Influence of ligand variation on the deactivation process of metal-to-ligand charge transfer excited states in quadruply bonded dimolybdenum complexes

文献信息

发布日期 2023-11-09
DOI 10.1039/D3CP03679K
影响因子 3.676
作者

Yuqing Shi, Juanjuan Li, Can Cui, Guanzhi Wu, Tao Cheng


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摘要

To explore the dynamics of metal-to-ligand charge transfer (MLCT) excited states involving covalently bonded dimetal units, a series of quadruply bonded dimolybdenum (Mo2) complexes, namely, [Mo2]-ph, [Mo2]-naph, and [Mo2]-anth, were synthesized and characterized. Our investigations reveal a non-radiative process associated with the deactivation of the MLCT state into a low-lying dimetal-centered triplet state (3Mo2-δδ*), resulting in the populated MLCT states in these molecular systems exhibiting either extremely weak emission or being non-emissive. The influence of ligand variation on the dynamics of MLCT states was examined using femtosecond transient absorption spectroscopy, with deactivation time constants determined to be 1.9 ps for [Mo2]-ph, 6.5 ps for [Mo2]-naph, and 49 ps for [Mo2]-anth. This electron transfer behaviour follows an inverse energy-gap law, contrary to the general guideline that applies to the decay of the MLCT state back to the electronic ground state. This result offers valuable insights into understanding the photochemical and photophysical properties of covalently bonded dimetal complexes.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
自引率: 10.3%
年发文量: 3036

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