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 FM′. 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, FZn and FCd are only weakly luminescent in the solid-state at low temperature