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Ma C, Chan CT, To WP, et al. Deciphering Photoluminescence Dynamics and Reactivity of the Luminescent Metal-Metal-Bonded Excited State of a Binuclear Gold(I) Phosphine Complex Containing Open Coordination Sites. Chemistry. 2015;21(40):13888-93doi: 10.1002/chem.201503045.
Ma, C., Chan, C. T., To, W. P., Kwok, W. M., & Che, C. M. (2015). Deciphering Photoluminescence Dynamics and Reactivity of the Luminescent Metal-Metal-Bonded Excited State of a Binuclear Gold(I) Phosphine Complex Containing Open Coordination Sites. Chemistry (Weinheim an der Bergstrasse, Germany), 21(40), 13888-93. https://doi.org/10.1002/chem.201503045
Ma, Chensheng, et al. "Deciphering Photoluminescence Dynamics and Reactivity of the Luminescent Metal-Metal-Bonded Excited State of a Binuclear Gold(I) Phosphine Complex Containing Open Coordination Sites." Chemistry (Weinheim an der Bergstrasse, Germany) vol. 21,40 (2015): 13888-93. doi: https://doi.org/10.1002/chem.201503045
Ma C, Chan CT, To WP, Kwok WM, Che CM. Deciphering Photoluminescence Dynamics and Reactivity of the Luminescent Metal-Metal-Bonded Excited State of a Binuclear Gold(I) Phosphine Complex Containing Open Coordination Sites. Chemistry. 2015 Sep 28;21(40):13888-93. doi: 10.1002/chem.201503045. PMID: 26376326.
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Chemistry. 2015 Sep 28;21(40):13888-93. doi: 10.1002/chem.201503045.

Deciphering Photoluminescence Dynamics and Reactivity of the Luminescent Metal-Metal-Bonded Excited State of a Binuclear Gold(I) Phosphine Complex Containing Open Coordination Sites.

Chemistry (Weinheim an der Bergstrasse, Germany)

Chensheng Ma, Chris Tsz-Leung Chan, Wai-Pong To, Wai-Ming Kwok, Chi-Ming Che

Affiliations

  1. 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).
  2. School of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen, 518060 (P. R. China).
  3. Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong (P. R. China).
  4. Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong (P. R. China). [email protected].
  5. 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). [email protected].
  6. HKU Shenzhen Institute of Research and Innovation, Shenzhen 518053 (P. R. China). [email protected].

PMID: 26376326 DOI: 10.1002/chem.201503045

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.

© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Keywords: femtosecond time-resolved fluorescence; gold; photocleavage; substrate binding; transient absorption

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