Designing Zero-Dimensional Cadmium-Based Organic-Inorganic Hybrids: The Role of Halogen Doping in Modulating Multifunctional Properties.

Advances in materials science are increasingly dependent on the development of multifunctional materials capable of improving system efficiency and reducing the environmental impact. In this study, two zero-dimensional (0D) cadmium-based organic-inorganic hybrid materials (BEMPD)2CdBr4 (BEMPD-Br, 1) and (BEMPD)2CdBr2Cl2 (BEMPD-ClBr, 2) (BEMPD = 1-(2-bromoethyl)-1-methylpiperidine) were prepared by halogen doping. Compound 2 is a mixed halide in which there are two halogen sites, Cl and Br, and in a disordered state, which has a regulatory effect on the structural distortion and properties of the compound. The Curie temperatures of compounds 1 and 2 are 348 and 390 K, respectively, and the UV-vis absorption spectra showed that the direct band gaps of compounds 1 and 2 were 4.68 and 4.8 eV, respectively. In addition, room-temperature photoluminescence experiments show broadband emission peaks at 717 and 683 nm for compounds 1 and 2, respectively, with fluorescence lifetimes of 2.414 and 3.915 µs. These 0D hybrids provide an avenue for the development of smart materials and optoelectronic devices, and also provide positive clues for manipulating the properties of organic-inorganic hybrid compounds.

High-Temperature Phase Transition with Switchable Dielectric Behavior and Significant Photoluminescence Changes in a Zero-Dimensional Hybrid SbBr6 Perovskite.

In the past decade, metal halide materials have been favored by many researchers because of their excellent physical and chemical properties under thermal, electrical, and light stimuli, such as ferroelectricity, dielectric, nonlinearity, fluorescence, and semiconductors, greatly promoting their application in optoelectronic devices. In this study, we successfully constructed an unleaded organic-inorganic hybrid perovskite crystal: [Cl-C6H4-(CH2)2NH3]3SbBr6 (1), which underwent a high-temperature reversible phase transition near Tp = 368 K. The phase transition behavior of 1 was characterized by differential scanning calorimetry, accompanied by a thermal hysteresis of 6 K. In addition, variable-temperature Raman spectroscopy analysis and PXRD further verified the sensitivity of 1 to temperature and the phase transition from low symmetry to high symmetry. Temperature-dependent dielectric testing shows that 1 can be a sensitive switching dielectric constant switching material. Remarkably, 1 exhibits strong photoluminescence emission with a wavelength of 478 nm and a narrow band gap of 2.7 eV in semiconductors. As the temperature increases and decreases, fluorescence undergoes significant changes, especially near Tc, which further confirms the reversible phase transition of 1. All of these findings provide new avenues for designing and assembling new phase change materials with high Tp and photoluminescence properties.

Silver/Antimony-Base Multifunctional Double Perovskite with H/F Substitution Enhance Properties.

Two-dimensional double perovskites have experienced rapid development due to their outstanding optoelectronic properties and diverse structural characteristics. However, the synthesis of high-performance multifunctional compounds and the regulation of their properties still lack relevant examples. Herein, we synthesized two multifunctional compounds, (C6H14N)4AgSbBr8 (1) and (F2-C6H12N)4AgSbBr8 (2), which exhibit high solid-state phase transition temperature, bistable dielectric constant switching, second harmonic generation (SHG), and bright emission. Through H/F substitution, the transition temperature increases and achieves a smaller band gap attributed to reduced interlayer spacing. Furthermore, we investigated the broad emission mechanism of the compounds through first-principles calculation and variable-temperature fluorescence, confirming the presence of the STE1 emission. Our work provides insight into the further development of multifunctional compounds and chemical modification that enhances compound properties.

Investigating the Structure-property Relationships of Two Cd-based Hybrid Multifunctional Compounds with High Tc, Bright Fluorescence and Wide Band-gap.

Organic-inorganic hybrid multifunctional materials have shown significant application in lighting and sensor fields, owing to their prominent performance and diversity structures. Herein, we synthesized two multifunctional compounds: (propyl-quinuclidone)2 CdBr4 (1) and (F-butyl-quinuclidone)2 CdBr4 (2). By introducing light-emitting organic cation with flexible long chain, 1 and 2 exhibit excellent transition properties and bright blue-white fluorescence. Then, combine fluorescence lifetime and first-principal calculation, providing evidence for the electron transfer emission. Subsequently, investigated the impact of substituent carbon chain length (methyl to butyl), structural rigidity (C-C to C-F) and halide framework (Cl to I) on the fluorescence properties. Results indicate that Cd⋅⋅⋅Cd distance and structural rigidity play an important role in fluorescence. Overall, our research provides valuable insight and example for chemical modifications enhance compound performance.

Halogen-regulating induced reversible high-temperature dielectric and thermal transitions in novel layered organic-inorganic hybrid semiconducting crystals.

Organic-inorganic hybrid metal halides for high-temperature phase transition have become increasingly popular owing to their wide operating temperature range in practical applications, e.g., energy storage, permittivity switches and opto-electronic devices. This paper describes the subtle assembly of two new hybrid perovskite crystals, [Cl-C6H4-(CH2)2NH3]2CdX4 (X = Br 1; Cl 2), undergoing high-T reversible phase transformations around 335 K/356 K. Differential scanning calorimetry (DSC), differential thermal analysis (DTA) and VT PXRD tests uncover their reversible first-order phase transition behaviors. Furthermore, the compounds exhibit switchable dielectricity near T, making them potential dielectric switching materials. Hirshfeld surface analysis well discloses a distinct difference in hydrogen-bonding interaction between 1 and 2. UV spectra and computational analysis demonstrate that the compounds are a type of direct-band-gap semiconductor. This research will contribute an effective approach to the structure and development of multifunctional molecular hybrid crystals.

2-Chloroethylamine·trifluoromethanesulfonate combined with 18-crown-6: a ferroelectric with excellent dielectric switching properties.

Ferroelectric materials are not only important electronic functional materials, but also considered as the most promising intelligent basic materials, because they show good application prospects. Therefore, it is an urgent task to develop and explore new ferroelectric material systems. In addition, the most important feature of crown ethers is their ability to complex with positive ions, which is extremely useful in synthesis. We report that [NH3C2H4Cl(18-crown-6)](CF3SO3) (1) has a phase transition temperature Tc = 255 K, and there is an obvious SHG switch below Tc. At the same time, the saturation polarization value Ps = 1.25 µC cm-2 is obtained from the hysteresis loop, which directly proves the ferroelectric nature of compound 1. It is noteworthy that the second harmonic response test of compound 1 shows a symmetric transition from a non-centrosymmetric to a centrosymmetric point group, that is a symmetry break from the paraelectric phase to the ferroelectric phase. This work is expected to promote the further exploration of organic crown ether ferroelectrics and provide a way to design and synthesize organic crown ether ferroelectrics.

Zero-Dimensional Sn-Based Enantiomeric Phase-Transition Materials with High-Tc and Dielectric Switching.

The combination of chirality and phase-transition materials has broad application prospects. Therefore, based on the quasi-spherical theory and the thought strategy of introducing chirality, we have successfully synthesized a pair of chiral enantiomeric ligands (R/S)-triethyl-(2-hydroxypropyl)ammonium iodide, which can be combined with a tin hexachloride anion to obtain a pair of new organic-inorganic hybrid enantiomeric high-temperature plastic phase-transition materials: (R/S)-[CH3 CH(OH)CH2 N(CH2 CH3 )3 ]2 SnCl6 (1-R/1-S), which have a high temperature phase transition of Tc =384 K, crystallize in the P21 chiral space group at room temperature, and have obvious CD signals. In addition, compounds 1-R and 1-S have a good low-loss dielectric switch and broadband gap. This work is conducive to the research into chiral high-temperature reversible plastic phase-transition materials, and promotes the development of multi-functional phase-transition materials.

Excellent Switchable Properties, Broad-Band Emission, Ferroelectricity, and High Tc in a Two-Dimensional Hybrid Perovskite: (4,4-DCA)2PbBr4 Exploited by H/F Substitution.

Switchable materials have gained significant attention due to their potential applications in data storage, sensors, and switching devices. Two-dimensional (2D) hybrid perovskites have demonstrated promising prospects for designing switchable materials, where the dynamic motion of the organic components coupled with the distortion of the inorganic framework provides the driving force for triggering multifunctional switchable properties. Herein, through the H/F substitution strategy, we report a polar 2D hybrid lead-based perovskite, (4,4-DCA)2PbBr4 (4,4-DCA = 4,4-difluorocyclohexylammonium) (1), which exhibits dual-stable behavior in a dielectric and second harmonic generation (SHG) response during the reversible phase transition process near the high Curie temperature Tc ∼ 409 K. The phase transition temperature is significantly increased by 41 K compared to the corresponding non-fluorinated (CHA)2PbBr4 (CHA = cyclohexylammonium). Remarkably, the material shows rare broad-band yellow emission under UV excitation, attributed to the induction of self-trapped exciton emission by the distortion of the [PbBr6]4- octahedra, as confirmed by the first-principles analysis. 1 also exhibited ferroelectricity with a saturation polarization value and a small coercive field. This study provides a new insight into the modification of multifunctional switchable materials through the H/F substitution strategy.

High-Temperature Ferroelasticity and Photoluminescence in a 2D Monolayer Perovskite Compound: (C5NH8Br)2PbBr4.

Hybrid organic-inorganic perovskites (HOIPs) have attracted much attention due to their excellent properties and easy synthesis. As far as we know, most documented ferroelastics mainly focus on the 3D (three-dimensional) perovskites, the 2D monolayer perovskite ferroelastics are rarely reported before. In this work, we synthesized a 2D lead-based perovskite (C5NH13Br)2PbBr4 (1) (C5NH13Br = 5-bromoamylamine cation) by introducing flexible chain organic cations. The evolution of ferroelastic domains observed by a polarized light microscope confirms that compound 1 undergoes a ferroelastic phase transition at 392/384 K. In addition, its direct band gap is 2.877 eV. Interestingly, the material emits an attractive blue light (quantum yield 5.06%) under UV light. Three structural descriptors are introduced to quantitatively analyze the relationship between structural distortion and the shape of emission peak. This work provides a way to design multifunctional perovskite-type materials.

Large Spontaneous Polarization Ferroelectric Property, Switchable Second-Harmonic Generation Responses, and Magnetism in an Fe-Based Compound.

Since the switchable spontaneous polarization of ferroelectric materials endows it with many useful properties such as a large pyroelectric coefficient, switchable spontaneous polarization, and semiconductor, it has a wide range of application prospects, and the research of high-performance molecular ferroelectric materials has become a hot spot. We obtained a 0D organic-inorganic hybrid ferroelectric [(CH3)3NCH2CH2CH3]2FeCl4 (1) with well-defined ferroelectric domains and excellent domain inversion and exhibited a relatively large spontaneous polarization (Ps = 9 µC/m-2) and a Curie temperature (Tc) of 394 K. Furthermore, compound 1 belongs to the non-centrosymmetrical space group Cmc21 and has a strong second-harmonic generation signal. Interestingly, we also performed magnetic tests on 1, which confirmed that it is a magnetic material. This work provides clues for exploring the application of high-performance molecular ferroelectric materials in future multifunctional smart devices.

High-Tc 1D Phase-Transition Semiconductor Photoluminescent Material with Broadband Emission.

One dimensional (1D) organic-inorganic halide hybrid perovskites have the advantages of excellent organic cation modifiability and diversity of inorganic framework structures, which cannot be ignored in the development of multi-functional phase-transition materials in photoelectric and photovoltaic devices. Here, we have successfully modified and synthesized an organic-inorganic hybrid perovskite photoelectric multifunctional phase-transition material: [C7 H13 ONCH2 F]⋅PbBr3 (1). The synergistic effect of the order double disorder transition of organic cations and the change of the degree of distortion of the inorganic framework leads to its high temperature reversible phase-transition point of Tc =374 K/346 K and its ultra-low loss high-quality dielectric switch response. Through in-depth research and calculation, compound 1 also has excellent semiconductor characteristics with a band gap of 3.06 eV and the photoluminescence characteristics of self-trapped exciton (STE) broadband emission. Undoubtedly, this modification strategy provides a new choice for the research field of organic-inorganic hybrid perovskite reversible phase-transition photoelectric multifunctional materials with rich coupling properties.

1D Chiral Lead Bromide Perovskite with Superior Second-Order Optical Nonlinearity, Photoluminescence, and High-Temperature Reversible Phase Transition.

Multifunctional materials are an attractive research area. Organic-inorganic hybrid perovskites are widely used in the design of these materials due to their rich properties and flexible composition. It is easy to obtain more photoelectric properties by introducing chiral groups as ligands. In this work, we synthesized chiral one-dimensional organic-inorganic hybrid perovskites, namely (R/S-3-HP)PbBr3 (1R/1S) (3-HP=3-hydroxy-piperidine). The enantiomer compounds undergo reversible phase transition at 349/336 K. Under the excitation light of 339 nm, 1R and 1S have a wide emission peak at 635 nm, showing orange light. In addition, the indirect bandgap is 3.29 eV and the SHG intensity is comparable to that of KDP. This work provides a way to design multifunctional chiral perovskite materials.

Targeting inflammatory macrophages rebuilds therapeutic efficacy of DOT1L inhibition in hepatocellular carcinoma.

Epigenetic reprogramming is a promising therapeutic strategy for aggressive cancers, but its limitations in vivo remain unclear. Here, we showed, in detailed studies of data regarding 410 patients with human hepatocellular carcinoma (HCC), that increased histone methyltransferase DOT1L triggered epithelial-mesenchymal transition-mediated metastasis and served as a therapeutic target for human HCC. Unexpectedly, although targeting DOT1L in vitro abrogated the invasive potential of hepatoma cells, abrogation of DOT1L signals hardly affected the metastasis of hepatoma in vivo. Macrophages, which constitute the major cellular component of the stroma, abrogated the anti-metastatic effect of DOT1L targeting. Mechanistically, NF-κB signal elicited by macrophage inflammatory response operated via a non-epigenetic machinery to eliminate the therapeutic efficacy of DOT1L targeting. Importantly, therapeutic strategy combining DOT1L-targeted therapy with macrophage depletion or NF-κB inhibition in vivo effectively and successfully elicited cancer regression. Moreover, we found that the densities of macrophages in HCC determined malignant cell DOT1L-associated clinical outcome of the patients. Our results provide insight into the crosstalk between epigenetic reprogramming and cancer microenvironments and suggest that strategies to influence the functional activities of inflammatory cells may benefit epigenetic reprogramming therapy.

Dielectric Relaxation and Dielectric Switching Behaviors in (N,N-Diisopropylethylamine) Tetrachloroantimonate(III).

Dielectric switches have drawn renewed attention to the study of their many potential applications with the adjustable switch temperatures (Ts ). Herein, a novel antimony-based halide semiconductor, (N,N-diisopropylethylamine) tetrachloroantimonate ((DIPEA)SbCl4 , DIPEA+ =N,N-diisopropylethylamine), with dielectric relaxation behavior and dielectric switches has been successfully synthesized. This compound, consisting of coordinated anion S b C l 4 ∞ - ${{\left[{{\rm S}{\rm b}{\rm C}{\rm l}}_{4}\right]}_{\infty }^{-}}$ chains and isolated DIPEA+ cations, undergoes an isostructural order-disorder phase transition and shows a step-like dielectric anomaly, which can function as a frequency-tuned dielectric switch with highly adjustable switch temperature (Ts ). Variable-temperature single-crystal structure analyses and first-principles molecular dynamics simulations give information about the general mechanisms of molecular dynamics. This work enriches the dielectric switch family and proves that hybrid metal halides are promising candidates for switchable physical or chemical properties.

Two Manganese(II)-Based Hybrid Multifunctional Phase Transition Materials with Strong Photoluminescence, High Quantum Yield, and Switchable Dielectric Properties: (C6NH16)2MnBr4 and (C7NH18)2MnBr4.

Multifunctional materials have always been an attractive research area, but how to combine multiple excellent properties in one compound remains a considerable challenge. Organic-inorganic hybrid compounds are widely used in the design of such materials due to their rich properties and flexible assembly. Herein, two new manganese(II)-based organic-inorganic hybrid compounds, (C6NH16)2MnBr4 (1) and (C7NH18)2MnBr4 (2), are prepared by the solution method. Compounds 1 and 2 both emit extremely strong green light under UV excitation, with high quantum yields of 45.93 and 50.98%, respectively. In addition, reversible solid-state phase transitions and obvious switchable dielectric properties are shown at 378/366 and 361/352 K, respectively. The coexistence of the dual stimulus-response characteristics of temperature and light in compounds 1 and 2 opens a new path for exploring more multifunctional phase transition materials.

Unusual symmetry breaking in high-temperature enantiomeric ferroelectrics with large spontaneous polarization.

Chiral organic-inorganic hybrid perovskites have gained extensive research interest due to their combination of chirality and the excellent optical, electrical and spin properties of perovskite materials, especially in two-dimensional hybrid perovskites. Herein, we report two-dimensional organic-inorganic perovskite enantiomeric ferroelectric [(R)-ß-MPA]2CdCl4 (1) and [(S)-ß-MPA]2CdCl4 (2) (MPA+ =methylphenethylammonium). Their mirror relationships are verified by both circular dichroism (CD) and crystal structures. At the same time, the two exhibit very similar ferroelectricity and related properties, including high Curie temperature (343 K), large spontaneous polarization (4.65 µC cm-2), and low coercive force field (13 kV cm-1). Unusually, at room temperature the crystal phase is monoclinic with the space group C2 and above the phase transition temperature it is triclinic with the space group P1, which means that the symmetry decreases with the increase of temperature. In addition, it exhibits a flexible switchable SHG response, while [(R)-ß-MPA]2CdCl4 and [(S)-ß-MPA]2CdCl4 have wide band gaps of 4.21 and 4.26 eV, respectively, mainly contributed by inorganic CdCl6 octahedra. This discovery opens a new way for the construction of two-dimensional enantiomeric molecular ferroelectrics.

Neutral 1D Perovskite-Type ABX3 Phase Transition Material with a Narrowband Emission and Semiconductor Property.

Cyclic organic amines are emerging as excellent building blocks to assemble organic-inorganic hybrid phase transition materials due to their flexible cyclic structure. Here, we have assembled a 1D organic-inorganic hybrid dielectric material C5 H6 NOPbBr3 (1) by alloying the cyclic organic amine 3-hydroxypyridine. 1 displays a remarkable switchable dielectric response induced by an order-disorder transformation of the organic moiety, this transformation behaviour is confirmed by DSC and Hirshfeld surface measurements. More interestingly, 1 has a narrowband emission (FWHM=4.64 nm) at 590 nm; FWHM is a major quality figure for narrowband photodetectors. In addition, 1 exhibits semiconducting properties with an indirect bandgap of 2.78 eV by the analysis of the UV-Vis absorption results.

High-Temperature Phase Transition Containing Switchable Dielectric Behavior, Long Fluorescence Lifetime, and Distinct Photoluminescence Changes in a 2D Hybrid CuBr4 Perovskite.

A novel organic-inorganic hybrid perovskite crystal, [ClC6H4(CH2)2NH3]2CuBr4 (1), having experienced an invertible high-temperature phase transition near Tc (the Curie temperature Tc = 355 K), has been successfully synthesized. The phase-transition characteristics for compound 1 are thoroughly revealed by specific heat capacity (Cp), differential thermal analysis, and differential scanning calorimetry tests, possessing 16 K broad thermal hysteresis. Multiple-temperature powder X-ray diffraction analysis further proves the phase-transition behavior of compound 1. Moreover, compound 1 exhibits a significant steplike dielectric response near Tc, revealing that it can be deemed to be a promising dielectric switching material. The variable-temperature fluorescence experiments show distinct photoluminescence (PL) changes of compound 1. Further investigation and calculation disclose that the fluorescence lifetime of compound 1 can reach as long as 55.46 µs, indicating that it can be a potential PL material. All of these researches contribute a substitutable avenue in the design and construction of neoteric phase-transition compounds combining high Curie temperature and PL properties.

A multifunctional molecular ferroelectric with chiral features, a high Curie temperature, large spontaneous polarization and photoluminescence: (C9H14N)2CdBr4.

Low-dimensional chiral organic-inorganic hybrid metal halides have attracted a lot of attention in recent years due to their unique intrinsic properties, including having potential applications in optoelectronic and spintronic devices. However, low-dimensional chiral molecular ferroelectrics are very rare. In this paper, we report a novel zero-dimensional molecular ferroelectric (C9H14N)2CdBr4 (C9H14N+ = protonated 3-phenylpropylamine), which has obvious dielectric and thermal anomalies and shows a high Curie temperature at 395 K. It crystallizes in the P21 space group at room temperature, showing a strong CD signal, large spontaneous polarization (P s = 13.5 µC cm-2), and a clear ferroelectric domain. In addition, it also exhibits a flexible SHG response. The photoluminescence spectrum shows that 1 has broadband luminescence. At the same time, compound 1 has a wide band gap, which is mainly contributed to by the inorganic CdBr4 tetrahedron. The high tunability of low-dimensional chiral molecular ferroelectrics also opens up a way to explore multifunctional chiral materials.

Ferroelectric properties, narrow band gap and ultra-large reversible entropy change in a novel nonlinear ionic chromium(VI) compound.

A novel chromium(VI)-based compound, [(CH3CH2)3N(CH2Cl)][CrO3Cl] (1), undergoes a high-temperature phase transition at around 340.9 K, accompanied by an ultra-large entropy change of 63.49 J mol-1 K-1. Compound 1 exhibits a moderate ferroelectric polarization of 0.48 µC cm-2 and a remarkable CD signal. Strikingly, 1 occupies a narrow band gap of 2.22 eV, which is chiefly attributed to the inorganic [CrO3Cl]- tetrahedron. It is believed that these findings will contribute to an alternative pathway for the design of multifunctional ferroelectric materials, whose potential applications will be in semiconductors, energy storage, etc.