KGaA, Weinheim. Luminescent metal complexes having open coordination sites hold promise in the design of sensory materials and photocatalysts. As a prototype example, [Au2(dcpm)2)]2+ (dcpm = bis(dicyclohexylphosphanyl) is known for its intriguing environmental sensitive photoluminescence. By integrating a range of complementary ultrafast time-resolved spectroscopy to interrogate the excited state dynamics, this study uncovers that the events occurring in extremely rapid timescales and which are modulated strongly by environmental conditions play a pivotal role in the luminescence behavior and photochemical outcomes. Formed independent of the phase and solvent property within 0.15 ps, the metal-metal bonded 35dσ6pσ state is highly reactive possessing strong propensity toward increasing coordination number at AuI center, and with 510 ps lifetime in dichloromethane is able to mediate light induced C-X bond cleavage.
- femtosecond time-resolved fluorescence
- substrate binding
- transient absorption
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