Copper (I) halide complexes formulated as [(L)2Cu(μ2-L)2Cu(L)2]2+ 2χ−, (X = Cl, Br and L = pyridine-2-thione (py2SH) or 4,6-dimethylpyrimidine-2-thione (dmpymtH)) were prepared, and their photoluminescence and thermal properties were investigated. The complexes are strongly emissive in the solid state, with the emissions being dominated by large Stokes shifts (>200 nm), which are depending on both the heterocyclic thione and the nature of the halogen. These emissions can be assigned to MLCT with some mixing of the halide-to-ligand (XL) CT characters. Simultaneous TG/DTG–DTA technique was used for two complexes with the dmpymtH ligand to determine their thermal degradation, which was found to be very complicated. In inert atmosphere the residues at 1,000 °C (verified with PXRD) were mainly Cu2S, while at 1,300 °C a mixture of Cu2S and Cu. In oxygen atmosphere the residues were CuO.
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