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In this paper, three zero-dimensional organic–inorganic hybrid compounds [(CH3)3S]2[CdBr4] (1), [(CH3)3S]2[MnBr4] (2) and [(CH3)3S]2[ZnBr4] (3) were synthesized. The phase transition behavior of 1, 2 and 3 was well characterized by differential scanning calorimetry (DSC) and variable temperature single crystal diffraction measurements. The phase transition temperature of 1, 2 and 3 was at ca. 315 K in the heating process. The vigorous ordered–disordered reorientation and displacement motion of [(Me3)3S]+ and [MBr4]2− of 1, 2 and 3 induce the structural phase transition from the centrosymmetric (CS) space group Pnma to the non-centrosymmetric (NCS) space group P212121. The apparent second-harmonic generation (SHG) switching responses further confirm this CS to NCS symmetry breaking. Moreover, dielectric studies illustrate that 1, 2 and 3 display distinctly switchable dielectric behavior, revealing their potential application in dielectric switches. This finding suggests that sulfonium-based organic–inorganic hybrids can be used to build phase transition materials, broadening the way for exploring dielectric and nonlinear optical (NLO) switching materials. [ABSTRACT FROM AUTHOR]

A novel organic–inorganic ABX3 perovskite-type material with specific hydrogen bonding interactions, N,N-dimethylethanolammonium trichlorocadmate ([DMEA]CdCl3), has been synthesized as a phase transition material. It is notable that the DMEA cations are arranged to form one-dimensional chains connected by hydrogen bonds at room temperature, which are very sparse in other perovskite-type compounds. The strong intermolecular interactions have made the phase transition temperature of the material reach up to 429 K, as confirmed by differential scanning calorimetry measurements, variable-temperature structural analyses, and dielectric measurements. The origin of the symmetry-breaking phase transition is associated with the motion or reorientation of the DMEA cations, accompanied by the crystal structures from orthorhombic Pnma to monoclinic P21/c with the temperature decreases. The finding of [DMEA]CdCl3 with unprecedented hydrogen bonding interactions has opened a new avenue to design novel phase transition materials with higher transition temperatures. [ABSTRACT FROM AUTHOR]

Bistable optical-electrical duplex switches represent a class of highly desirable intelligent materials because of their potential applications in the fields of next-generation flexible devices. However, controllable photoelectric switchable materials with high-performance dielectric-switching and optical-switching properties are still scarce, with triplex bistable switches being rarely reported. Herein, a novel optoelectronic triple-functional organic–inorganic material, 5-azonia-spiro[4,4]nonane tetrabromomanganese (1, [ASN]2[MnBr4], ASN = (CH2)4N(CH2)4), which undergoes a reversible solid-state phase transition around 327 K and exhibits a recognizable second harmonic generation (SHG) effect between SHG-on and SHG-off states, has been successfully synthesized and grown as block crystals. Intriguingly, the bromine-doped crystal can exhibit intense green luminescence with a high quantum yield of 13.07% under UV excitation, extending its application in the field of photoelectric seamless integration and/or flexible multifunctional devices. [ABSTRACT FROM AUTHOR]

Two isostructural ionic cobalt(ii) halides, trimethylchloromethyl ammonium tetrachlorocobalt(ii) (1, [Me3NCH2Cl]2[CoCl4]) and trimethylbromomethyl ammonium tetrabromocobalt(ii) (2, [Me3NCH2Br]2[CoBr4]), have been discovered as new high-temperature phase transition materials. 1 exhibits two successive structural phase transitions from P212121 to P21/c at 252 K and then to Pnma at 335 K, accompanied by step-like dielectric anomalies. The two-step sequential reversible phase transitions of 1 derive from the order–disorder transformation of CoCl4 anions and organic Me3NCH2Cl cations, respectively. Its analogue 2 also crystallizes in P21/c at 293 K by changing the halogen atoms of both cations and anions of 1. Unlike 1, 2 displays only one structural phase transition with a much higher transition temperature at 387 K, which is mainly influenced by intermolecular interactions and more energy is required to provide the freedom of the motion. All the findings in the present work indicate that the phase transition temperature and properties of materials can be tuned by using halogens in this series of compounds, which could open a new way to design and assemble novel high-temperature phase transition materials. [ABSTRACT FROM AUTHOR]

Following our recent findings on dielectric materials, we synthesized a new host–guest supramolecular metal–halide compound, [(2-AMPD)(18-crown-6)]CuCl4 (1, 2-AMPD = 2-aminomethylpiperidinium). Systematic characterization techniques such as variable-temperature crystal structure analyses, differential scanning calorimetry (DSC) measurements, temperature-dependent dielectric measurements and powder X-ray diffraction (PXRD) measurements demonstrate that 1 undergoes a reversible phase transition at room temperature, accompanied by switchable dielectric responses and remarkable anisotropy along three different crystallographic axes. The structural phase transition mechanism is triggered by the order–disorder transition of the 18-crown-6 molecules. We believe that these findings might further promote the application of a host–guest inclusion compound in the field of switchable dielectric materials. [ABSTRACT FROM AUTHOR]

A novel zigzag chain organic–inorganic hybrid compound of the general formula R2MI5, [n-C3H7NH3]2[SbI5] (1), was successfully synthesized, in which the n-propylammonium cations were located in the free cavities between the one-dimensional zigzag chains. Systematic characterization was performed to investigate the phase transition of 1. A pair of sharp peaks at 211.8 K (heating) and 203.7 K (cooling) with a hysteresis 8.1 K were observed in the differential scanning calorimetry (DSC) curve, indicating the first-order phase transition behavior of 1. The temperature dependence dielectric measurement demonstrated a step-like change at around 211.8 K, which makes 1 a potential switchable dielectric material. Frequency dependence measurement revealed that the frequency exerts a weak influence on the dielectric permittivity. Further structural analysis shows that both anionic and cationic moieties contribute to the phase transition, accompanied by weak hydrogen bond interactions between cations and the [SbI5]n2− chains. [ABSTRACT FROM AUTHOR]

A novel zigzag chain organic–inorganic hybrid compound of the general formula R2MI5, [n-C3H7NH3]2[SbI5] (1), was successfully synthesized, in which the n-propylammonium cations were located in the free cavities between the one-dimensional zigzag chains. Systematic characterization was performed to investigate the phase transition of 1. A pair of sharp peaks at 211.8 K (heating) and 203.7 K (cooling) with a hysteresis 8.1 K were observed in the differential scanning calorimetry (DSC) curve, indicating the first-order phase transition behavior of 1. The temperature dependence dielectric measurement demonstrated a step-like change at around 211.8 K, which makes 1 a potential switchable dielectric material. Frequency dependence measurement revealed that the frequency exerts a weak influence on the dielectric permittivity. Further structural analysis shows that both anionic and cationic moieties contribute to the phase transition, accompanied by weak hydrogen bond interactions between cations and the [SbI5]n2− chains. [ABSTRACT FROM AUTHOR]

A novel organic–inorganic hybrid layered perovskite-type compound of the general formula A2BX4, bis(IBA)tetrabromolead(ii) (1, IBA = isobutyl-ammonium cation), has been successfully synthesized and grown as flake-like crystals, and undergoes two reversible solid-state phase transitions at 315 K and 250 K, and has been systematically characterized using differential scanning calorimetry measurements, variable-temperature structural analyses, variable-temperature powder X-ray diffraction measurements and dielectric measurements. 1 exhibits a remarkable temperature-dependent dielectric behavior, which could be switched between high and low dielectric states above room temperature, and a broad peak exists below room temperature. The most striking dielectric property is the remarkable anisotropy along the various crystallographic axes. All of these demonstrate its potential application as a high temperature switchable molecular dielectric and low temperature phase transition material. [ABSTRACT FROM AUTHOR]

A novel organic–inorganic hybrid layered perovskite-type compound of the general formula A2BX4, bis(IBA)tetrabromolead(ii) (1, IBA = isobutyl-ammonium cation), has been successfully synthesized and grown as flake-like crystals, and undergoes two reversible solid-state phase transitions at 315 K and 250 K, and has been systematically characterized using differential scanning calorimetry measurements, variable-temperature structural analyses, variable-temperature powder X-ray diffraction measurements and dielectric measurements. 1 exhibits a remarkable temperature-dependent dielectric behavior, which could be switched between high and low dielectric states above room temperature, and a broad peak exists below room temperature. The most striking dielectric property is the remarkable anisotropy along the various crystallographic axes. All of these demonstrate its potential application as a high temperature switchable molecular dielectric and low temperature phase transition material. [ABSTRACT FROM AUTHOR]

A new organic–inorganic hexagonal perovskite-type compound with the formula ABX3, thiazolium tribromocadmate(ii) (1), in which thiazolium cations are situated in the space between the one-dimensional chains of face-sharing CdBr6 octahedra, has been successfully synthesized. Systematic characterizations including differential scanning calorimetry measurements, variable-temperature structural analyses, and dielectric measurements reveal that it undergoes two structural phase transitions, at 180 and 146 K. These phase transitions are accompanied by remarkable dielectric relaxation and anisotropy. The thiazolium cations remain orientationally disordered during the two phase transition processes. The origins of the phase transitions at 180 and 146 K are ascribed to the slowing down and reorientation of the molecular motions of the cations, respectively. Moreover, the dielectric relaxation process well described by the Cole–Cole equation and the prominent dielectric anisotropy are also connected with the dynamics of the dipolar thiazolium cations. [ABSTRACT FROM AUTHOR]

A new organic–inorganic hexagonal perovskite-type compound with the formula ABX3, thiazolium tribromocadmate(ii) (1), in which thiazolium cations are situated in the space between the one-dimensional chains of face-sharing CdBr6 octahedra, has been successfully synthesized. Systematic characterizations including differential scanning calorimetry measurements, variable-temperature structural analyses, and dielectric measurements reveal that it undergoes two structural phase transitions, at 180 and 146 K. These phase transitions are accompanied by remarkable dielectric relaxation and anisotropy. The thiazolium cations remain orientationally disordered during the two phase transition processes. The origins of the phase transitions at 180 and 146 K are ascribed to the slowing down and reorientation of the molecular motions of the cations, respectively. Moreover, the dielectric relaxation process well described by the Cole–Cole equation and the prominent dielectric anisotropy are also connected with the dynamics of the dipolar thiazolium cations. [ABSTRACT FROM AUTHOR]

Bistable optical-electrical duplex switches represent a class of highly desirable intelligent materials because of their potential applications in the fields of next-generation flexible devices. However, controllable photoelectric switchable materials with high-performance dielectric-switching and optical-switching properties are still scarce, with triplex bistable switches being rarely reported. Herein, a novel optoelectronic triple-functional organic–inorganic material, 5-azonia-spiro[4,4]nonane tetrabromomanganese (1, [ASN]2[MnBr4], ASN = (CH2)4N(CH2)4), which undergoes a reversible solid-state phase transition around 327 K and exhibits a recognizable second harmonic generation (SHG) effect between SHG-on and SHG-off states, has been successfully synthesized and grown as block crystals. Intriguingly, the bromine-doped crystal can exhibit intense green luminescence with a high quantum yield of 13.07% under UV excitation, extending its application in the field of photoelectric seamless integration and/or flexible multifunctional devices. [ABSTRACT FROM AUTHOR]