Synthesis, structural studies, and photophysical properties of heteroleptic inverse-coordination clusters

Abstract

Two series of hyper-coordinated halide-centered M12 cuboctahedral clusters, [M12(μ12-X){S2P(OnPr)2}6{C≡CPh}4](PF6), 1a-c and 2a-c (where M = Cu, 1; Ag, 2; X = Cl, a; Br, b; I, c), were synthesized and...

Recent progress in dichalcophosphate coinage metal clusters and superatoms

“…More recently, the halide-templating approach was used for the construction of new clusters [M 12 (μ 12 -X){S 2 P(OPr) 2 } 6 {C ≡ CPh} 4 ](PF 6 ) (M = Cu and Ag; X = Cl, Br, and I), revealing a similar cuboctahedral M 12 cage with a hypercoordinated halide anion in the centre. 128 Interestingly, the change of a halide does not affect the absorption spectra, and slightly impacts emission maxima within both Cu 12 and Ag 12 series. It should be remarked that the Ag 12 (μ 12 -Br) pattern is unprecedented, and μ 12 -X coordination is overall very uncommon in the literature.…”

A heteroleptic fused bi-cuboctahedral Cu21S2 cluster

“…The addition of acid leads to the structural degradation of the template cluster, which disconnects the linear [CuH 2 ] À unit, cleaves out two [CuC 2 Ph] units and assembles two cuboctahedra to form a fused bi-cuboctahedral Cu 21 S 2 kernel. We expect to produce more copper clusters of this kind via the fusion of two halide-centered Cu 12 cuboctahedral structures, [X@Cu 12 (dtc/dtp) 6 (C 2 Ph) 4 ] + (X = Cl, Br, I), 25,31 after working out appropriate synthetic conditions.…”