A coordination polymer based on the polymetallic [Cu4I4] center was synthesized by coordination with a phenyl-based-diphosphine ligand. The structure of this solid formulated as [Cu4I4(Ph2P(C6H4)2PPh2)2]n, although crystalline, could not be completely resolved using powder X Ray diffraction analysis. Nevertheless, combining different characterization techniques, in particular 63Cu and 31P solid-state NMR analyses, provided insights into the polymeric structure. This coordination polymer appears to be of high dimensionality with possible interpenetrated networks, resulting in low porosity. Photoluminescence characterization revealed that the original luminescence thermochromic properties could be ascribed to the photoactive cluster unit.
