T-symmetric 40-nucleus silver clusters assembled by hetero-anions

We report two anion-templated Ag-40 clusters, [Ag-40(E)(4)(SO4){S2P(OEt)(2)}(24)](PF6)(6) (E = S, 1; Se, 2). The anionic templates were generated in situ from the decomposition of dithiophosphate (dtp) ligands. The extrusion of sulfur undergoes disproportionation reactions to generate sulfide and sulfate anions, which provide the source of templates in the subsequent cluster assembly reactions. Two Ag-40 clusters display high similarity in their structures. The sulfide (selenide) anions and the central sulfate anion reveal a six-coordinate and a rare dodecametallic dodecaconnective pattern, respectively. Four near-equivalent [Ag-10(E){S2P(OEt)(2)}(6)](2+) motifs were assembled via the connection of central sulfate anion to construct Ag-40 clusters. The cluster cation, [Ag-40(E)(4)(SO4){S2P(OEt)(2)}(24)](6+), displayed in T symmetry, is unprecedented in anion-templated silver clusters.