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A new polyoxometalate-based compound {[Ag3L4 (CH3OH)]PMo12O40·CH3OH} has been synthesized and characterized by IR,elemental analysis and X-ray crystallography.The compound crystallized in the triclinic space group P(T),Ag(1) center has a three-coordinated environment,which consists of two Nimine donors from two ligands and one O donor from CH3OH.Ag(2) adopts three-coordinated geometry with N2O donors from two ligands and Ag(3) center has a two-coordinated environment with a N2 donor set from two ligands.Adjacent trinuclear cation units [Ag3L4(CH3OH)]3+ were linked with each other to form a dimer.In addition,[PMo12O40]3-anions link trinuclear cation units through multiform intermolecular hydrogen bonds to form a three-dimensional supramolecular structure.The luminescent properties of the title compound were investigated in the solid at room temperature.