The green coloured μ-phenoxo, μ-chloro and μ-phenoxo, μ1,1-azido bridged complexes of formula [Ni2(L)(Cl)(H2O)]·(C2H5)2O, 1·(C2H5)2O, and [Ni2(L)(N3)(H2O)]·CH3OH·H2O, 2·CH3OH·H2O have been synthesized, where L3−is the deprotonated form of 2,6-bis[N-(2-hydroxybenzyl)-N-{2-(dimethylamino)ethyl}aminomethyl]-4-methylphenol, H3L. In the complexes, one nickel(II) center has distorted square pyramidal (τ = 0.18 and 0.15) and other one has distorted octrahedral geometry. Both the complexes display a couple of one electron anodic responses near 0.70 and 1.10 V. Complexes 1and 2show weak antiferro and ferromagnetic interactions respectively. The calculated Jvalue using broken symmetry DFT method is consistent with the experimentally observed value. Moreover, the calculation also reveals that the antiferromagnetic interaction between the Ni(II) centers takes place viathe phenoxo bridge while that of ferromagnetic interaction is through the azido and chloro group. The presence of competitive interaction in the molecule reduces the overall magnetic behavior of the complex. [ABSTRACT FROM AUTHOR]