Reversible Switchability of Magnetic Anisotropy and Magnetodielectric Effect Induced by Intermolecular Motion

Angew Chem Int Ed Engl. 2022 Aug 26;61(35):e202204700. doi: 10.1002/anie.202204700. Epub 2022 Jun 21.

Abstract

Introducing magnetic switchability into artificial molecular machines is fascinating for precise control of magnetism via external stimuli. Herein, a field-induced CoII single-molecule magnet was found to exhibit the reversible switch of Jahn-Teller distortion near room temperature, along with thermal conformational motion of the 18-crown-6 rotor, which pulls the coordinated H2 O to rotate through intermolecular hydrogen bonds and triggers a single-crystal-to-single-crystal phase transition with Twarm =282 K and Tcool =276 K. Interestingly, the molecular magnetic anisotropy probed by single-crystal angular-resolved magnetometry revealed the reorientation of easy axis by 14.6°. Moreover, ON/OFF negative magnetodielectric effects were respectively observed in the high-/low-temperature phase, which manifests the spin-lattice interaction in the high-temperature phase could be stronger, in accompanied by the hydrogen bonding between the rotating 18-crown-6 and the coordinated H2 O.

Keywords: Jahn-Teller Distortion; Magnetic Anisotropy; Magnetodielectric Effect; Phase Transition; Rotor.