Coordination-driven supramolecular syntheses of new homo- and hetero-polymetallic Cu(i) assemblies: solid-state and solution characterization

Abstract

Coordination-driven supramolecular (CDS) syntheses between the pre-assembled tetrametallic flexible precursor A and pseudo-halide dicyanamide N(CN)₂⁻ (DCM) and azido N₃⁻ ions afforded selectively the discrete Cu₈ assembly D and the one-dimensional coordination polymer E, respectively. Upon the reaction of E with M′(II) salts (M′ = Cu, Zn, Cd), straightforward self-dissociation/re-organisation processes take place yielding new discrete Cu₈ assemblies F_M′. Preservation in a solution of polymetallic Cu(I) CDS assemblies is evidenced for the first time. Solid-state luminescence properties of these derivatives are reported, revealing that D is a moderate room temperature luminophore upon UV-vis light excitation (emission quantum yield of 13%) while derivatives E, F_Zn and F_Cd are only weakly luminescent in the solid-state at low temperature.