The thermal cis-to-trans isomerization rate of various azobenzenes was followed by means of spectrophotometric and flash photolysis techniques. For para-donor/para′-acceptor-substituted azobenzenes such as 4-nitro-4′-dimethylaminoazobenzene, the rate was distinctly accelerated, the activation energy decreasing with the increase in the polarity of solvents. Introduction of substituents in para positions with respect to azo group increased the rate irrespective of substituent. The effect is additive and a Hammett-type equation holds. For 4-dimethylamino-and 4-nitroazobenzenes, while the 2-methyl group accelerated the rate, the 2′-methyl group did not. The results suggest that the isomerization proceeds via inversion mechanism and the rate is controlled mainly by the resonance stabilization in the coplanar transition state. The inversion center for asymmetric azobenzenes is discussed.
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