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Updated: Jun 6, 2025

Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
Assembly of silver(I)-copper(I) bimetallic thiolate complexes assisted by phenylacetylene stabilizers
Jun-Ling Jin1, Sheng-Fa Zhang1, Jun-Jie Fang2
1Henan Key Laboratory of Functional Salt Materials, Center for Advanced Materials Research, Zhongyuan University of Technology, Zhengzhou, 450007, China. jinjunling@zut.edu.cn.
Abstract:
AgI/CuI bimetallic clusters have been widely reported, but synthesis of such clusters via simple self-assembly of heterometallic ions in air remains challenging due to the susceptibility of CuI ions to oxidation. In this study, protected by the phenylacetylene auxiliary ligand, we utilized [Cu(CH3CN)4]PF6 in conjunction with the (PrSAg) polymer to form Ag(I)-Cu(I) oligomer precursors, serving as the starting point for constructing a new [Ag11-Cu(PrS)9(DPPM)3](PF6)2 cluster (DPPM = bis(diphenylphosphino)methane, Ag11-xCux, x = 5-9). When the (PrSAg) precursor was replaced by (BuSAg), another cluster [Ag21Cu4S2(BuS)18(CH3CN)4](CH3OH)2(H3O)(PF6)4 (Ag21Cu4) was obtained. By combining crystallographic data and electrospray ionization mass spectrometry (ESI-MS) results, the compositions and structures of these two new clusters were determined. Additionally, the optical physical properties of the luminescent Ag11-xCux were investigated, showing red phosphorescence emission in both solid-state and solution phases. The solid-state phosphorescence quantum yield (QY) is 8%, with a lifetime of 7.2 μs. These findings suggest that phenylacetylene auxiliary ligands can effectively stabilize CuI ions and guide the assembly of silver-copper bimetallic thiolate motifs into new compounds under ambient conditions.
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