Monovalent K, Cs, Tl, and Ag nitrosodicyanomethanides: completely different 3D networks with useful properties of luminescent materials and nonelectric sensors for gases.

Four K, Cs, Ag(I), and Tl(I) compounds with a nitrosodicyanomethanide ONC(CN)2− anion have been obtained and characterized using IR spectroscopy; UV−visible spectroscopy; room temperature, solid-state photoluminescence; and solutions electrical conductivity measurements. Cesium and thallium(I) complexes were obtained for the first time, and crystal structures were determined for Cs{ONC(CN)2}, Ag{ONC(CN)2}, and Tl{ONC(CN)2}. These structures indicate the formation of completely different 3D polymeric networks in which the anion acts as a bridging ligand of different capacity. The cyanoxime ligand in all complexes studied is in the nitroso form and adopts a planar configuration. The structure of the cesium salt is ionic. The structure of Ag{ONC(CN)2} represents a 3D coordination polymer where the anion acts as a tetradentate ligand with all four bonds between Ag(I) and donor atoms (three N and one O) significantly shorter than the sum of the ionic radii for these elements. The silver(I) atom in this compoun...