[1] Univ Edinburgh, Sch Chem, Edinburgh EH9 3JJ, Midlothian, Scotland
来源：
PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES | 2010年 / 9卷 / 07期
关键词：
SUBSTITUTED AZOBENZENES; THERMAL-ISOMERIZATION; INVERSION MECHANISM; SOLVENT; DERIVATIVES; PHOTOISOMERIZATION; TEMPERATURE; ABSORPTION; LIGHT;
D O I：
10.1039/c0pp00056f
中图分类号：
Q5 [生物化学]; Q7 [分子生物学];
学科分类号：
071010 ; 081704 ;
摘要：
In a combined experimental and computational study of a group of para-substituted azobenzenes, the effects of substituents and solvent on the kinetics of thermal cis-to-trans isomerisation have been examined and the success of DFT calculations in predicting kinetic parameters assessed. Mono-substituted species are predicted to isomerise by inversion in both non-polar and polar solvent, whereas for push-pull azobenzenes the mechanism is predicted to change from inversion to rotation on going from non-polar to polar solvent. Computed free energies of activation qualitatively reproduce experimental trends but do not quantitatively predict the kinetics of cis-trans isomerisation. The polarisable continuum model of solvation fails to predict the experimentally observed influence of solvent on the entropy of activation.
引用
收藏
页码：968 / 974
页数：7
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