Magnetic and Dielectric Switchings Actuated by the Rotation of the Picoline Ligand in an Iron-Based Dinuclear Phase-Transition Complex

Multifunctional materials with switchable magnetic and dielectric properties are crucial for the development of memory and sensor devices. Herein, we report a methoxy-bridged dinuclear iron-pyridyl complex [Fe₂(4-picoline)₄(NCS)₄(μ-OCH₃)₂] (1), which shows simultaneous thermal-induced magnetic and dielectric switchings. Within the phase-transition temperature range, both magnetic switching and the dielectric anomaly were detected, in which the thermal hysteresis loops were 23 and 21 K, respectively. Detailed structural analyses revealed that these simultaneous switchings were rooted in the flexible rotatable ligands, which were actuated by readjusting the π-π intermolecular interactions between the pyridine ligands in the trans positions of the metal centers. These results were comprehensively investigated both experimentally and theoretically. This study presents a new guideline to control both the magnetic and dielectric properties of molecular complexes by external stimuli.