title: A homoleptic, all-alkynyl-stabilized highly luminescent Au8Ag8 cluster with a single crystal X-ray structure.
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.
authors.affiliation: Department of Chemistry, Renmin University of China, Beijing 100872, China. ruicao@ruc.edu.cn.
authors.forename: Rui
authors.initials: R
authors.lastname: Zhang
authors.affiliation: 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.
authors.forename: Chongyang
authors.initials: C
authors.lastname: Zhao
authors.affiliation: Department of Chemistry, Renmin University of China, Beijing 100872, China. ruicao@ruc.edu.cn.
authors.forename: Xiumin
authors.initials: X
authors.lastname: Li
authors.affiliation: Department of Chemistry, Renmin University of China, Beijing 100872, China. ruicao@ruc.edu.cn.
authors.forename: Zongyao
authors.initials: Z
authors.lastname: Zhang
authors.affiliation: Department of Chemistry, Renmin University of China, Beijing 100872, China. ruicao@ruc.edu.cn.
authors.forename: Xicheng
authors.initials: X
authors.lastname: Ai
authors.affiliation: 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.
authors.forename: Hui
authors.initials: H
authors.lastname: Chen
authors.affiliation: 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.
authors.forename: Rui
authors.initials: R
authors.lastname: Cao