期刊
JOURNAL OF PHYSICAL CHEMISTRY B
卷 118, 期 7, 页码 1891-1899出版社
AMER CHEMICAL SOC
DOI: 10.1021/jp4125205
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资金
- Japan Society for the Promotion of Science (JSPS) [24655015]
- Grants-in-Aid for Scientific Research [24655015] Funding Source: KAKEN
Spectral and kinetic behavior of thermal cis-to-trans isomerization of 4-aminoazobenzene (AAB) is examined in various solvents of different polarities. In contrast to azobenzene (AB), it is found the rate of thermal isomerization of AAB is highly dependent on solvent polarity. Accelerated rates are observed in polar solvents as compared to nonpolar solvents. Moreover, a decrease in the barrier height with an increase in medium polarity is observed. Our observations suggest that inversion is the preferred pathway in cis-to-trans thermal isomerization in a nonpolar medium; however, in a polar medium, the isomerization path deviates from the inversion route and rotational behavior is incorporated. Differences in the kinetics and in mechanisms of isomerization in different media are rationalized in terms of modulation in barrier height by polarity of the medium and solute-solvent interaction. It is found that kinetics as well as the mechanism of thermal isomerization in AAB is controlled by the polarity of the medium.
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