tert-Butyl thiol and pyridine ligand co-protected 50-nuclei clusters: the effect of pyridines on Ag-SR bonds

Yang-Lin Shen; Jun-Ling Jin; Yun-Peng Xie; Xing Lu

doi:10.1039/d0dt02003f

tert-Butyl thiol and pyridine ligand co-protected 50-nuclei clusters: the effect of pyridines on Ag-SR bonds

Dalton Trans. 2020 Sep 22;49(36):12574-12580. doi: 10.1039/d0dt02003f.

Authors

Yang-Lin Shen¹, Jun-Ling Jin², Yun-Peng Xie¹, Xing Lu¹

Affiliations

¹ State Key Laboratory of Materials Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology (HUST), Wuhan 430074, China. xieyp@hust.edu.cn lux@hust.edu.cn.
² Henan Key Laboratory of Functional Salt Materials, Center for Advanced Materials Research, Zhongyuan University of Technology, Zhengzhou, 450007, China.

PMID: 32852489
DOI: 10.1039/d0dt02003f

Abstract

Constructing silver(i)-thiolate clusters from simple building blocks usually involves elusive self-assembly processes and remains a long-standing challenge. In this work, we report 6 silver(i)-thiolate clusters protected by pyridines, namely, [Ag3(tBuS)2(Py)(NO3)]n (Py = pyridine) (1), [Ag10(tBuS)6(Py)6(CF3CO2)4]·3Py (2), [Ag12(iPrS)6(Py)8(NO3)6]·2H2O (3), Ag12(iPrS)6(Py)8(CF3CO2)6 (4), Ag12(iPrS)6(4-ap)6(NO3)6 (4-ap = 4-aminopyridine) (5), and [Ag50S13(tBuS)20(Py)12]·4BF4·4Py·4CH3OH·2H2O (6). Single-crystal X-ray crystallography analysis reveals that six clusters are constructed by four types of structural blocks, including the PyAg(tBuS)2 monomer, Py2Ag2(tBuS)2 dimer, Py3Ag3(tBuS)3 trimer and (4-ap)6Ag6(iPrS)6 hexamer. Notably, cluster 6 consists of a rhombic dodecahedron S@Ag14 kernel with 12 interstitial S2- atoms encapsulated by 8 μ4-tBuS- ligands, as well as six unique butterfly-like (Py)2Ag6(tBuS)2 staple motifs composed of a Py2Ag2(tBuS)2 dimer and four silver ions. Moreover, it is found that pyridine ligands have important influence on the construction of silver thiolate clusters and their Ag-SR bond lengths.