A Promising Phase Change Material with Record High Ionic Conductivity over a Wide Temperature Range of a Plastic Crystal Phase and Magnetic Thermal Memory Effect

The emerging organic ion plastic crystals (OIPCs) are the most promising candidates used as solid-state electrolytes in a range of ionic devices. To endow an OIPC with additional functionality may create a new type of material for multifunctional devices. Herein, we present an ion plastic crystal, [EMIm][Ni(mnt)2] (1; [EMIm]+ = 1-ethyl-3-methylimidazolium and mnt2- = maleonitriledithiolate), and its crystal consists of twin dimeric chains of [Ni(mnt)2]- anions, embraced by [EMIm]+ cations. A crystal-to-plastic crystal transformation with a large latent heat that occurred at ∼367/337 K on heating/cooling is confirmed by the differential scanning calorimetry (DSC) technique. The plastic crystal phase in 1, characterized by variable temperature powder X-ray diffraction (PXRD) and optical microscopy images, spans a broad temperature range with ΔT ∼123/153 K on heating/cooling (DSC measurement), and the wide ΔT is relevant to an extra stable anion chain owing to the strong antiferromagnetic (AFM) interactions protecting the chain from collapse in the plastic crystal state. 1 is a single-component ion plastic crystal with a record high ion conductivity, 0.21 S·cm-1, at 453 K. The crystal-to-plastic crystal transformation in 1 is coupled to a bistable magnetic transition to give a multi-in-one multifunctional material. This study provides a creative thought for the design of OIPCs with striking thermal, electrical, and magnetic multifunctionality.