Rotaxane CoII Complexes as Field-Induced Single-Ion Magnets

Mechanically chelating ligands have untapped potential for the engineering of metal ion properties. Here we demonstrate this principle in the context of Co-II-based single-ion magnets. Using multi-frequency EPR, susceptibility and magnetization measurements we found that these complexes show some of the highest zero field splittings reported for five-coordinate Co-II complexes to date. The predictable coordination behaviour of the interlocked ligands allowed the magnetic properties of their Co-II complexes to be evaluated computationally a priori and our combined experimental and theoretical approach enabled us to rationalize the observed trends. The predictable magnetic behaviour of the rotaxane Co-II complexes demonstrates that interlocked ligands offer a new strategy to design metal complexes with interesting functionality.