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Dalton Trans. 2016 Aug 9;45(32):12772-8. doi: 10.1039/c6dt02187e.

A homoleptic, all-alkynyl-stabilized highly luminescent Au8Ag8 cluster with a single crystal X-ray structure.

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Department of Chemistry, Renmin University of China, Beijing 100872, China.
Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
Department of Chemistry, Renmin University of China, Beijing 100872, China. and School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710119, China.


A homoleptic, all-alkynyl-stabilized [Au8Ag8(ArC[triple bond, length as m-dash]C)16] (1, Ar = 3,5-di-tert-butylphenyl) cluster was synthesized and characterized with a single crystal X-ray structure. Reactions of 3,5-di-tert-butyl-phenylacetylene with Ag(i) and Au(i) gave [Ag(ArC[triple bond, length as m-dash]C)]n and Au(PPh3)(ArC[triple bond, length as m-dash]C), respectively, where both have unusually high solubility in nonpolar organic solvents. In addition to drastically increased solubility, the two bulky tert-butyl substituents on the phenyl ring can confine the metal core to a certain size by preventing infinite aggregation of d(10) metals. This feature makes the isolation of an all-alkynyl-stabilized Au-Ag cluster possible. Complex 1 is intensely luminescent with a very high quantum yield of 0.67 in solution at room temperature. Theoretical studies offered valuable insights into the intriguing photophysical properties, and revealed the significant role of metal-alkynyl bond interactions and enhanced molecular rigidity provided by tert-butyl groups.


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