Pressure Dependence of the Forward and Backward Rates of 9-tert-Butylanthracene Dewar Isomerization

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• 作者：Fei Tong ; Chad D. Cruz ; Sebastian R. Jezowski ; Xiaoquan Zhou ; Lingyan Zhu ; Rabih O. Al-Kaysi ; Eric L. Chronister ; Christopher J. Bardeen
• 刊名：Journal of Physical Chemistry A
• 出版年：2014
• 出版时间：July 17, 2014
• 年：2014
• 卷：118
• 期：28
• 页码：5349-5354
• 全文大小：329K
• ISSN：1520-5215

文摘

9-tert-Butylanthracene undergoes a photochemical reaction to form its strained Dewar isomer, which thermally back-reacts to reform the original molecule. When 9-tert-butylanthracene is dissolved in a polymer host, we find that both the forward and reverse isomerization rates are pressure-dependent. The forward photoreaction rate, which reflects the sum of contributions from photoperoxidation and Dewar isomerization, decreases by a factor of 1000 at high pressure (1.5 GPa). The back-reaction rate, on the other hand, increases by a factor of 3 at high pressure. Despite being highly strained and higher volume, the back-reaction reaction rate of the Dewar isomer is at least 100脳 less sensitive to pressure than that of the bi(anthracene-9,10-dimethylene) photodimer studied previously by our group. These results suggest that the high pressure sensitivity of the bi(anthracene-9,10-dimethylene) photodimer reaction is not just due to the presence of strained four-membered rings but instead relies on the unique molecular geometry of this molecule.