Stepwise formation of a pentanuclear Ni4Cu heterometallic complex exhibiting a vertex-sharing defective double-cubane core and diphenoxo- and phenoxo/azide bridging groups: a magnetostructural and DFT theoretical study.

Sequential reaction of a N5O3 octadentate tripodal ligand with Ni(2+) and subsequently with Cu(2+) and azide ligand afforded the first example of a heterobridged (phenoxo/µ(1,1)-azido) pentanuclear heterometallic (Ni4Cu) compound, which exhibits a centrosymmetric vertex-sharing defective double-cubane structure. The study of the magnetic properties reveals that the compound shows ferromagnetic interaction interactions, leading to an S = 9/2 spin ground state. Density functional theory calculations on the X-ray structure and model compounds predict ferromagnetic interactions through the magnetic exchange pathways involving each couple of metal ions.