The effort for synthesis complexes of unsymmetrical Schiff base ligands derived from 2,2-dimethyl-1,3-propanediamine, o-hydroxyacetophenone and salicylaldehyde by modified Edler's method resulted in the isolation of mononuclear [CuL]·CH3OH (1), where H2L = N-(α-methylsalicylidene)-N′-(salicylidene)-2,2-dimethyl-1,3-propanediamine. Complex 1 on reaction with Mn(II) ion in presence of ClO4−, N(CN)2−, or N3− yielded three tri-nuclear complexes [(CuL)2Mn(CH3OH)2](ClO4)2·3H2O (2) [(CuL)2Mn(N(CN)2)2] (3) and [(CuL)2Mn(N3)2]∙2H2O (4), respectively. X-ray crystallography revealed square planar geometry of Cu(II) and distorted octahedral geometry of Mn(II) in the complexes. Temperature dependent molar magnetic susceptibility measurements illustrated overall anti-ferromagnetic coupling between the Cu(II) and Mn(II) centres in complexes 2–4 with exchange coupling parameters, J = −16.82 cm−1 and g = 2.06 for 2, J = −19.40 cm−1 and g = 2.10 for 3 and J = −18.98 cm−1 and g = 2.11 for 4. Among these hetero-metallic complexes only the azide derivative (4) presented prominent ac signals under an applied dc bias field. Cyclic voltammetry measurements showed reversible Cu(II)/Cu(I) couple for complex 1 whereas complexes 2–4 showed irreversible reduction of Cu(II).
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