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RESEARCH PAPER · Trends in Chemistry · 2021

H/F substitution for advanced molecular ferroelectrics

Yong Ai, Hui‐Peng Lv, Zhong‐Xia Wang, Wei‐Qiang Liao, Ren‐Gen Xiong

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H/F substitution for advanced molecular ferroelectricsOriginalChemical design of homochiral heterocyclic organic ferroelectric crystals8Ferroelastic phase transition with large spontaneous strain caused by freezing the conformational dynamics of ammonium8Ferroelasticity, thermochromism, semi-conductivity, and ferromagnetism in a new layered perovskite: (4-fluorophenethylaminium) 2 [CuCl 4 ]50Ferroelectricity in organic materials: from materials characteristics to de novo design39H/F Substitution induced switchable coordination bonds in a cyano-bridged hybrid double perovskite ferroelastic51High temperature hybrid perovskite multifunctional switching materials constructed through precise molecular design20Tailoring the coercive field in ferroelectric metal-free perovskites by hydrogen bonding66Crystal structures and phase transitions in two new hybrid crystals: (Me3NCH2CH2X)4[Ni(NCS)6] (X = Cl and Br)18H/F Substitution on the Spacer Cations Leads to 1D-to-2D Increment of the Pyrrolidinium-Containing Lead Iodide Hybrid Perovskites18Ferroelasticity in Organic–Inorganic Hybrid Perovskites63Employing halogen-halogen interaction to construct high-temperature hybrid perovskite phase transition materials12Chlorine Substitution in Spirocyclic Derivatives Triggers SHG Response in Noncentrosymmetric Crystal14NH4+/K+-substitution-induced C–F–K coordination bonds for designing the highest-temperature hybrid halide double perovskite ferroelastic11Recent progress of bulk photovoltaic effect in acentric single crystals and optoelectronic devices62The First Chiro‐Inositol Organosilicon Ferroelectric Crystal3The First Chiro‐Inositol Organosilicon Ferroelectric Crystal34H/F-Substitution-Induced Confinement Effect for Designing High-Phase-Transition-Temperature Organic–Inorganic Hybrid Materials16Axial-Chiral BINOL Multiferroic Crystals with Coexistence of Ferroelectricity and Ferroelasticity67Ferroelectric hybrid organic–inorganic perovskites and their structural and functional diversity195Emerging Halide Perovskite Ferroelectrics161Design, synthesis, and characterization of a new hybrid organic–inorganic perovskite with a high- T c dielectric transition9Dielectrics and possible ferroelectricity in diol/glycerol covalently grafted kaolinites1High‐Tc 1D Phase‐Transition Semiconductor Photoluminescent Material with Broadband Emission14An organic–inorganic hybrid material [Me 3 NCH 2 CH 2 F]FeBr 4 exhibits three-step SHG on/off15Halogenation triggering rules in hybrid materials for fluorescence and dielectric phase transitions31High-Tc Fe-based ferroelectric compound with large spontaneous polarization and narrow bandgap3Impact of hydrophobicity on local solvation structures and its connection with the global solubilization thermodynamics of amphiphilic molecules4Structural dimension engineering and high-temperature dielectric–optical switching in fluorine-substituted lead bromide hybrid perovskites5High-Tc Single-Component Organosilicon Ferroelectric Crystal Obtained by H/F Substitution19Solid–Liquid Crystal Biphasic Ferroelectrics with Tunable Biferroelectricity12The First Enantiomeric Stereogenic Sulfur‐Chiral Organic Ferroelectric Crystals41The First Enantiomeric Stereogenic Sulfur‐Chiral Organic Ferroelectric Crystals0Crystal engineering regulation achieving inverse temperature symmetry breaking ferroelasticity in a cationic displacement type hybrid perovskite system16Precise Design of Molecular Ferroelectrics with High T C and Tunable Band Gap by Molecular Modification28A Two-Dimensional Hybrid Lead Bromide Ferroelectric Semiconductor with an Out-of-Plane Polarization31Large Phase-Transition Temperature Enhancement Achieved in a Layered Lead Iodide Hybrid Crystal by H/F Substitution15Introducing Ferroelasticity into 1D Hybrid Lead Halide Semiconductor by Halogen Substitution Strategy38Organic radical ferroelectric crystals with martensitic phase transition40Ferroics in Hybrid Organic–Inorganic Perovskites: Fundamentals, Design Strategies, and Implementation42Advancements and challenges in molecular/hybrid perovskites for piezoelectric nanogenerator application: A comprehensive review50Volume‐Confined Fabrication of Large‐Scale Single‐Crystalline Molecular Ferroelectric Thin Films and Their Applications in 2D Materials9H/F substitution activating tunable dimensions and dielectric–optical properties in organic lead-bromide hybrids19Tuning Structure and Excitonic Properties of 2D Ruddlesden–Popper Germanium, Tin, and Lead Iodide Perovskites via Interplay between Cations60H/F substitution achieves high piezoelectricity in enantiomeric molecular crystals4Switchable coordination bonds in 3D cyano-bridged perovskite ferroelastics: achieving the largest leap of symmetry breaking and enhanced dielectric switching performance13Symmetry breaking through molecular engineering to achieve “on–off–on” nonlinear optical switch in a [SnCl 6 ] 2− framework4The H/F substitution strategy can achieve large spontaneous polarization in 1D hybrid perovskite ferroelectrics29The past 10 years of molecular ferroelectrics: structures, design, and properties173Room-Temperature Photoferroelectrics Semiconductor Driven by the Interlayer Confinement Effect20Organic‐Inorganic Hybrid Ferroelectric and Antiferroelectric with Afterglow Emission49Organic‐Inorganic Hybrid Ferroelectric and Antiferroelectric with Afterglow Emission10Tuning ferroelectric phase transition temperature by enantiomer fraction34B-site ion regulation strategy enables performance optimization and multifunctional integration of hybrid perovskite ferroelectrics15Efficient Charge Transport in Inverted Perovskite Solar Cells via 2D/3D Ferroelectric Heterojunction25A Lead‐Free Ferroelectric 2D Dion–Jacobson Tin Iodide Perovskite35Perovskite solar cells with ferroelectricity21Piezoelectricity in Molecular Ferroelectrics1Mechanically deformable organic ferroelectric crystal with adaptive shape locking0A Multiferroic Spin‐Crossover Molecular Crystal32Exploiting the Cationic Size Effect to Improve the Curie Temperature of Hybrid Perovskites Photoferroelectric Semiconductors6Dual-Channel Control of Ferroelasticity in a Soft Molecular Crystal Induced by Perfluorinated Substitution2A molecular ferroelectric thin film of imidazolium perchlorate on silicon8Designing Zero-Dimensional Cadmium-Based Organic–Inorganic Hybrids: The Role of Halogen Doping in Modulating Multifunctional Properties9Halogen Substitution Strategy for Exploiting High‐Performance Molecular Ferroelectrics1A novel zero-dimensional germanium-based ferroelectric hybrid material with dual phase transitions6Effective enhancement of mechanical properties via H/F substitution in 3D cyanide hybrid perovskites10Ferroelectricity in perovskites realized by a switchable skewed conformation2Three-dimensional perchlorate-based alkali metal hybrid perovskite molecular ferroelastic crystals5Unconventional Inverse Temperature Symmetry Breaking in a Ferroelastic Crystal3The First Kleinman‐type Second‐Harmonic Generation Circular Dichroism On/Off Switchable Ferroelectrics28The First Kleinman‐type Second‐Harmonic Generation Circular Dichroism On/Off Switchable Ferroelectrics4Spatial Symmetry Operation Breaking Sulfur-Chiral Photoswitchable Ferroelectrics22Zero-Dimensional Plastic Phase Transition Iron-Based Compounds with High T c and Switchable SHG Responses5Mechanically deformable organic ferroelectric crystal with plasticity optimized by fluorination20Photogalvanic effects in non-centrosymmetric halide perovskites17Multifunctional Polar 2D Lead Iodide Perovskites Exhibiting Persistent Spin Texture15Halogen-substitution-induced magnetic-phase transition photoelectric synergy in l-valine crown ether inclusion complexes3Potential Multiaxial Molecular Ferroelectricity through Chiral Cation Replacement0Lone pair expression in fluorinated two-dimensional hybrid perovskite enables multiaxial ferroelectricity and nonlinear optical response24H/F Substitution‐Engineered Argentophilic Interactions for Enhanced Photoluminescence in 1D Hybrid Silver Halides3Record Second‐Harmonic Generation in a Lead‐Free 2D Hybrid Halide Perovskite13Jahn–Teller Distortion Enables Enhanced Piezoelectric Energy Harvesting Properties of a Metal-Pyrazolylborate Complex2A 2D Van Der Waals Molecular Ferroelectric3Multiple non-covalent interactions synergistically construct room-temperature photoferroelectric semiconductor (Cl-PA)2PbCl41Disorder in the Crystal Structures of Pseudosymmetrical Amino-Phenylbenzothiazoles1Two-dimensional mixed tetrahedral–octahedral hybrid perovskites with coexisting ferroelectricity and intralayer antiferromagnetism6Molecular Symmetry and Geometry Engineering for High‐Temperature Ferroelectricity and Low Coercive Field in Hybrid Metal Halides1Molecular Symmetry and Geometry Engineering for High‐Temperature Ferroelectricity and Low Coercive Field in Hybrid Metal Halides4An organic–inorganic hybrid indium molecular ferroelectric originating from a “butterfly-flapping” model of 1,5-diazabicyclo[3.3.0]octane2Decoupling high-temperature phase transition and charge-transfer emission in a crown ether-based crystal1H/F Substitution Strategy in 0D Organic–Inorganic Hybrid Metal Cyanides Designing Ferroelastic Phase-Transition Materials3Leveraging Conformational and Nitrogen Atom Inversion for Room-Temperature Ferroelectricity1Intrinsically Weak Polarization in (4-(Aminomethyl)piperidinium) SnI 40Emerging halide perovskite ferroelectric semiconductors: Structural diversity, chemical design and optoelectronic applications3Controllable Photoluminescence Modulation of 2D Hybrid Materials Based on (DFCBA) 2 PbX 4 (X = I, Br) via Halogen Regulation2Dimensionality Engineering: A Pathway to Ferroelectric Halide Perovskites3H/F substitution strategy for molecular ferroelectrics: From design principles to emerging materials0Beyond Conventional Pyroelectrics: 2D‐Layered Perovskites for Next Generation Pyro‐Phototronic Devices1Engineering Small-Molecule Proton-Transfer Ferroelectrics by Crystal Structure Prediction: Design Limits at the Salt–Cocrystal Boundary0Halide Substitution Driven Symmetry Breaking in a Ferroelectric Mixed-Halide Halogenometallate for Piezoelectric Energy Harvesting0Multistage Fluorination in a Metal‐Free Perovskite Ferroelectric Enables Multidirectional Self‐Powered X‐Ray Detection0Multistage Fluorination in a Metal‐Free Perovskite Ferroelectric Enables Multidirectional Self‐Powered X‐Ray Detection0Molecular Ferroelectric Catalysis: From Material Design Strategies to Catalytic Applications0H/CH3 Organic-Cation Substitution Regulates Structural Evolution toward High- T c Ferroelectricity and Enhanced Blue Emission in Gallium-Based Organic–Inorganic Hybrids0

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