The structural manipulation of a series of Ni4 defective dicubanes: Synthesis, X-ray Structures, Magnetic and Computational analyses

We report the synthesis and characterization of four new tetranuclear Ni(II) complexes, C1-C4, all of which exhibit defective dicubane cores. C1-C4 are derived from the same salicylaldoxime derived ligand, H(2)L1. Complexes C1 and C4 have isostructural cores, differing in structure only by solvate molecules. Magnetic and computational analyses have revealed that complexes C1, C2, and C4 exhibit competing ferro- and antiferromagnetic interactions, however the different solvated species in C1 and C4 leads to notably different magnitudes in their magnetic coupling constants. Theoretical magneto-structural studies show that the pairwise magnetic exchange interaction is highly dependent on the Ni-X-Ni angle, as revealed by orbital overlap calculations.

Automated summary

The four new tetranuclear Ni(II) complexes have defective dicubane cores derived from the same salicylaldoxime derived ligand. Magnetic and computational analyses revealed competitive ferro- and antiferromagnetic interactions, with differences in magnetic coupling constants due to different solvated species. Theoretical magneto-structural studies showed that the magnetic exchange interaction is highly dependent on the Ni-X-Ni angle.