Luminescent cuprous complexes are of great importance among coordination compounds due to their relative abundance, low cost and ability to display excellent luminescence. The title heteroleptic cuprous polymer solvate, catena-poly[[[(9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphane)-κP,P'](μ-pyridine-3-carbonitrile-κN:N)copper(I)] hexafluorophosphate dichloromethane trisolvate], {[Cu(CHN)(CHOP)]PF·3CHCl}, conventionally abbreviated as {[Cu(3-PyCN)(Xantphos)]PF·3CHCl}, where Xantphos and 3-PyCN represent (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphane) and pyridine-3-carbonitrile, respectively, has been described. In this polymer solvate, the asymmetric unit consists of three dichloromethane solvent molecules, a hexafluorophosphate anion and a polymeric heteroleptic cuprous complex cation, in which the cuprous centre is in a CuPN tetrahedral coordination and is coordinated by two P atoms from the Xantphos ligand and two N atoms from two 3-PyCN ligands (the pyridyl and cyano N atoms). It is through the connection of the μ-bridging 3-PyCN ligand that these cuprous centres are linked into a one-dimensional helical chain structure. The chains are further assembled through C-H...π interactions to form a supramolecular metal-organic framework containing solvent-accessible channels. The UV-Vis absorption and photoluminescence properties of this heteroleptic cuprous polymer have been studied on as-synthesized samples. Its luminescence emission should mainly originate from the metal-to-ligand charge transfer excited state.
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