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

Coordination-driven supramolecular (CDS) syntheses between the pre-assembled tetrametallic flexible precursor A and pseudo-halide dicyanamide N(CN)(2)(-) (DCM) and azido N-3(-) ions afforded selectively the discrete Cu-8 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 Cu-8 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.

Automated summary

Coordination-driven supramolecular syntheses between flexible precursor A and pseudo-halide ions resulted in the selective formation of discrete Cu-8 assembly D and one-dimensional coordination polymer E. Subsequent reactions with M'(II) salts led to the self-dissociation and reorganization processes, yielding new discrete Cu-8 assemblies. The solid-state luminescence properties of these derivatives showed D as a moderate room temperature luminophore, while E, F-Zn, and F-Cd exhibited weak luminescence at low temperature.