Intermolecular Forces Regulating the Phase-Transition Temperatures in Organic-Inorganic Hybrid Materials.

Organic-inorganic hybrid phase-transition materials have attracted widespread attention in energy storage and sensor applications due to their structural adaptability and facile synthesis. However, increasing the phase-transition temperature (Tc) effectively remains a formidable challenge. In this study, we employed a strategy to regulate intermolecular interactions (different types of hydrogen bonds and other weak interactions), utilizing bismuth chloride as an inorganic framework and azetidine, 3,3-difluoro azetidine, and 3-carboxyl azetidine as organic components to synthesize three compounds with different Tc values: [C3H8N]2BiCl5 (1, 234 K), [C3H6NF2]3BiCl6 (2, 256 K), and [C4H8O2N]3BiCl6 (3, 350 K). 1 is a one-dimensional chain structure and 2 and 3 are zero-dimensional structures. Analysis of the crystal structure and the Hirshfeld surface and 2D fingerprints further suggests that the intermolecular forces are efficiently modulated. These findings emphasize the efficacy of our strategy in enhancing Tc and may facilitate further research in this area.

Dehydration Induced a Structural Transformation into a One-Dimensional Hybrid Perovskite with Second Harmonic Generation and Dual Dielectric Switching.

Hybrid organic-inorganic perovskites with structural transformation have garnered continued interest in recent years for their potential as multifunctional materials in the field of optoelectronics and smart devices. Herein, we report a novel hybrid organic-inorganic halide, [C5NOH12]2[Cd1.5Cl5(H2O)] (1). Remarkably, the centrosymmetric compound 1 undergoes a structural transformation to a novel noncentrosymmetric hybrid perovskite [C5NOH12][CdCl3] (2) after dehydration. Accompanied by the chemical bond cleavage and reorganization, the zero-dimensional (0D) trinuclear cluster in compound 1 transforms into an intriguing one-dimensional (1D) hexagonal perovskite structure in compound 2, generating multiple optoelectronic switching behaviors. It is worth mentioning that compound 2 demonstrates successive structural phase transitions at 353 and 405 K, resulting in switchable second harmonic generation (SHG) and a dual dielectric response. In addition, compounds 1 and 2 both feature blue-light luminescence, with respective photoluminescence lifetimes of 0.73 and 1.42 ns. This work will offer a pioneering approach and expansive potential for the preparation and development of hybrid organic-inorganic perovskite materials with superior properties.

Design, synthesis, and characterization of a new hybrid organic-inorganic perovskite with a high-Tc dielectric transition.

Phase change materials (PCMs) have drawn increasing attention for their promising applications in thermal switches, data communication, and energy storage. Because of the complexity of the interactions between molecules, it is still a challenge to design PCMs with a desired high phase transition temperature (Tc). In this study, a one-dimensional hybrid perovskite of (TEACCl)PbBr3 (1, TEACCl = Et3NCH2Cl) was successfully designed and synthesized with a Tc = 390 K. Disordering of TEACCl+ on the heating process is the origin of the structural phase transition of 1 from the P21/c to P63/mmc structure. It is noted that the phase transition is associated with an excellent switchable dielectric property, which indicates that 1 has the potential to be applied to sensor equipment. After calculation, 1 is an infrequent indirect bandgap semiconductor with an energy gap of 3.57 eV. Moreover, 1 exhibits strong red fluorescence under irradiation of UV light. This work will provide guidance for designing high Tc switching materials.

Dielectric property and energy storage performance enhancement for iron niobium based tungsten bronze ceramic.

Ceramic dielectric capacitors have attracted increasing interest due to their wide applications in pulsed power electronic systems. Nevertheless, synchronously achieving the high energy storage density, high energy storage efficiency and good thermal stability in dielectric ceramics is still a great challenge. Herein, lead free Sr3SmNa2Fe0.5Nb9.5O30 (SSNFN) ceramic with tetragonal tungsten bronze structure was synthesized and characterized, high total energy storage density (2.1 J cm-3), recoverable energy storage density (1.7 J cm-3), energy storage efficiency (80%) and good thermal stability are obtained simultaneously in the compound, due to the contribution of high maximum polarization (P max), low remanent polarization (P r) and large breakdown strength (E b). The high P max is related with the intrinsic characteristic of Sr4Na2Nb10O30 (SNN) based system, while the small P r and good thermal stability stem from the significantly enhanced relaxor behavior. In addition, the large E b originates from the improved microstructure with fewer defects and decreased average grain size, and the reduction of electrical heterogeneity compared with SNN. The capacitive performance obtained in this work points out the great potential of tungsten bronze ceramic designed for energy storage applications and pave a feasible way to develop novel lead-free dielectric capacitors.

Novel pharmaceutical salts of cephalexin with organic counterions: structural analysis and properties.

Three novel pharmaceutical salts of cephalexin (CPX) with 2,6-dihydroxybenzoic acid (DHBA), 5-chlorosalicylic acid (CSA) and 5-sulfosalicylic acid (SSA), which were obtained and thoroughly explored by various analytical techniques, were found to be crystallized invariably in hydrated forms. It is the proton transfer from carboxylic or sulfonic counterions to the CPX molecules that results in the salt formation. Crystal structure analyses reveal that the N-H⋯O and O-H⋯O hydrogen bonding interactions among the CPX, acidic guest molecules and water molecules play a crucial role in the packing motifs of crystal stabilization. All the salts exhibit higher solubility compared with the parent drug. These salts offer an alternative way of increasing the number of solid forms for CPX, which facilitates selection of a suitable form in the context of drug formulation development for further repurposing investigations.

Two-step nonlinear optical switch in a hydrogen-bonded perovskite-type crystal.

Switchable nonlinear optical (NLO) materials have aroused broad interest on account of their captivating optical and electronic properties. We demonstrate a novel perovskite-type crystal with exceptional hydrogen bond interactions that are associated with the onset of reorientational motions of organic cations and thus induce the occurrence of two successive phase transitions to be a two-step NLO switch. This finding affords an alternative approach for the design and assembly of switchable NLO materials.

Optical-Dielectric Duple Bistable Switches: Photoluminescence of Reversible Phase Transition Molecular Material.

Molecular optical-dielectric duple bistable switches are photoelectric (dielectric and fluorescent) multifunctional materials that can simultaneously convert optical and electrical signals in one device for seamless integration. However, exploring optical-dielectric duple channels of dielectric and photoluminescence is still a bigger challenge than single dielectric or photoluminescence bistable ones, which are hardly reported but probably will be heavily researched owing to the new generation artificial intelligence development needs in the future. Herein, a new optical-dielectric duple bistable switches material, [(CH3 )3 NCH2 CH3 ]2 MnCl4 (I), was obtained by a simple method for volatilization of solvents. Variable temperature single crystal X-ray analysis indicates that material I has a reversible bistable structure (order-disorder structure phase transition) corresponding to switching "ON'' and "OFF''. Unlike the single dielectric bistable structures that were previously reported, material I also own bistable features in terms of fluorescence property. This material enriches the specific examples of photoelectric duple function switch materials and facilitates the development of required devices.

Above room-temperature dielectric and nonlinear optical switching materials based on [(CH3)3S]2[MBr4] (M = Cd, Mn and Zn).

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.

Ultrahigh phase transition temperature in a metal-halide perovskite-type material containing unprecedented hydrogen bonding interactions.

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.

[C6N2H18][SbI5]: A Lead-free Hybrid Halide Semiconductor with Exceptional Dielectric Relaxation.

[C6N2H18][SbI5] (1), a novel metal halide semiconductor with dielectric relaxation behavior, has been successfully synthesized, in which the cavities between the one-dimensional [SbI5] n2- polyanions are occupied by 2-methyl-1,5-pentanediammonium (2-MPDA) cations. 1 undergoes a reversible solid-state phase transition at TC = 192.7 K and shows a step-like dielectric anomaly. Interestingly, above TC, distinct dielectric dispersion in a wide temperature range is also witnessed. Remarkably, the solid state UV-vis diffuse reflectance spectrum of 1 exhibits a slightly gentler absorption edge at about 650 nm; that is, 1 adopts an indirect band gap with 1.92 electron volts. The combined narrow band gap, strong photoconductivity effect, and excellent dielectric relaxation might shed light on the exploitation of lead-free hybrid metal halide molecular materials with promising application prospects in thermoresponsive relaxation-type dielectric materials and photovoltaic conversion devices.

A Semiconducting Organic-Inorganic Hybrid Perovskite-type Non-ferroelectric Piezoelectric with Excellent Piezoelectricity.

Piezoelectric materials are a class of important functional materials applied in high-voltage sources, sensors, vibration reducers, actuators, motors, and so on. Herein, [(CH3 )3 S]3 [Bi2 Br9 ](1) is a brilliant semiconducting organic-inorganic hybrid perovskite-type non-ferroelectric piezoelectric with excellent piezoelectricity. Strikingly, the value of the piezoelectric coefficient d33 is estimated as ≈18 pC N-1 . Such a large piezoelectric coefficient in non-ferroelectric piezoelectric has been scarcely reported and is comparable with those of typically one-composition non-ferroelectric piezoelectrics such as ZnO (3pC N-1 ) and much greater than those of most known typical materials. In addition, 1 exhibits semiconducting behavior with an optical band gap of ≈2.58 eV that is lower than the reported value of 3.37 eV for ZnO. This discovery opens a new avenue to exploit molecular non-ferroelectric piezoelectric and should stimulate further exploration of non-ferroelectric piezoelectric due to their high stability and low loss characteristics.

A temperature-triggered triplex bistable switch in a hybrid multifunctional material: [(CH2)4N(CH2)4]2[MnBr4].

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.

A Room-Temperature Hybrid Lead Iodide Perovskite Ferroelectric.

Organic-inorganic hybrid perovskite, [CH3NH3]PbI3, holds a great potential for next-generation solar devices. However, whether the ferroelectricity exists in [CH3NH3]PbI3 and results in the ultrahigh performance is not at present clear. Beyond that, no hybrid lead iodide perovskite ferroelectric has yet been found. Here, using precise molecular modifications, we successfully designed a room-temperature hybrid perovskite ferroelectric, [(CH3)3NCH2I]PbI3. Because of the high-symmetry and nearly spherical shape of [(CH3)4N]+ cation, [(CH3)4N]PbI3 crystallizes in a centrosymmetric space group P63/ m at room temperature and undergoes a structural phase transition at 184 K. Accompanied by the introduction of halogen atoms on the cation from F to I, the phase transition temperature gradually increases to 312 K and the space group transforms into a polar C2 at room temperature. The strongest halogen bond energy of [(CH3)3NCH2I]-I and the largest volume of [(CH3)3NCH2I]+ among these compounds might be possible reasons for the stabilization of ordered [(CH3)3NCH2I]+ cation array and further reservation of its ferroelectricity at relatively high temperature. This work provides an efficient molecular design strategy toward the targeted harvest of room-temperature organic-inorganic perovskite ferroelectrics, and should inspire further exploration of the interplay between structure and ferroelectricity. The discovery of lead iodide perovskite ferroelectric also offers a foothold to the possibility for the existence of ferroelectricity in [CH3NH3]PbI3.

Metal-free three-dimensional perovskite ferroelectrics.

Inorganic perovskite ferroelectrics are widely used in nonvolatile memory elements, capacitors, and sensors because of their excellent ferroelectric and other properties. Organic ferroelectrics are desirable for their mechanical flexibility, low weight, environmentally friendly processing, and low processing temperatures. Although almost a century has passed since the first ferroelectric, Rochelle salt, was discovered, examples of highly desirable organic perovskite ferroelectrics are lacking. We found a family of metal-free organic perovskite ferroelectrics with the characteristic three-dimensional structure, among which MDABCO (N-methyl-N'-diazabicyclo[2.2.2]octonium)-ammonium triiodide has a spontaneous polarization of 22 microcoulombs per square centimeter [close to that of barium titanate (BTO)], a high phase transition temperature of 448 kelvins (above that of BTO), and eight possible polarization directions. These attributes make it attractive for use in flexible devices, soft robotics, biomedical devices, and other applications.

Experimental Evidence for a Triboluminescent Antiperovskite Ferroelectric: Tris(trimethylammonium) catena-Tri-µ-chloro-manganate(II) Tetrachloromanganate(II).

The perovskite structure is rich in ferroelectricity. In contrast, ferroelectric antiperovskites have been scarcely confirmed experimentally since the discovery of M3 AB-type antiperovskites in the 1930s. Ferroelectricity is now revealed in an organic-inorganic hybrid X3 AB antiperovskite structure, which exhibits a clear ferroelectric phase transition 6/mmmF6mm with a high Curie point of 480 K. The physical properties across the phase transition are obviously changed along with the symmetry requirements, providing solid experimental evidence for the ferroelectric phase transition. More interestingly, the discovered antiperovskite shows intense photoluminescence and triboluminescence properties. The confirmation of the triboluminescent ferroelectric antiperovskite will open new avenues to explore excellent optoelectronic properties in the antiperovskite family.

Three-dimensional organic-inorganic hybrid sodium halide perovskite: C4H12N2·NaI3 and a hydrogen-bonded supramolecular three-dimensional network in 3C4H12N2·NaI4·3I·H2O.

The rational selection of ligands is vitally important in the construction of new organic-inorganic hybrid three-dimensional perovskite complexes. As part of an exploration of perovskite-type materials, two new Na-I compounds based on the piperazine ligand, namely poly[piperazinediium [tri-µ-iodido-sodium]], {(C4H12N2)[NaI3]}n, 1, and catena-poly[tris(piperazinediium) [[triiodidosodium]-µ-iodido] triiodide monohydrate], {(C4H12N2)3[NaI4]I3·H2O}n, 2, have been synthesized by adjusting the stoichiometric ratio of sodium iodide and piperazine, and were characterized by single-crystal X-ray diffraction. In the crystal structures of 1 and 2, each NaI cation is linked to six I atoms, but the compounds show completely different configurations. In 1, the structure includes a perovskite-like array of vertex-sharing NaI6 octahedra stretching along the direction of the three axes, and each piperazinediium dication is enclosed in the NaI3 perovskite cage. However, in 2, each NaI atom bridges a single I atom to form a one-dimensional linear chain, and complex intermolecular hydrogen bonds connect these one-dimensional chains into a three-dimensional supramolecular network.

High-temperature reversible phase transitions and exceptional dielectric anomalies in cobalt(ii) based ionic crystals: [Me3NCH2X]2[CoX4] (X = Cl and Br).

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.

A new two-dimensional polymeric cadmium(II) complex containing dicyanamide bridging ligands.

As part of an exploration of new coordination polymers, a cadmium-dicyanamide complex, namely poly[benzyltriethylammonium [tri-µ-dicyanamido-κ6N1:N5-cadmium(II)]], {(C13H22N)[Cd(C2N3)3]}n, has been synthesized by the reaction of benzyltriethylammonium bromide, cadmium nitrate tetrahydrate and sodium dicyanamide in aqueous solution, and characterized by single-crystal X-ray diffraction at room temperature. In the crystal structure, each CdII cation is coordinated by six nitrile N atoms from six anionic dicyanamide (dca) ligands to furnish a slightly distorted octahedral geometry. Neighbouring CdII cations are linked by dicyanamide bridges to construct a two-dimensional anionic layer coordination polymer. One amide N atom in the bridging dca ligand is disordered over two sites. The cations lie between the anionic frameworks and there are no hydrogen-bond interactions between the cations and anions. The organic cations are not involved in the formation of the supramolecular network.

A room temperature reversible phase transition containing dielectric switching of a host-guest supramolecular metal-halide compound.

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.

Crystal structure of poly[(4-amino-pyridine-κN)(N,N-di-methyl-formamide-κO)(µ3-pyridine-3,5-di-carboxyl-ato-κ(3) N:O (3):O (5))copper(II)].

The title compound, [Cu(C7H3NO4)(C5H6N2)(C3H7NO] n , is an amino-function-alized chiral metal-organic framework with (10,3)-a topology. It has been constructed via the assembly of the achiral triconnected pyridine-3,5-di-carboxyl-ate (3,5-PDC) building block and a triconnected Cu(II) atom. Each Cu(II) ion is coordinated by two O atoms and one N atom, respectively, of three crystallographically independent 3,5-PDC ligands. The square-pyramidal (CuN2O3) coordination geometry of the Cu(II) ion is completed by an N atom of a terminal 4-amino-pyridine (4-APY) ligand and the O atom of a terminal N,N-di-methyl-formamide (DMF) ligand to give a triconnected 'T'-shaped secondary building unit, which becomes trigonal in the resulting (10,3)-a topology. In the three-dimensional structure, weak N-H⋯O hydrogen bonds are observed in which the donor N-H groups are provided by the 4-APY ligands and the acceptor O atoms are provided by the non-coordinating carboxylate O atoms of the 3,5-PDC ligands.