期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 -, 期 -, 页码 -出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202217620
关键词
Ab Initio Calculations; Femtochemisty; Fluorescence; Molecular Dynamics; Photophysics
The mechanism of reverse intersystem crossing (rISC) in metal-based TADF emitters is still not clear, as the small singlet/triplet energy gaps necessary for thermal rISC in donor-acceptor systems with charge-transfer excited states have spin-orbit couplings that are too small for effective rISC. In this study, the first nonadiabatic dynamics simulation of rISC process in a carbene-copper(I)-carbazolyl TADF emitter is reported. Efficient rISC on a picosecond time scale is demonstrated, involving an intermediate higher-lying triplet state of metal-to-ligand charge transfer character ((MLCT)-M-3) that enables large spin-orbit couplings with the lowest singlet charge transfer state. The mechanism is completed in the S-1 state where the complex can return to a co-planar coordination geometry with high fluorescence efficiency.
The mechanism behind reverse intersystem crossing (rISC) in metal-based TADF emitters is still under debate. Thermal rISC necessitates small singlet/triplet energy gaps as realized in donor-acceptor systems with charge-transfer excited states. However, their associated spin-orbit couplings are too small to account for effective rISC. Here, we report the first nonadiabatic dynamics simulation of the rISC process in a carbene-copper(I)-carbazolyl TADF emitter. Efficient rISC on a picosecond time scale is demonstrated for an initial triplet minimum geometry that exhibits a perpendicular orientation of the ligands. The dynamics involves an intermediate higher-lying triplet state of metal-to-ligand charge transfer character ((MLCT)-M-3), which enables large spin-orbit couplings with the lowest singlet charge transfer state. The mechanism is completed in the S-1 state, where the complex can return to a co-planar coordination geometry that presents high fluorescence efficiency.
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