Picosecond Metal-to-Ligand Charge-Transfer Deactivation in Co(ppy)3 via Jahn–Teller Distortion

The excited-state dynamics of fac-Co­(ppy)3, where ppy = 2-[2-(pyridyl)­phenyl], are measured with femtosecond UV–vis transient absorption spectroscopy. The initial state is confirmed with spectroelectrochemistry to have significant metal-to-ligand charge transfer (MLCT) character, unlike other Co c...

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Bibliographic Details
Published in:Inorganic chemistry 2024-07, Vol.63 (30), p.13825-13830
Main Authors: Malme, Justin T., Weaver, Jenelle N., Girolami, Gregory S., Vura-Weis, Josh
Format: Article
Language:English
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Summary:The excited-state dynamics of fac-Co­(ppy)3, where ppy = 2-[2-(pyridyl)­phenyl], are measured with femtosecond UV–vis transient absorption spectroscopy. The initial state is confirmed with spectroelectrochemistry to have significant metal-to-ligand charge transfer (MLCT) character, unlike other Co complexes that generally have ligand-to-metal charge transfer or ligand-field transitions in this energy range. Ground-state recovery occurs in 8.65 ps in dichloromethane. Density functional theory calculations show that the MLCT state undergoes Jahn–Teller distortion and converts to a five-coordinate triplet metal-centered state in which one Co–N bond is broken. The results highlight a potential pitfall of heteroleptic bidentate ligands when designing strong-field ligands for transition-metal chromophores.
ISSN:0020-1669
1520-510X
1520-510X
DOI:10.1021/acs.inorgchem.4c01959