Anion-templated nanosized silver clusters protected by mixed thiolate and diphosphine.

S, MoO, and MoO were successfully employed as templates in the formation of six high-symmetry polynuclear silver clusters as exemplified in the single-crystal X-ray structures of [S@Ag(BuCHS)(dppp)]·DMF·5CHCN·3CHOH (1), [MoO@Ag(MeCHS)(dppm)(MoO)]·2BF·CHNO (2), [MoO@Ag(MeCHS)(dppm)(MoO)]·2CFSO (3), [MoO@Ag(MeCHS)(dppf)(MoO)]·2CFSO (4), [MoO@Ag(MeCHS)(dppb)(MoO)]·2CFSO (5) and [MoO@Ag(BuCHS)(dppm)(CHCN)]·6CFSO (6) (dppp = 1,3-bis(diphenylphosphino)propane, dppm = bis(diphenylphosphino)methane, dppf = 1,1'-bis(diphenylphosphino)ferrocene and dppb = 1,4-bis(diphenylphosphino)butane). Cluster 1 is a S-centered octadecanuclear banana-shaped molecule. Clusters 2-5 have similar structures consisting of a tetrahedron of a MoO core and four MoO where three silver atoms cap each face and a pair sits on each edge, giving tetraicosanuclear ball-shaped molecules. Although different diphosphine ligands and silver salts were used in the syntheses, 2-5 contain a common building cluster unit with similar geometry and nuclearity. With (BuN)MoO as a template, a giant 46-silver-atom cluster encapsulates an in situ modified MoO unit. The nuclearity and geometry depend on the size and shape of the templates. High-resolution electrospray mass spectrometry (HR-ESI-MS) analyses of 4 indicate its exceptionally high stability in acetonitrile. The solid-state luminescence of 1 as a function of the temperature exhibits thermochromism from red to yellow due to the different intensities of the two bands. This work established a new strategy for the construction of polynuclear silver clusters using an anionic template and mixed S- and P-donor ligands where a promising approach for building novel dual emissive materials is unraveled.