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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >DFT/TDDFT Study on the Sensing Mechanism of a Fluorescent Probe for Hydrogen Sulfide: Excited State Intramolecular Proton Transfer Coupled Twisted Intramolecular Charge Transfer
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DFT/TDDFT Study on the Sensing Mechanism of a Fluorescent Probe for Hydrogen Sulfide: Excited State Intramolecular Proton Transfer Coupled Twisted Intramolecular Charge Transfer

机译：DFT / TDDFT研究硫化氢荧光探针的传感机理：激发态分子内质子转移耦合扭曲的分子内电荷转移

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摘要

By using density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods, the sensing mechanism of a fluorescent probe 2-(2-hydroxyphenyl) benzothiazole (HBT) derivative HBTPP-S for hydrogen sulfide has been thoroughly studied. The thiolysis reaction has a moderate reaction barrier of 18.40 kcal mol(-1), which indicates that the hydrogen sulfide sensing process has a favorable response speed. Because of the nonradiative donor-excited photoinduced electron transfer (d-PET, fluorophore as the electron donor) from the excited HBTPP group to the electron-withdrawing 2,4-dinitrophenyl group, as well as the inhibition of the proton transfer (PT) and the excited state intramolecular proton transfer (ESIPT) process by 2,4-dinitrophenyl group, the probe HBTPP-S is essentially nonfluorescent. On the other hand, the added hydrogen sulfide induces the thiolysis of the 2,4-dinitrophenyl ether bond, and then the thiolysis product HBTPP comes into existence. The theoretically simulated potential energy surface demonstrates that without the electron-withdrawing 2,4-dinitrophenyl group, the thiolysis product HBTPP undergoes the excited state intramolecular proton transfer (ESIPT) coupled twisted intramolecular charge transfer (TICT) processes in the first excited state. The absence of the d-PET and the process mentioned above may explain the significant fluorescent turn-on response and large Stokes shift of the thiolysis product HBTPP.
机译：通过使用密度函数理论（DFT）和时间依赖性密度泛函理论（TDDFT）方法，已经彻底研究了荧光探针2-（2-羟基苯基）苯并噻唑（HBT）衍生物HBTPPP-S的感测机理。硫酸分解反应的中等反应屏障为18.40kcal摩尔（-1），表明硫化氢传感过程具有有利的反应速度。由于非辐射供体的光突出的电子转移（D-PET，荧光团），从激发的HBTPP组到吸电子的2,4-二硝基苯基，以及质子转移（PT）的抑制作用并且激发的状态分子内质子转移（ESIPT）工艺通过2,4-二硝基苯，探针HBTPP-S基本上是非荧光的。另一方面，添加的硫化氢诱导2,4-二硝基苯醚键的硫酸分解，然后将硫酸分解产物HBTPP存在。理论上模拟的电位能表面表明，没有吸电子的2,4-二硝基苯基，硫酸分解产物HBTPP经历激发状态分子内质子转移（ESIPT）耦合扭曲的扭曲分子内电荷转移（TICT）过程中的第一种激发态。不存在D-PET和上述方法可以解释硫酸分解产物HBTPP的显着荧光导数响应和大型斯托克斯偏移。

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