A rare Cu(I)/Cu(II)-azide complex showing honeycomb-type net structure: Synthesis, structure, and magnetic studies

Via hydrothermal synthesis, the self-assembly of CuCl2 · 2H2O, NaN3, and 2,2′-bpy generated a new azide complex, namely [Cu2(2,2′-bpy)(N3)3]n1(2,2′-bpy = 2,2′-bipyridyl). In this reaction, the original Cu(II) ions are partly deoxidized to be Cu(I) by 2,2′-bpy and N3- ligands, and the Cu(I) ions are associated together by N3- ions to give the infinitely helical chain of {Cu(N3)}n. Afterwards, these chains are connected by the [Cu(2,2′-bpy)(N3)2]2 fragments to furnish the 2D honeycomb-type net, where the Cu(I) ions act as 3-connected nodes and the Cu(II) ions locate on the edge. The magnetic measurement suggests the antiferromagnetic interaction of the dinuclear copper fragment mediated by EO azido bridges, which is consisted with the fitting results upon a dinuclear copper mode.