Silver(I) and Thioether-bis(pyrazolyl)methane Ligands: The Correlation between Ligand Functionalization and Coordination Polymer Architecture

This work examines the crystal structures of 15 Ag(I) complexes with thioether functionalized bis(pyrazolyl)methane derivatives to rationalize the influence of the ligand on the formation of (a) coordination polymers (CPs), (b) oligonuclear (hexameric and dinuclear) complexes, and (c) mononuclear complexes. It was previously reported how this ligand class could generate microporous architectures with permanent porosity. Some ligand modifications could induce a cavity size modulation while preserving the same overall architecture. The bis(pyrazolyl)methane scaffold can be easily functionalized with various structural fragments; hence the structural outcomes were studied in this work using various ligand modifications and Ag(I) salts. In particular, six new ligand classes were prepared with the following features: (1) The steric hindrance on the pyrazole rings L3,3′Me, L5,5′Me, L5,3′Me, LCF3, and LBr was modified. (2) The steric hindrance was reduced on the peripheral thioether group: LSMe. (3) Finally, the...