Pseudohalide Ions as Ligands to Tune Architecture and Luminescence of Polymetallic CU(I) Assemblies.

The reaction of preassembled Cu(I) bimetallic units {Cu(dppm)} and {Cu(dppa)} (dppm: bis(diphenylphosphino)methane and dppa: bis(diphenylphosphino)amine) with pseudohalide linkers (azido, dicyanamide, and tricyanomethanide) allows for the quantitative and selective preparation of three discrete tetrametallic metallacycles of formula [Cu(μ-dppm)(N)](PF), [Cu(μ-dppm)(N(CN))](PF), and [Cu(μ-dppm)(C(CN))]. To explore further the impact of the linker on the architecture and dimensionality of the molecular edifice, the study was extended to more sophisticated tetradentate cyanocarbanion ligands (tcnsMe: 2-(methylthio)-1,1,3,3-propanetetracarbonitrile and tcnsEt: 2-(ethylthio)-1,1,3,3-propanetetracarbonitrile). Three ladder-like one-dimensional coordination polymers and an octametallic metallacycle have been obtained.