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Unraveling the Mechanism for Tuning the Fluorescence of Fluorescein Derivatives: The Role of the Conical Intersection and nπ* State
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2021-07-09 , DOI: 10.1021/acs.jpclett.1c01774 Panwang Zhou 1 , Zhe Tang 1 , Peng Li , Jianyong Liu 2
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2021-07-09 , DOI: 10.1021/acs.jpclett.1c01774 Panwang Zhou 1 , Zhe Tang 1 , Peng Li , Jianyong Liu 2
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Although a large number of fluorescein derivatives have been developed and applied in many different fields, the general mechanisms for tuning the fluorescence of fluorescein derivatives still remain uncovered. Herein, we found that the fluorescence quenching of neutral form of fluorescein derivatives in acidic medium resulted from a dark nπ* state, whereas the fluorescence of the anionic form of fluorescein derivatives in the gas phase and alkaline solutions was tuned by minimal energy conical intersection (MECI). The formation of MECI involved significant rotation of benzene ring and flip-flop motion of xanthene moiety, which would be restricted by intermolecular hydrogen bonding and lowering temperature. The energy barrier for reaching MECI depended on the substituents in the benzene moiety in accordance with experimentally observed substituent effects. These unprecedented mechanisms would lead to a recognition of fluorescein derivatives and could provide a correct and instructive design strategy for further developing new fluorescein derivatives.
中文翻译：
揭示荧光素衍生物荧光的调节机制：圆锥交点和 nπ* 状态的作用
尽管已经开发了大量荧光素衍生物并应用于许多不同的领域，但调节荧光素衍生物荧光的一般机制仍未得到揭示。在此，我们发现酸性介质中中性形式的荧光素衍生物的荧光猝灭是由暗 nπ* 状态引起的，而气相和碱性溶液中阴离子形式的荧光素衍生物的荧光是通过最小能量锥形相交来调节的。 MECI）。MECI的形成涉及苯环的显着旋转和呫吨部分的翻转运动，这将受到分子间氢键和降低温度的限制。根据实验观察到的取代基效应，达到 MECI 的能垒取决于苯部分中的取代基。这些前所未有的机制将导致对荧光素衍生物的认识，并可以为进一步开发新的荧光素衍生物提供正确和有指导意义的设计策略。
更新日期：2021-07-22
中文翻译：
揭示荧光素衍生物荧光的调节机制：圆锥交点和 nπ* 状态的作用
尽管已经开发了大量荧光素衍生物并应用于许多不同的领域，但调节荧光素衍生物荧光的一般机制仍未得到揭示。在此，我们发现酸性介质中中性形式的荧光素衍生物的荧光猝灭是由暗 nπ* 状态引起的，而气相和碱性溶液中阴离子形式的荧光素衍生物的荧光是通过最小能量锥形相交来调节的。 MECI）。MECI的形成涉及苯环的显着旋转和呫吨部分的翻转运动，这将受到分子间氢键和降低温度的限制。根据实验观察到的取代基效应，达到 MECI 的能垒取决于苯部分中的取代基。这些前所未有的机制将导致对荧光素衍生物的认识，并可以为进一步开发新的荧光素衍生物提供正确和有指导意义的设计策略。
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