Rotaxane CoII Complexes as Field-Induced Single-Ion Magnets

Abstract

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.

Keywords: electron paramagnetic resonance; magnetism; rotaxanes; single ion magnets; zero-field splitting.