High-nuclearity silver(I) cluster-based coordination polymers assembled with multidentate oligo-α-heteroarylsulfanyl ligands.

Two novel coordination polymers [Ag16(SO4)8][Ag4(SO4)2]3(L1)12·nH2O (n = 72) (1) and [Ag10(SO4)5(L2)4(H2O)2]·8H2O (2) based on conformationally variable oligo-α-heteroarylsulfanyl ligands 2-(pyrazin-2-ylthio)-6-(pyridin-2-ylthio)pyrazine (L1) or 2,6-bis(pyrazin-2-ylthio)pyrazine (L2) and sulfate-templated high-nuclearity Ag(I) clusters as structure-building units (SBUs) have been synthesized under mild conditions. Single-crystal X-ray analysis showed that complex 1 exhibits a porous three-dimensional framework containing Ag16(SO4)8 and Ag4(SO4)2 SBUs that are interconnected by L1 ligands, whereas 2 has a much denser network constructed from Ag10(SO4)5 SBUs and L2 linkers. To our knowledge, the Ag16(SO4)8 cluster core found in 1 is the largest sulfate-based polynuclear SBU in coordination polymers, and the 14-connected Ag10(SO4)5 in 2 is the highest-connectivity Ag(I) cluster SBU reported to date. These two complexes were fully characterized by infrared spectroscopy, elemental analysis, powder X-ray diffraction, thermogravimetric analysis and differential scanning calorimetry.