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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.

Author information

1
Department of Chemistry, Renmin University of China, Beijing 100872, China. ruicao@ruc.edu.cn.
2
Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China. chenh@iccas.ac.cn.
3
Department of Chemistry, Renmin University of China, Beijing 100872, China. ruicao@ruc.edu.cn and School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710119, China.

Abstract

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.

PMID:
27461071
DOI:
10.1039/c6dt02187e

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