Crystal lattice desolvation effects on the magnetic quantum tunneling of single-molecule magnets

Abstract

High-frequency electron paramagnetic resonance (HFEPR) and AC susceptibility measurements are reported for a new high-symmetry Mn12 complex, [Mn12O12(O2CCH3)16(CH3OH)4].CH3OH. The results are compared with those of other high-symmetry spin S = 10 Mn12 single-molecule magnets (SMMs), including the original acetate, [Mn12(O2CCH3)16(H2O)4].2CH3CO2H.4H2O, and the [Mn12O12(O2CCH2Br)16(H2O)4].4CH2Cl2 & [Mn12O12(O2CCH2But)16(CH3OH)4].CH3OH complexes. These comparisons reveal important insights into the factors that influence the values of the effective barrier to magnetization reversal, Ueff, deduced on the basis of AC susceptibility measurements. In particular, we find that variations in Ueff can be correlated with the degree of disorder in a crystal which can be controlled by desolvating (drying) samples. This highlights the importance of careful sample handling when making measurements on SMM crystals containing volatile lattice solvents. The HFEPR data additionally provide important spectroscopic evidence suggesting that the relatively weak disorder induced by desolvation strongly influences the quantum tunneling interactions, and that it is under-barrier tunneling that is responsible for a consistent reduction in Ueff that is found upon drying samples. Meanwhile, the axial anisotropy deduced from HFEPR is found to be virtually identical for all four Mn12 complexes, with essentially no measurable reduction upon desolvation.