A blue photoluminescent coordination polymer Ag4Cl4(dppe)2n has been prepared solvothermally and characterized structurally. The crystal structure was determined by single-crystal X-ray diffraction. The crystal is of tetragonal, space group I41 / a, a=b=1.936 03(6) nm, c=1.465 63(8) nm, V=5.493 5(4) nm3, Z=4, Dcalcd=1.657 Mg·m-3, μ=1.749 mm-1. Reflections collected: 17 147, independent reflections: 3 247, Rint=0.021 1. Final R indices I > 2σ(I): R1=0.044 8, wR2=0.111 0. The structure of Ag4Cl4(dppe)2n is a 3D-diamond highly symmetrical polymeric network containing Ag4Cl4 cubane-like clusters connected by 1,2-bis(diphenylphosphino)ethane (dppe). Each Ag4Cl4 cluster is composed of four silver and four chlorine atoms situated at alternate vertexes of a highly distorted cube with each silver atom being further coordinated to one phosphorus atom from a dppe ligand. The stripping of chloride ions from CHCl3 provides the source for chlorine in the formation of Ag髣 clusters. In addition, the emission spectrum of the complex 1 in solid state has been studied. CCDC: 288080.
