X-ray crystal structure and doping mechanism of bimetallic nanocluster Au36−xCux(m-MBT)24 (x = 1–3). Issue 2 (11th December 2017)

• Record Type: Journal Article
• Authors: Rao, Bo; Zhao, Tong; Yang, Sha; Chai, Jinsong; Pan, Yiting; Weng, Shiyin; Yu, Haizhu; Li, Xiaowu; Zhu, Manzhou
• Is Part Of: Dalton transactions. Volume 47:Issue 2(2017)
• Page Start: 475
• Page End: 480
• Publication Date: 2017-12-11
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c7dt02959d
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Combined experimental and theoretical methods have been used to explore the doping preference of Cu atoms in novel Au36− x Cu x ( m -MBT)24 ( x = 1–3) nanoclusters. Abstract : A novel Au36− x Cu x ( m -MBT)24 ( x = 1–3, m -MBT = 3-methylbenzenethiolate) nanocluster has been prepared. According to the X-ray single crystal diffractometer, the structure of Au36− x Cu x ( m -MBT)24 is similar to that of Au36 (SPh t Bu)24 . The Au36− x Cu x ( m -MBT)24 nanocluster contains a face-centered cubic (FCC) M28 core, which is protected by 4 M2 S3 (M = Au/Cu) staple motifs and 12 bridging SR ligands. The Cu dopants could possibly occupy 14 sites (six in the sub-surface and eight in the staple motifs). Spectral monitoring indicates that the number of Cu dopants sequentially increased on increasing the amount of Cu precursors (relative to a Au control). Meanwhile, DFT calculations imply that the maximum doping number of Cu is 3, and doping occurs preferentially at the staple sites and sub-surface sites (instead of the centre of the core). Because the atomic orbital of the peripheral locations hardly contributes to the frontier molecular orbitals, the UV-vis of the AuCu alloy is almost the same as that of its homometallic Au counterpart.