Mixed macrocyclic coordination compounds containing thiosemicarbazide and crown-ether moieties (synthesis, structure and properties)

The results of tandem s-3d metal template assembling of bis-compartmental h eterobinuclear macrocyclic compounds with one "hard" and one "soft" cavitie s, obtained by condensation of isothiosemicarbazide (or amidrazone) with li near polyether dialdehyde are described. The nature of employed reagents and the reactions conditions have an essent ial influence on the structural peculiarities of the synthesized compounds. The "hard" cavity is easily demetallated from s-metal with the formation of mononuclear complexes which become able to react with other species (Li+, Na+, K+, NH4+, Ca2+, Ba2+, Sr2+, Mg2+) forming different new compounds. The x-ray diffraction data of fifteen complexes are briefly discussed. The obtained compounds were studied in detail by suitable methods (mass-spectro metry, ESR, UV-Vis, calorimetric measurement), which permitted to elucidate the most specific properties of the considered systems.