An Extended Ag^I Cluster‐Based Framework Solid: Silver‐Thiolate Cluster Linked Polyoxometalate Including Ag^I···H–C Anagostic Interactions

Abstract

In this contribution, a new crystalline silver(I) cluster‐based coordination polymer, {[Ag 11 ( i BuS) 9 (CH 3 CN)](Mo 6 O 19 )} n ( SD/Ag11a ) has been prepared and structurally characterized by single‐crystal X‐ray diffraction. The structure of SD/Ag11a consists of an asymmetric unit of Ag 11 S 9 cluster, in which the coordination number of the eleven silver atoms varies from two to four and the Ag ··· Ag contacts in the cluster range from 2.897 to 3.374 Å. Each Ag 11 S 9 cluster is interconnected by thiolate ligands i BuS – , thus forming one‐dimensional (1‐D) coordination polymer. An extended two‐dimensional (2‐D) infinite sheet formed by linking 1‐D silver(I) cluster‐based polymeric motifs and [Mo 6 O 19 ] 2– anions through intermolecular Ag ··· O weak interactions. One of the interesting structural features of SD/Ag11a is the presence of obvious Ag ··· H–C interactions between hydrogen atoms of the methylene and methyl groups on the i BuS – ligands and silver atoms. The solution behavior and the solid‐state optical properties of SD/Ag11a were also investigated.