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Deciphering Photoluminescence Dynamics and Reactivity of the Luminescent Metal–Metal‐Bonded Excited State of a Binuclear Gold(I) Phosphine Complex Containing Open Coordination Sites
Author(s) -
Ma Chensheng,
Chan Chris TszLeung,
To WaiPong,
Kwok WaiMing,
Che ChiMing
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201503045
Subject(s) - luminescence , photoluminescence , excited state , phosphine , photochemistry , metal , spectroscopy , dichloromethane , reactivity (psychology) , chemistry , chemical physics , materials science , solvent , optoelectronics , organic chemistry , catalysis , atomic physics , physics , medicine , alternative medicine , quantum mechanics , pathology
Luminescent metal complexes having open coordination sites hold promise in the design of sensory materials and photocatalysts. As a prototype example, [Au 2 (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 3 5dσ*6pσ state is highly reactive possessing strong propensity toward increasing coordination number at Au I center, and with ∼510 ps lifetime in dichloromethane is able to mediate light induced C–X bond cleavage.