Synthesis and spectrothermal studies of thermochromic diamine complexes of cobalt(III), nickel(II) and copper(II) squarate. Crystal structure of [Co(en)(3)](sq)(1.5) center dot 6H(2)O

Abstract

New adducts of ethylenediamine (en), N,N-dimethylethylenediamine (ndmen) and N,N'-dimethylethylenediamine (dmen) with squarate as counter-ions were synthesized and characterized by physico-chemical methods (IR and UV/vis spectroscopy, magnetic susceptibility and thermoanalytical measurements). The crystal structure of tris(ethylenediamine)cobalt(III) 1.5 squarate hexahydrate, [Co(en)(3)](sq)(1.5) center dot 6H(2)O, was determined by single crystal X-ray diffraction. Co(III), Ni(II) and Cu(II) ions in the monomeric octahedral tris(ethylenediamine)cobalt(III) 1.5 squarate hexahydrate (1), tris(ethylenediamine)nickel(II) squarate 0.5 hydrate (2) and diaquabis(ethylenediamine)copper(II) squarate dihydrate (3) are chelated by ethylenediamines through two amine nitrogen atoms. Cu(II) atoms in the diaquabis(ndmen)copper(II) squarate (4) and diaquabis(dmen)copper(II) squarate (5) monomeric octahedral complexes are coordinated by ndmen and dmen molecules through two amine nitrogen atoms in a bidentate chelating manner. Water molecules complete the octahedral coordination. The orange (1), violet (4) and violet (5) complexes upon heating transform to claret, green and green species on dehydration, respectively, which revert immediately after cooling in the open atmosphere. The violet (3) complex upon heating loses water molecules yielding a deep blue dehydrated species, which on further heating undergoes an exothermic phase transition accompanied by thermochromism, deep blue to brown in the solid state. The decomposition mechanism and thermal stability of the solid complexes are interpreted in terms of their structures. The final decomposition products - the respective metal oxides - were identified by IR spectroscopy.