S1/S0 Potential Energy Surfaces Experience Different Types of Restricted Rotation: Restricted Z/ e Photoisomerization and E/ Z Thermoisomerization by an Out-of-Plane Benzyl Group or In-Plane m-Pyridinium Group?

Jun Jia Xu, Robert Sung, Kuangsen Sung

研究成果: Article同行評審

8 引文 斯高帕斯(Scopus)

摘要

Any method that can enhance the fluorescence of fluorophores is highly desirable. Fluorescence enhancement accomplished by restricted Z/E photoisomerization through intramolecular steric hindrance or relatively high bond order of a C?C double bond in a S1 excited state has rarely been studied. In this article, we used green fluorescent protein (GFP) chromophore analogues as a model to get new physical insights into the restricted Z/E photoisomerization and E/Z thermoisomerization phenomena. We found that the S1 and S0 potential energy surfaces (PESs) of the GFP chromophore analogues experience two dramatically different types of restricted rotation, and 2b can be a representative example. In its S1 PES, it is not the intramolecular steric hindrance between the out-of-plane benzyl group and the in-plane m-pyridinium group but the relatively high bond order of the I-bond in the S1 excited state of 2b that makes it have a higher barrier for the Z/E photoisomerization, a smaller Z/E photoisomerization quantum yield, and a higher fluorescence quantum yield. In its S0 PES, it is not the reduced bond order of the I-bond in the S0 ground state of 2b but the intramolecular steric hindrance between the out-of-plane benzyl group and the in-plane m-pyridinium group that makes it have an extra higher barrier for E/Z thermoisomerization and a much smaller E/Z thermoisomerization rate constant.

原文English
頁(從 - 到)4708-4716
頁數9
期刊Journal of Physical Chemistry A
123
發行號22
DOIs
出版狀態Published - 2019 6月 6

All Science Journal Classification (ASJC) codes

  • 物理與理論化學

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