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RESEARCH PAPER · Chemical Society Reviews · 2024

The past 10 years of molecular ferroelectrics: structures, design, and properties

Qiang Pan, Zhuxiao Gu, Ru‐Jie Zhou, Zi‐Jie Feng, Yu‐An Xiong, Tai‐Ting Sha, Yu‐Meng You, Ren‐Gen Xiong

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The past 10 years of molecular ferroelectrics: structures, design, and propertiesOriginalEnhancing the performance of molecule-based piezoelectric sensors by optimizing their microstructures5Metal-free small molecule-based piezoelectric energy harvesters16Organic–Inorganic Hybrid Perovskite Ferroelectric Nanosheets Synthesized by a Room‐Temperature Antisolvent Method11Solid Solutions of Plastic/Ferroelectric Crystals: Toward Tailor-Made Functional Materials20Experimental Observation of the Fully Ferroelectric–Fully Ferroelastic Effect in Multiferroic Hybrid Perovskites90Chiral 3D Perovskite Formation Induced by Chiral Templates29Second-Order Nonlinear Switching and Photoluminescence Properties of Cd-Based Hybrid Perovskite with High-Temperature Phase Transition8Quantifying Structural Polarization by Continuous Regulation of Lone-Pair Electron Expression in Molecular Crystals52Exploiting 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 Substitution2Halogen Substitution Strategy for Exploiting High‐Performance Molecular Ferroelectrics1A Melt-Processable Metal Halide Perovskite Ferroelectric5Noncollinear ferrielectricity and hydrogen-induced ferromagnetic polar half-metallicity in MnO 3 Cl5Enhanced phase transition temperature achieved by CH3/H substitution in Sn-based perovskite3Strain‐Induced Tunable Enhancement of Piezoelectricity in a Novel Molecular Multiferroic Material29Humidity modulated surface pattering of large-scale molecular ferroelectric thin films based on natural alkaloids1Self‐Healing and Stretchable Molecular Ferroelectrics with High Expandability2Optical memory effect in a dynamic gadolinium–tetracyanidoplatinate coordination polymer for sensing deviations in temperature and humidity5Piezoelectric Energy Harvesting and Body Motion Sensing of a Pair of 0D Chiral Hybrid Metal Halides5Impact of H/D isotopic effects on the physical properties of materials24A highly moisture-stable ferroelectric ammonium phosphate salt showing piezoelectric energy harvesting and rotation sensing applications9An NIR-luminescent nitrate-bridged hybrid bimetal dielectric with a switchable dielectric constant2Constructing a photoferroelectric semiconductor by regulating non-covalent interactions through halogen substitution7Dynamic control of halide perovskite structures for tailored ferroelectric and second-order nonlinear optical functionalities39Exploitation of pseudo-symmetry in the Cambridge Structural Database for molecular ferroelectric discovery2Ferroelectricity and phase transition of halide solid-solution dabcoH(Br x I 1− x )0Ferroelectricity and piezoelectric energy harvesting of an A 3 M 2 X 9 -type 0D bromobismuthate hybrid with a bulky organic quaternary amine9First-principles investigation of auxetic piezoelectric effect in nitride perovskites2High phase transition temperature and photoluminescence properties in low-dimensional molecular perovskite ferroelastic crystals2Metal selection tactic in a nitronyl nitroxide biradical-3d–4f macrocycle for boosting photothermal conversion and the application of solar-driven water evaporation2Synthesis, crystallographic study and solid-state properties of metal-free perovskites with P-atom containing A-site cations2Review of Ferroelectric Materials and Devices toward Ultralow Voltage Operation75Hot-pressing boosted nonlinear optical properties in a new ferroelectric plastic crystalline material3Molecular Ferroelectrics for Highly Sensitive Detection Toward Low‐Frequency Sound Recognition14Hafnium-Based Chiral 2D Organic–Inorganic Hybrid Metal Halides: Engineering Polarity and Nonlinear Optical Properties via Para -Substituent Effects86Large Polarization Change Induced by Spin Crossover-Driven Fe(II) Ion Shuttling within a Tripodal Ligand27Artificial piezoelectric metamaterials83The First Kleinman‐type Second‐Harmonic Generation Circular Dichroism On/Off Switchable Ferroelectrics28The First Kleinman‐type Second‐Harmonic Generation Circular Dichroism On/Off Switchable Ferroelectrics4A Lithium Complex Ferroelectric with High Curie Temperature: [Li(1,10-Phenanthroline)2]I1Self‐Powered Artificial Neuron Devices: Towards the All‐In‐One Perception and Computation System38Halogen Engineering Enables Tunable Dielectric Response and Dimensional Regulation in Organic–Inorganic Hybrid Halides9Cholesterol Cocrystal Ferroelectrics Modulated by Solvent Effect6A Self‐Adaptive Quantum Dots/BaTiO 3 Junction Together with Giant Charge Separation‐Driving Force for CO 2 Photoreduction via Ferroelectric Polarization Engineering2The First Recyclable Molecular Ferroelectric Can Catalyze Difunctionalization of Olefin7Spiro‐Driven Ferroelectric Coordination Polymer Exhibiting Distinct Phase Transitions Under Thermal and Pressure Stimuli0Spiro‐Driven Ferroelectric Coordination Polymer Exhibiting Distinct Phase Transitions Under Thermal and Pressure Stimuli5Spatial Symmetry Operation Breaking Sulfur-Chiral Photoswitchable Ferroelectrics22A hybrid indium chloride with switching dielectric behavior and X-ray response1Precise Design of Organic–Inorganic Hybrid Indium Molecular Ferroelectrics Based on Halogen Substitution13Active Polarization Engineering between Symmetry Inequivalent Polar States Using Electron Transfer: A Nonferroelectric Approach9Facile Fabrication of Large‐Area and High‐Quality Organic–Inorganic Hybrid Perovskite Ferroelectric Films Through Electrohydrodynamic Printing5Enantiomeric Ferroelectric Chiral Domains18Exploring the Structural Phase Transition, Dielectric Response, and Magnetic Properties of a New Isothiocyanate-Based Dinuclear Manganese Compound1Alkyl Substitution on the Phase Transition and Optical Properties of Lead-Based Molecular Ferroelastic Materials0Visible‐Photoactive Ferroelectric Semiconductor Incorporating Aromatic Dynamic Spacer Enables Optoelectronic Synaptic Plasticity9Structural Phase Transition‐Associated Ferroelectricity and Piezoelectric Energy Harvesting in 0D Halogenozincate Hybrid via Cation's Terminal Group Lengthening4Ferroelectric-like Polarization Switching in Plastic Crystalline Succinonitrile3Emerging molecular ferroelectrics for high-performance perovskite optoelectronic devices9Progress in polarization synergistic mechanism and cross-domain application of multi-field modulated piezo-photocatalysis for ferroelectric materials26Enantiomeric Cobalt(II)‐Based Frameworks with Various Helical Structures Formed by Achiral N‐/O‐Mixed Rigid Ligands1Dual Structure Reinforces Interfacial Polarized MXene/PVDF-TrFE Piezoelectric Nanocomposite for Pressure Monitoring58Unraveling Lattice Void Occupancy Engineering for Regulating Optical/Dielectric Responses in Hybrid Crystals2Large vertical spontaneous polarization and strong second harmonic generation in a layered perovskite ferroelectric1Taming Tautomerism in Organic Crystal Structure Prediction6A Bendable Photoluminescent Molecular Crystal with Phase Transition Accompanied by SHG Switching6Ligand-directed assembly of tetranuclear cobalt clusters: structural modulation via a lactate derivative and azacyclic linkers1Polarization‐Switching Controlled Luminescence in Hybrid Ferroelectric4Polarization‐Switching Controlled Luminescence in Hybrid Ferroelectric34Self‐Powered Ferroelectric Bi‐Based Perovskite X‐Ray Detector for Radiation Monitoring and Intelligent Imaging Recognition7A Piezoelectric Molecular Cocrystal with Unconventional π-Stacking0Emergent multiferroic altermagnets and spin control via noncollinear molecular polarization22Jahn–Teller Distortion Enables Enhanced Piezoelectric Energy Harvesting Properties of a Metal-Pyrazolylborate Complex2Al3+ doping-induced proton spatial inversion symmetry breaking in two-dimensional vermiculite: Intrinsic polarization and ferroelectric switching0The First Ferrocene‐Based Molecular Ferroelectric Accompanied by Spatial Symmetry Operation Breaking2The First Ferrocene‐Based Molecular Ferroelectric Accompanied by Spatial Symmetry Operation Breaking7Synergistic Ultrasound‐Photo Enhancement of Ferroelectric Catalysis via Molecular Multiferroics4Asymmetric Coordination Designed Heterocrown Ether Host–Guest Ferroelectrics with Ultrahigh Tc10Molecular design and physical properties of alkylamide-substituted 3-fold symmetric molecules1A 2D Van Der Waals Molecular Ferroelectric3Twisting organic molecules to switch altermagnetism0Anisotropic Atomic Displacement Induced Thermosalience in Hybrid Zinc Halide Crystals8Opto-lattice coupling and thermally switchable dielectric transition in [N(CH3)3H]2CdCl40Organic–inorganic perovskite ferroelectric catalytic selective alkyne coupling under ultrasound sonication2Molecular 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 Halides4Progress in chiral organic ferroelectrics5Giant SHG Switching in a Molecular Crystal via Pressure‐Driven Conformational Isomerization2Hybrid rare-earth double perovskite based on K(I)/pr(III) exhibiting two isostructural phase transitions, switchable dielectric properties, and long fluorescence lifetime43D Chiral Perovskitoid‐to‐Perovskite Reconstructive Phase Transition Designed Molecular Ferroelectric Thin‐Film with out‐of‐Plane Polarization15Mechanically driven polarization for wireless and bioadaptive piezoelectric cardiac patches2Programmable piezoelectric domains and amplified d33 in 2D perovskites A2PbBr4 enabled by chain-length directed polar order0A ferroelectric induction strategy for a zero-dimensional lead-free hybrid material based on chemical modification0A one-dimensional hybrid ferroelectric exhibiting lone pair stereoactivity based on square pyramids1A zero-dimensional cadmium-based hybrid phase transition material with a switchable dielectric response and wide bandgap0An all-molecular-ferroelectric composite electrolyte couples spontaneous polarization with competitive coordination for durable nickel-rich solid-state lithium metal batteries0An organic–inorganic hybrid indium molecular ferroelectric originating from a “butterfly-flapping” model of 1,5-diazabicyclo[3.3.0]octane2An organic–inorganic hybrid piezoelectric exhibiting high-temperature structural phase transition and moderate second harmonic generation response0Angular strain-induced polarization in a ferroelectric ammonium cyclic phosphate and its wind speed sensing application0Assembly of a non-centrosymmetric molecular ferroelectric Cu( ii ) complex from a chiral pybox ligand: applications in energy harvesting0Construction of ratiometric optical thermometers by linking chiral cyclometalated dicyanidoiridates( iii ) with europium( iii ) luminophores into cluster compounds6Decoupling high-temperature phase transition and charge-transfer emission in a crown ether-based crystal1Ferroelectric Properties of Polyvinylidene Fluoride (PVDF): Advances and Prospects for Emerging Applications1Halogen-engineered molecular ferroelectrics for efficient mechanical energy harvesting toward sustainable alkane oxidation0Halogen-mediated interaction engineering enables tailored order–disorder phase transitions in photoactive nitroprusside hybrids0Helical Zn-based Chiral Coordination Polymers with Nonlinear Optical Property Constructed from Lactic Acid Derivatives0Inorganic Ge-based ferroelectric perovskites towards quasi-phase-matching in the infrared region0Metal-Directed Structural Diversity of Lactate-Based Coordination Polymers: From Pillared-layer Framework to Multi-Helical Interpenetrating Networks0New smectogenic azobenzene photoswitches and the effects of chirality and lateral substituents0Nonlinear optical-dielectric dual switching and narrow band gap in a one-dimensional hybrid compound: [(CH 3 ) 2 S(CH 2 ) 3 NH 3 ][SbBr 5 ]0Organic–inorganic hybrid materials with high phase transition temperatures regulated by halogen substitution1Reversible red-green photoluminescence transformation induced by dynamic coordination bonds in a phase-transition hybrid crystal4Strong SHG, piezoelectricity, and fluorescence coexisting in a single-component organic polar crystal enabled by σ-hole interactions0Structural Modulation of Co(II)-Based Chiral Coordination Polymers Based on Helixes and Lactic Derivatives via N-Donor Co-ligands0Dielectric, Ferroelectric, and Electric Applications of Polymers: Recent Advances and Progress6A Ferroelectric Zinc-Based Complex with Ultraviolet Emission3Divergent catalysis powered by external thermal fluctuations: A novel molecular ferroelectric approach0Composition optimization to regulate the dielectric energy storage performance of lead-free superparaelectric relaxor ferroelectrics3A multifunctional organic crystal synergizing aggregation-induced emission and ferroelectric switching0Robust Polarized Fields Generated by Organic–Inorganic Hybrid Perovskite Ferroelectrics Crystallization for Boosting Hydrogen Production Activity2Lattice dynamics of piezoelectric response of organic–inorganic hybrid perovskites0Compositing halide perovskites for multifunctionalities beyond optoelectronics13-Electron, Nonpolyhedral Cu Nanocluster Showing Distinct Dielectric, Magnetic, and Mechanical Properties1Emerging halide perovskite ferroelectric semiconductors: Structural diversity, chemical design and optoelectronic applications3Halogen Substitution Dual Regulation of Structure and Symmetry in an Edge-Shared ABX 3 Hybrid Ferroelectric3Regulating Noncovalent Interactions to Construct High-Temperature Multiaxial Lead-Free Metal Halide Hybrid Ferroelectrics4Exploring the Effect of Electronic Symmetry on the Hyperpolarizabilities of Co(II) and Ni(II) Coordination Complexes with Cytidine Nucleotide7Strain-enhanced stretchable molecular ferroelectric acoustic fibers3Gallium-based molecular ferroelectrics define a new photocatalytic paradigm toward selective C(sp3)–H oxidation0Ultralow-force-driven polarization switching in molecular ferroelectrics0Martensitic Transition Associated with Spin-Crossover Enabling Crystal Jumping and Pyroelectric Response5Boosting the piezoelectric energy harvesting in glycine polarized array through electric field-assisted PVD0Organosilicon cluster goes ferroelectric0Evaluation of organic–inorganic hybrid ferroelectric TMCM-GaCl4 synthesized via hand mixing0Halide Perovskite Single Crystals: A Promising Semiconductor Platform for Advanced X-ray Detection4Effect of Alkyl Chain Length on the Bandgap, Ferroelectric, and Photoelectric Properties of Lead‐Based Molecular Ferroelectrics0Structural modulation of Co(II)-based helical coordination polymers with lactic derivatives via N-donor co-ligands1Quantifying Magnetic Anisotropy of Ferroelectric Fe(II) Square‐Pyramidal Systems Using Torque Magnetometry0High-entropy 1D halide perovskite piezoelectrics found by megalibrary synthesis and rapid nonlinear optical screening0Molecular rotation and large polarization in charge-transfer ferroelectric cocrystals0Surface morphology modulation in chlorine-doped diisopropylammonium bromide film via Cl-induced domain refinement0From central chirality to helical chirality: two chiral coordination polymers based on a lactic acid derivative and their SHG responses2Interlayer Decoupling Growth for Atomically Thin Hybrid Perovskite Ferroelectrics with Giant Rashba Splitting Energy0Chiral Ni2+/Yb3+ molecular complex with room-temperature magnetic-field driven 180° polarization reversal0Direct Observation of Noncollinear Ferrielectricity in a Two-Dimensional Hybrid Germanium Perovskite1Ferroelectrically Modulated Photoresponse in a Zero-Dimensional Hybrid Perovskite [C 4 N 2 H 14 ][BiBr 5 ] with a High Ferroelectric Curie Temperature0Improving the ferroelectric and photovoltaic properties of Nd-modified bismuth titanate ceramics via cobalt doping and oxygen vacancy regulation2Chiral Zn-based coordination polymers with helical structures and SHG activity assembled from lactic acid derivatives0Water‐Triggered Domino‐Like Phase Transition in a Molecular Ferroelectric1Distinct Uniaxial Negative Thermal Expansion and Dielectric Behaviors Arising from Different Phase Transition Mechanisms in One-Dimensional Lead Halide Hybrids0

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