Synthesis of Two‐Electron Bimetallic Cu–Ag and Cu–Au Clusters by using [Cu₁₃(S₂CNⁿBu₂)₆(C≡CPh)₄]⁺ as a Template

Abstract

Atomically precise Cu-rich bimetallic superatom clusters have been synthesized by adopting a galvanic exchange strategy. [Cu@Cu (S CN Bu ) (C≡CPh) ][CuCl ] (1) was used as a template to generate compositionally uniform clusters [M@Cu (S CN Bu ) (C≡CPh) ][CuCl ], where M=Ag (2), Au (3). Structures of 1, 2 and 3 were determined by single crystal X-ray diffraction and the results were supported by ESI-MS. The anatomies of clusters 1-3 are very similar, with a centred cuboctahedral cationic core that is surrounded by six di-butyldithiocarbamate (dtc) and four phenylacetylide ligands. The doped Ag and Au atoms were found to preferentially occupy the centre of the 13-atom cuboctahedral core. Experimental and theoretical analyses of the synthesized clusters revealed that both Ag and Au doping result in significant changes in cluster stability, optical characteristics and enhancement in luminescence properties.

Isolation and Structural Elucidation of 15‐Nuclear Copper Dihydride Clusters: An Intermediate in the Formation of a Two‐Electron Copper Superatom

“…This result implies that the Au@Cu 12 alloy is generated through formation of [Cu 13 {S 2 CN i Bu 2 } 6 (C 2 Ph) 4 ] + . [ 17 ]…”

Simple and Selective Synthesis of Copper‐Containing Metal Nanoclusters Using (PPh3)2CuBH4 as Reducing Agent

“…By this methodology, a series of Cu‐alloyed NCs have been prepared, including Au 12+ n Cu 32 ( n = 0, 2, 4, 6), [ 1o ] Au 2 Cu 6 , [ 9 ] Au 19 Cu 30 , [ 10 ] Ag 28 Cu 12 , [ 11 ] Au 21− x Cu x ( X = 0,1,2–5), [ 12 ] etc. The second strategy is metal exchange utilizing the reaction of the templated metal NCs with foreign metal atoms, [ 13 ] as exemplified by AuCu 12 , [ 14 ] Au 38 Cu [ 15 ] clusters ( B ). The third strategy is hydride‐induced transformation developed by Tsukuda and co‐workers, in which, (HPd@Au 8 ) + selectively grew into (HPd@Cu 2 Au 8 ) 3+ superatom by nucleophilic addition of two CuCl units ( C ).…”

Observation of Non‐FCC Copper in Alkynyl‐Protected Cu53Nanoclusters

“…Half of them are positioned between and bonded with the first AB layers, while the others are stapled to BC layers (Figure A, in blue). As mentioned, the recently reported Cu 0 NCs are characterized by their respective polyhedron kernels with one central 12‐fold coordinated Cu . In Cu 53 , there are 5 such atoms, shaping into a triangular bipyramid (Figure C).…”

“…Cu 25 H 22 (PPh 3 ) 12 Cl featuring a Cu 13 icosahedron core was first reported in 2015 . A Cu 13 cuboctahedron and Cu 20 NCs were also captured very recently . We have noticed that during the preparation of this work, another Cu 53 NC bearing core–shell structure was reported .…”