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

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(1)-thiolate clusters protected by pyridines, namely, [Ag-3((BuS)-Bu-t)(2)(Py)(NO3)](n) (Py = pyridine) (1), [Ag-10((BuS)-Bu-t)(6)(Py)(6)(CF3CO2)(4)]center dot 3Py (2), [Ag-12((PrS)-Pr-i)(6)(Py)(8)(NO3)(6)]center dot 2H(2)O (3), Ag-12((PrS)-Pr-i)(6)(Py)(8)(CF3CO2)(6) (4) Ag-12((PrS)-Pr-i)(6)(4) Ag-12((i)Prs)(6)(4-ap)(6)(NO3)(6) (4-ao = 4-amino-Pyridine) (5), and [Ag50S13((BuS)-Bu-t)(20)(PY)(12)]center dot 4BF(4)center dot 4Py center dot 4CH(3)OH center dot 2H(2)O (6). Single-crystal X-ray crystallography analysis reveals that six clusters are constructed by four types of structural blocks, including the PyAg ((BuS)-Bu-t)(2) monomer, Py2Ag2((BuS)-Bu-t)(2) dimer, Py3Ag3((BuS)-Bu-t)(3) trimer and (4-ap)(6)Ag-6((PrS)-Pr-i)(6) hexamer. Notably, cluster 6 consists of a rhombic dodecahedron S@Ag-14 kernel with 12 interstitial S2- atoms encapsulated by 8 mu(4)-(BuS-)-Bu-t ligands, as well as six unique butterfly-like (Py)(2)Ag-6((BuS)-Bu-t)(2) staple motifs composed of a Py2Ag2((BuS)-Bu-t)(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.