Phase transition and ionic conduction enhancement induced by co-doping of LiI and MnI2 in a one-dimensional lead iodide perovskite.

Herein, we demonstrated the unique advantage of a mechanochemical reaction to prepare a salt with hard and soft acid and base ions concurrently by solution synthesis owing to the soft acid preferring to combine with the soft base and vice versa. We prepared Bu4N1-xLixMnxPb1-xI3 (x = 0.011-0.14) by mechanochemical synthesis. The doping induced a structural phase transition at ∼342 K and much enhancement of ionic conduction above 342 K for all co-doped hybrids regarding Bu4NPbI3 because of the voids around the Mn2+/Li+ ions by doping.

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.

A Rotorlike Supramolecular Assembly, {[K(18-crown-6)]PbI3}∞, with a Reversible Breaking-Symmetry Phase Transition near Room Temperature.

A rotorlike supramolecular crystal, {[K(18-crown-6)]PbI3}∞, is composed of a linear [PbI3]∞ chain acting as a stator and [K(18-crown-6)]+ cations fastened to the [PbI3]∞ chain and K-I bond like rotators and axes, respectively. A reversible breaking-symmetry phase transition occurs at ∼305 K. Variable-temperature 1H NMR spectra and dielectrics were used for the dynamic analysis of [K(18-crown-6)]+ cations in the crystal.

An organometallic half-sandwich supramolecular complex {K(18-Crown-6)(ηn-C6H5B(C6H5)3)} (n = 1-6) exhibiting a reversible breaking-symmetry phase transition and switchable dielectric behaviour.

A supramolecular crystal, built from a 1 : 1 molar ratio of potassium tetraphenylboron (KBPh4) with 1,4,7,10,13,16-hexaoxacyclooctadecane (18-Crown-6), contains an organometallic half-sandwich superstructure unit {K(18-Crown-6)(ηn-C6H5B(C6H5)3)} (1 with n = 1-6), and shows a reversible phase transition at ∼211 K. The analysis of crystal structures at 173 K in the low-temperature phase, and 293 and 423 K in the high-temperature phase revealed that the breaking-symmetry phase transition is associated with the order-disorder transformation of [K(18-Crown-6)]+ and the change of the coordination mode of the phenyl ring to K+. A dielectric anomaly appears at ca. 212 K and dielectric relaxation occurs above 375 K in 1. The dielectric and thermal anomaly temperatures are close to each other, and the dielectric relaxation is relevant to the relative displacement of [K(18-Crown-6)]+ and the tetraphenylboron anion.