Luminescence and thermal behavior by simultaneous TG/DTG-DTA coupled with MS of neutral copper (I) complexes with heterocyclic thiones

Copper(I) halide complexes formulated as [(L)CuX(mu(2)-L)(2)CuX(L)] (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, coupled with MS for the analysis of the gaseous decomposition products, 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 A degrees C (verified with PXRD) were a mixture of Cu2S and CuX, while at 1,300 A degrees C a mixture of Cu2S and Cu. In oxygen atmosphere the residues were CuO.