SELF-ASSEMBLY OF COPPER(I) AND SILVER(I) COMPLEXES WITH SQUARE-GRID AND CHANNEL STRUCTURES

Copper(I) and silver(I) complexes of 2-[bis(methylsulfanyl)methylene]p ropanedinitrilel (bmmp), [Cu(bmmp)(2)]ClO4 1 and [Ag(bmmp)(2)]ClO4 2, have been prepared and their molecular structures determined by X-ray crystallography. The network topology of bmmp is found to depend on th e metal-ion stereochemical preference. In 1 the copper(I) ion prefers a tetrahedral co-ordination geometry comprising four nitrogen atoms fr om four different bmmp molecules and each bmmp in turn bridges two cop per(I) centres leading to a square-grid arrangement of alternating met al cations and organic ligands. In 2, by contrast, the silver(I) ion i nvolves an elongated octahedral environment with four N atoms forming a basal plane and two thioether S atoms occupying the axial positions; each bmmp acts as a non-chelating tridentate ligand bridging three me tal centres, resulting in a three-dimensional channel structure. The i nfluence of the metal-ion stereochemical preference on the co-ordinati on networks of bmmp is discussed.