New metallomacrocyclic complexes based on acetamidrazone

Abstract The reaction of the linear polyether dialdehyde 3,3′-(3,6-dioxaoctane-1,8-diyldioxy)-bis(2-hydroxybenzaldehyde) ( 1 ) with acetamidrazone hydrochloride in the presence of barium triflate, followed by addition of metal(II) acetate, where metal(II)=nickel(II), copper(II) or zinc(II), yields dimeric heterometallic complexes [NiBaL(CF 3 SO 3 ) 2 ] 2 ( 2 ), [CuBaL(CF 3 SO 3 ) 2 ] 2 ( 4 ) and [ZnBaL(CF 3 SO 3 ) 2 (CH 3 OH)] 2 ( 6 ), where H 2 L=macrocyclic ligand. Removal of Ba 2+ from 2 , 4 and 6 by using an aqueous solution of guanidinium sulfate affords NiL·2H 2 O ( 3 ), CuL·1.5H 2 O ( 5 ) and ZnL·2H 2 O ( 7 ). The crystal structure of 2 has been determined by X-ray diffraction methods. The X-ray diffraction powder patterns show that 4 is isostructural with 2 . Electronic, EI, MALDI/TOF and ESI mass, NMR and ESR spectra are reported. Thermal degradation of 3 , 5 and 7 gives pure metal(II) oxides.