Tadpole-Like Polar Molecule Encapsulated in a Two-in-One Supramolecular Cage: Molecular Motion, Phase Transition and Ferroelectricity.

Molecule-inclusive closed cage compounds present a unique platform for molecular motion in an isolated environment. This study showcases the incorporation of a tadpole-like polar molecule (1-propyl-1H-imidazole, PIm) into a supramolecular cage formed by duad semicage p-tert-butylcalix[4]arene. The ferroelectric phase transition as well as the cage-confined motion of encapsulated PIm was studied in detail. The unusual quadrastable state of the PIm in the paraelectric phase allows for the modulation of dipolar polarization over a broad temperature/frequency range. This compound represents the first example of a clathrate molecular ferroelectric featuring a molecule-inclusive supramolecular cage, and it also contributes to the understanding of cage-confined molecular dynamics.

Controlling the Orientation-Dependent Second Harmonic Generation in Hybrid Germanium Perovskites.

Manipulating the crystal orientation plays a crucial role in the conversion efficiency during second harmonic generation (SHG). Here, we provide a new strategy in controlling the surface-dependent anisotropic SHG with the precise design of (101) and (2 1 ‾ ${\bar 1}$ 0) MAGeI3 facets. Based on the SHG measurement, the (101) MAGeI3 single crystal exhibits larger SHG (1.3×(2 1 ‾ ${\bar 1}$ 0) MAGeI3). Kelvin probe force microscopy imaging shows a smaller work function for the (101) MAGeI3 compared with the (2 1 ‾ ${\bar 1}$ 0), which indirectly demonstrates the stronger intrinsic polarization on the (101) surface. X-ray photoelectron spectroscopy confirms the band bending within the (101) facet. Temperature-dependent steady-state and time-resolved photoluminescence spectroscopy show shorter lifetime and wider emission band in the (101) MAGeI3 single crystal, revealing the higher defect states. Additionally, powder X-ray diffraction patterns show the (101) MAGeI3 possesses larger in-plane polar units [GeI3]- density, which could directly enhance the spontaneous polarization in the (101) facet. Density functional theory (DFT) calculation further demonstrates the higher intrinsic polarization in the (101) facet compared with the (2 1 ‾ ${\bar 1}$ 0) facet, and the larger built-in electric field in the (101) facet facilitates surface vacancy defect accumulation. Our work provides a new angle in tuning and optimizing hybrid perovskite-based nonlinear optical materials.

Three-Step Ferroelastic Transitions from Hexagonal to Triclinic Phases in a Hybrid Perovskite: (1-Fluoromethyl-1-methylpyrrolidine)[CdCl3].

Hybrid ferroelastic crystals have emerged as a hot research topic in recent years owing to their prospective applications in piezoelectric sensors, mechanical switches, and optoelectronic devices. Nevertheless, most of the documented materials exhibit one-step or two-step ferroelastic phase transition(s), and those with multistep ferroelastic transitions are extremely scarce. We present a new hexagonal molecular perovskite based on a fluoro-substituted flexible cyclic ammonium cation, (1-fluoromethyl-1-methylpyrrolidine)[CdCl3] (1), undergoing unusual three-step ferroelastic phase transitions from hexagonal paraelastic phase to orthorhombic, monoclinic, and triclinic ferroelastic phases at 388, 376, and 311 K, respectively, with Aizu notation of 6/mmmFmmm, mmmF2/m, and 2/mF-1, featuring spontaneous strain of 0.002, 0.023, and 0.110, respectively. Furthermore, variable-temperature single-crystal diffraction reveals that the phase-transition mechanism in 1 principally originates from intriguing dynamic change of organic cations and synchronous displacement of inorganic chains. This scarce instance of multistep hybrid ferroelastic provides important clues for finding advanced ferroelastic materials.

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.

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.

A Narrow Bandgap of 2D Ruddlesden-Popper Bilayer Perovskite with Giant Entropy Change and Photoluminescence.

The multifunctional two-dimensional (2D) organic-inorganic hybrid perovskites have potential applications in many fields, such as, semiconductor, energy storage and fluorescent device etc. Here, a 2D Ruddlesden-Popper (RP) perovskite (IPA)2 (FA)Pb2 I7 (1, IPA+ =C3 H9 NI+ , FA+ =CN2 H5 + ) is determined for its photophysical properties. Strikingly, 1 reveals a solid reversible phase transition with Tc of 382 K accompanied by giant entropy change of 40 J mol-1 K-1 . Further optical investigations indicate that 1 reveals a narrow direct bandgap (2.024 eV) attributed to the slight bending of I-Pb-I edge and inorganic [Pb2 I7 ]n layer and a superior photoluminescence (PL) emission with super long lifetime of 0.1607 ms. It is believed that this work will pave an avenue to further design multifunctional semiconductors that combines energy storage and photoelectric materials.

Coupling Narrow Band Gap and Switchable SHG Responses in a New Molecule Ferroelectric: Imidazolyl Propylamine Pentabromo Stibium(III).

Due to the existence of some cross properties such as SHG (second-harmonic generation), ferroelectricity, piezoelectricity, and thermoelectricity, molecular ferroelectrics have been widely used as a composite multipurpose material. Particularly, organic-inorganic molecular ferroelectrics have received much interest recently because of their unique flexible structures, friendly environment, ease of synthesis, etc. Also, these hybrids show great flexibility in band-gap engineering. Here we report a new molecular halide, [C6H13N3SbBr5]n (1; C6H13N3 = 1-(3-aminopropyl)imidazole), which experiences a unique ferroelectric to paraelectric phase transition at around 230 K from space group P21 to P21/c. Significantly, compound 1 exhibits a narrow band gap with a value of 2.52 eV, large pronounced SHG-active, perfect rectangle hysteresis loops with a large spontaneous polarization of 6.86 µC/cm2. DSC (differential scanning calorimetry) and dielectric dependence on temperature tests and the volume change before and after the phase transition show that compound 1 is characterized by a second-order phase transition. These findings will contribute to the multifunctional materials field of organic-inorganic hybrids.