Syntheses, crystal structures, magnetic properties and ESI-MS studies of a series of trinuclear CuIIMIICuII compounds (M = Cu, Ni, Co, Fe, Mn, Zn)

Abstract

Six trinuclear CuIIMIICuII compounds (M = Cu, Ni, Co, Fe, Mn, Zn) derived from the Schiff base ligand, H2L (2 + 1 condensation product of salicylaldehyde and trans-1,2-diaminocyclohexane) are reported in this investigation. The composition of the metal complexes are [{CuIIL(ClO4)}2CuII(H2O)]·2H2O (1), [{CuIIL(ClO4)}{NiII(H2O)2}{CuIIL}]ClO4·CH3COCH3 (2), [{CuIIL(ClO4)}{CoII(CH3COCH3)(H2O)}{CuIIL(CH3COCH3)}]ClO4 (3) and isomorphic [{CuIIL(ClO4)}2MII(CH3OH)2] (4, M = Fe; 5, M = Mn; 6, M = Zn). Two copper(ii) ions in 1-6 occupy N2O2 compartments of two L2- ligands, while the second metal ion occupies the O(phenoxo)4 site provided by the two ligands, i.e., the two metal ions in both CuIIMII pairs are diphenoxo-bridged. Positive ESI-MS of 1-6 reveals some interesting features. Variable-temperature and variable-field magnetic studies reveal moderate or weak antiferromagnetic interactions in 1-6 with the following values of magnetic exchange integrals (H = -2JS1S2 type): J1 = -136.50 cm-1 and J = 0.00 for the CuIICuIICuII compound 1; J1 = -22.16 cm-1 and J = -1.97 cm-1 for the CuIINiIICuII compound 2; J1 = -14.78 cm-1 and J = -1.86 cm-1 for the CuIICoIICuII compound 3; J1 = -6.35 cm-1 and J = -1.17 cm-1 for the CuIIFeIICuII compound 4; J1 = -6.02 cm-1 and J = -1.70 cm-1 for the CuIIMnIICuII compound 5; J = -2.25 cm-1 for the CuIIZnIICuII compound 6 (J is between two CuII in the N2O2 compartments; J1 is between CuII and MII through a diphenoxo bridge).