Two pairs of 1 : 2 nickel(ii) and copper(ii) metal-complex dyes showing the same trans configuration and azo–hydrazone transformation but different thermal properties

Abstract

Two pairs of 1 : 2 neutral trans mononuclear transition-metal (M = Ni^II and Cu^II) complexes of pyridine-2,4-dione and quinoline-2,4-dione based heterocyclic dyes have been structurally and spectrally characterized and compared herein. X-ray single-crystal diffraction analyses of four complexes, namely trans-[Ni(L_a)₂(DMF)₂] (1), trans-[Cu(L_a)₂(DMF)₂] (2), trans-[Ni(L_b)₂(DMF)₂] (3) and trans-[Cu(L_b)₂(DMF)₂] (4), reveal that they have the same trans configuration between the bidentate chelating dianionic ligands and two axially coordinated DMF molecules. Furthermore, a transformation from the hydrazone to azo configuration has been observed for both bidentate chelating ligands L_a⁻ and L_b⁻ after metal-ion complexation. More importantly, the simultaneous DSC/TG-MS-FTIR method has been used to explore the thermal stability of four neutral metal-complex dyes 1–4, where the two axially coordinated DMF molecules in Ni^II and Cu^II complexes exhibit distinguishable decomposition behavior because of their different M–O bond lengths originating from the Jahn–Teller distortions.