Red emissive 1D Copper(I) Thiolates vs. 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 non-critical 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 vs. 2D [Cu3Cl(p-SPhX)2]n and they exhibit distinct photophysical properties: [Cu(p-SPhX)]n show usual solid-state red emission, while [Cu3Cl(p-SPhX)2]n have intense solid-state green anti-Stokes emission, associated, for the non-centrosymmetric compounds, X = F and Br, to non-linear optical response (NLO), pointing out the effect of the weak halogen interactions of the thiolate ligands on the symmetry and the properties.