Magnetic coupling in EE and EO azido-bridged binuclear copper complexes: Synthesis,structure and magnetic studies

Four azide bridged dinuclear copper(II) complexes, Cu₂(L^X)₂(N₃)₂](ClO₄)₂, with L^X = substituted N,N-bis(3,5-dimethylpyrazole-1-yl)-methyl]benzylamine, X = H (1), OMe (2), Me (3) and Cl (4)] have been synthesized, out of which complexes 1 and 2 have been characterized structurally. In Complex 1 the two bridging azide ligands have connected the two metal centers in an end-on (EO) fashion with aSP (asymmetric Square Pyramidal) geometry and showed an weak antiferromagnetic interaction (J = −3.34 cm⁻¹). On the contrary, in complex 2, the two metal centers have been connected in end-to-end (EE) fashion exhibiting moderately strong ferromagnetic interaction (J = +19.7 cm⁻¹). Cyclic voltammetric studies performed on all the four complexes show a reasonably good correlations when E_1/2 for Cu^IICu^II → Cu^IICu^III and Cu^IICu^III → Cu^IIICu^III oxidations are plotted against σ (substituent constants) with ρ = −0.182 (R² = 0.92) and −0.684 (R² = 0.99) respectively.