title: Deciphering Photoluminescence Dynamics and Reactivity of the Luminescent Metal-Metal-Bonded Excited State of a Binuclear Gold(I) Phosphine Complex Containing Open Coordination Sites.
abstract: 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 (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.
authors.affiliation: State Key Laboratory of Synthetic Chemistry, Institute of Molecular Functional Materials, Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong (P. R. China).|School of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen, 518060 (P. R. China).
authors.forename: Chensheng
authors.initials: C
authors.lastname: Ma
authors.affiliation: Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong (P. R. China).
authors.forename: Chris Tsz-Leung
authors.initials: CT
authors.lastname: Chan
authors.affiliation: State Key Laboratory of Synthetic Chemistry, Institute of Molecular Functional Materials, Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong (P. R. China).
authors.forename: Wai-Pong
authors.initials: WP
authors.lastname: To
authors.affiliation: Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong (P. R. China). wm.kwok@polyu.edu.hk.
authors.forename: Wai-Ming
authors.initials: WM
authors.lastname: Kwok
authors.affiliation: State Key Laboratory of Synthetic Chemistry, Institute of Molecular Functional Materials, Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong (P. R. China). cmche@hku.hk.|HKU Shenzhen Institute of Research and Innovation, Shenzhen 518053 (P. R. China). cmche@hku.hk.
authors.forename: Chi-Ming
authors.initials: CM
authors.lastname: Che
keywords: femtosecond time-resolved fluorescence; gold; photocleavage; substrate binding; transient absorption