Influence of Guest Exchange on the Magnetization Dynamics of Dilanthanide Single-Molecule-Magnet Nodes within a Metal-Organic Framework

摘要

Multitopic organic linkers can provide a means to organize metal cluster nodes in a regular three-dimensional array. Herein, we show that isonicotinic acid N-oxide (HINO) serves as the linker in the formation of a metal-organic framework featuring Dy-2 single-molecule magnets as nodes. Importantly, guest solvent exchange induces a reversible single-crystal to single-crystal transformation between the phases Dy-2(INO)(4)(NO3)(2)center dot 2 solvent (solvent=DMF (Dy-2-DMF), CH3CN (Dy-2-CH3CN)), thereby switching the effective magnetic relaxation barrier (determined by ac magnetic susceptibility measurements) between a negligible value for Dy-2-DMF and 76 cm(-1) for Dy-2-CH3CN. Ab initio calculations indicate that this difference arises not from a significant change in the intrinsic relaxation barrier of the Dy-2 nodes, but rather from a slowing of the relaxation rate of incoherent quantum tunneling of the magnetization by two orders of magnitude.