Fluoride-bridged dinuclear dysprosium complex showing single-molecule magnetic behavior: supramolecular approach to isolate magnetic molecules

Abstract

Using Na-encapsulated benzo[18]crown-6 (Na)(B18C6) as a counter cation, we successfully magnetically isolated a fluoride-bridging Dy dinuclear complex {[(PW₁₁O₃₉)Dy(H₂O)₂]₂F} (Dy₂POM) with lacunary Keggin ligands. (Na)(B18C6) formed two types of tetramers through C–H⋯O, π⋯π and C–H⋯π interactions, and each tetramer aligned in one dimension along the c-axis to form two types of channels. One channel was partially penetrated by a supramolecular cation from the ±a-axis direction, dividing the channel in the form of a “bamboo node”. Dy₂POM was spatially divided by this “bamboo node,” which magnetically isolated one portion from the other. The temperature dependence of the magnetic susceptibility indicated a weak ferromagnetic interaction between the Dy ions bridged by fluoride. Dy₂POM exhibited the magnetic relaxation characteristics of a single-molecule magnet, including the dependence of AC magnetic susceptibility on temperature and frequency. Magnetic relaxation can be described by the combination of thermally active Orbach and temperature-independent quantum tunneling processes. The application of a static magnetic field effectively suppressed the relaxation due to quantum tunneling.