Red Emissive 1D Copper(I) Thiolates and Green Emissive 2D Copper(I) Halide Thiolates Displaying Second Harmonic Generation and Two-Photon Absorption Processes.

Copper(I), as a d10 metal, is a promising affordable noncritical raw material finding great interest for the development of photoluminescent materials. Halide and thiolate-based copper(I) compounds are known for their efficient emission and good stability. In order to rationalize the effect of these two anions in the structure and photoemission of Cu(I) compounds, two new families of coordination polymers have been synthesized: the copper(I)-thiolates: [Cu(p-SPhX)]n (X = F, Cl, Br), and the copper halide thiolates: [Cu3Cl(p-SPhX)2]n (X = F, Cl, Br). The two families display different structural dimensionalities: 1D [Cu(p-SPhX)]n versus 2D [Cu3Cl(p-SPhX)2]n and they exhibit distinct photophysical properties: [Cu(p-SPhX)]n shows usual solid-state red emission, while [Cu3Cl(p-SPhX)2]n hasintense solid-state green anti-Stokes emission, associated, for the noncentrosymmetric compounds, X = F and Br, to non-linear optical (NLO) response, pointing out the effect of the weak halogen interactions of the thiolate ligands on the symmetry and the properties.