Aggregation-induced emission spectra of triphenylamine salicylaldehyde derivatives via excited-state intramolecular proton transfer revealed by molecular spectral and dynamics simulations.
Aggregation-induced emission spectra of triphenylamine salicylaldehyde derivatives via excited-state intramolecular proton transfer revealed by molecular spectral and dynamics simulations.
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分子光谱和动力学模拟揭示了三苯胺水杨醛衍生物通过激发态分子内质子转移的聚集诱导发射光谱
DOI：
10.1039/d1ra07388e
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发表时间：
2021-11-17
期刊：
影响因子：
3.9
通讯作者：
Zhu, Chaoyuan
中科院分区：
文献类型：
--
作者：
Zhang, Qing;Li, Yuanyuan;Cao, Zexing;Zhu, Chaoyuan
在时间依赖密度泛函数理论的量子水平上，通过与混合量子力学/分子力学（QM/MM）相关的分子光谱和动力学模拟，研究了两种三苯胺水杨醛衍生物（即TS和TS- ome）的激发态质子转移（ESIPT）伴随的聚集诱导发射（AIE）光谱。模拟的发射光谱峰和Stokes位移与TS和TS- ome的实验结果吻合较好。此外，在聚集晶体状态下，TS和TS- ome单体的AIE光谱机制都与ESIPT过程有关，而TS- ome （TS）二聚体的AIE光谱机制则伴随着分子间电荷转移激发过程。此外，TS二聚体也促进了晶体中的AIE机制，使分子间电荷从一个单体转移到另一个单体。此外，TS二聚体还参与了晶体中分子间电荷从一个单体转移到另一个单体的AIE机制。另一方面，通过非绝热分子动力学模拟解释了TS和TS- ome单体在乙腈溶液中有和没有ESIPT过程的混合发射光谱。还简要地讨论了溶液中的发射光谱较弱，晶体中的发射光谱增强。本研究为高效AIE化合物的设计提供了一个很好的物理见解。
Aggregation-induced emission (AIE) spectra accompanied by excited state intramolecular proton transfer (ESIPT) for two triphenylamine salicylaldehyde derivatives (namely, TS and TS-OMe) are investigated by performing molecular spectral and dynamics simulations associated with the hybrid quantum mechanics/molecular mechanics (QM/MM) at the quantum level of the time-dependent density functional theory. The simulated emission spectral peaks and Stokes' shifts are in good agreement with the experimental results for both TS and TS-OMe. Furthermore, the AIE spectral mechanisms are well explained to be associated with the ESIPT processes for both TS and TS-OMe monomers in the aggregated crystal state, while the AIE spectra mechanism for the TS-OMe (TS) dimer is accompanied by intermolecular charge-transfer excitation process. Besides, the TS dimers also contributed to the AIE mechanisms in the crystal with the intermolecular charge-transfer from one monomer to another. In addition, the TS dimers are contributed to the AIE mechanisms in the crystal with the intermolecular charge-transfer from one monomer to another. On the other hand, simulated emission spectra for both the TS and TS-OMe monomers in acetonitrile solution are involved in mixed emission with and without the ESIPT process, as interpreted by nonadiabatic molecular dynamics simulation. It is also briefly addressed that the emission spectra in the solution are weak and enhanced in the crystal. The present study provides a great physical insight into the design of highly efficient AIE compounds.
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