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RESEARCH PAPER · Angewandte Chemie International Edition · 2022

Hybrid Germanium Bromide Perovskites with Tunable Second Harmonic Generation

Yang Liu, Ya-Ping Gong, Shining Geng, Mei‐Ling Feng, Despoina Manidaki, Zeyu Deng, Constantinos C. Stoumpos, Pieremanuele Canepa, Zewen Xiao, Wei‐Xiong Zhang, Lingling Mao

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Hybrid Germanium Bromide Perovskites with Tunable Second Harmonic GenerationOriginalBroadband emission originating from the stereochemical expression of 6s 2 lone pairs in two-dimensional lead bromide perovskites11Effect of Pd( ii ) uptake on high-temperature phase transitions in a hybrid organic–inorganic perovskite semiconductor3From H 12 C 4 N 2 CdI 4 to H 11 C 4 N 2 CdI 3 : a highly polarizable CdNI 3 tetrahedron induced a sharp enhancement of second harmonic generation response and birefringence50Second harmonic generation from symmetry breaking stimulated by mixed organic cations in zero-dimensional hybrid metal halides7Achieving Near‐unity Photoluminescence Quantum Yields in Organic‐Inorganic Hybrid Antimony (III) Chlorides with the [SbCl 5 ] Geometry129Achieving Near‐unity Photoluminescence Quantum Yields in Organic‐Inorganic Hybrid Antimony (III) Chlorides with the [SbCl5] Geometry16Halogen Engineering To Realize Regulable Multipolar Axes, Nonlinear Optical Response, and Piezoelectricity in Plastic Ferroelectrics21Two-Dimensional Hybrid Dion–Jacobson Germanium Halide Perovskites59Mono‐ and Bi‐Dentate Chiral Ligands Lead to Efficient Circularly Polarized Luminescence in 0D and 3D Semiconducting Copper(I) Iodides37Recent Progress of Low‐Toxicity Poor‐Lead All‐Inorganic Perovskite Solar Cells18Chiral Hybrid Germanium(II) Halide with Strong Nonlinear Chiroptical Properties114Chiral Hybrid Germanium(II) Halide with Strong Nonlinear Chiroptical Properties12A review of the relationship between the structure and nonlinear optical properties of organic-inorganic hybrid materials150Lone-Pair Stereochemistry Induces Ferroelectric Distortion and the Rashba Effect in Inorganic Halide Perovskites330D Pyramid‐intercalated 2D Bimetallic Halides with Tunable Electronic Structures and Enhanced Emission under Pressure180D Pyramid‐intercalated 2D Bimetallic Halides with Tunable Electronic Structures and Enhanced Emission under Pressure1Stereo‐Active Lone Pairs Induced Giant Polarization in a 2D Ge‐Based Halide Perovskite Antiferroelectric15Tuning Structure and Excitonic Properties of 2D Ruddlesden–Popper Germanium, Tin, and Lead Iodide Perovskites via Interplay between Cations60Rational Design of the Alkali Metal Sn‐Based Mixed Halides with Large Birefringence and Wide Transparent Range45Optical bandgap anomaly with tuning dimensionality in germanium perovskites: Interplay between quantum confinement and lone pair expression22In Situ Chiral Template Approach to Synthesize Homochiral Lead Iodides for Second‐Harmonic Generation11In Situ Chiral Template Approach to Synthesize Homochiral Lead Iodides for Second‐Harmonic Generation68Hybrid perovskite shows temperature-dependent photoluminescence and dielectric response triggered by halogen substitution22(C 13 N 3 H 14 ) 2 MBr 4 (M = Zn, Cd): two novel hybrid metal halides with balanced integrated nonlinear optical performance311D Cu( i )-based chiral organic–inorganic hybrid material with second harmonic generation and circular polarized luminescence10Achieving strong second harmonic generation effects induced via dimensional increase of PbX 6 octahedra and halogen substitutes in (C 10 H 11 N 3 )PbX 4 (X = Cl or Br)26Advancing nonlinear optics: discovery and characterization of new non-centrosymmetric phenazine-based halides6Halide-driven polarity tuning and optimized SHG-bandgap balance in (C 4 H 11 N 2 )ZnX 3 (X = Cl, Br, I)34High-entropy alloy screening for halide perovskites17High-throughput calculation for the screening of formamidinium halide perovskite for solar cells2N 2 H 4 Zn(HC 3 N 3 O 3 ): exceptionally strong second harmonic generation and ultra-long phosphorescence16Off‐Centering of Ge Atoms in GeBi 2 Te 4 and Impact on Thermoelectric Performance43Bright Circularly Polarized Mechanoluminescence from 0D Hybrid Manganese Halides101From C4H7N2Ge0.4Sn0.6Br3 to C6H11N2Ge0.4Sn0.6Br3: Effective Modulation of the Second Harmonic Generation Effect and Optical Band Gap by Planar π-Conjugated Organic Cation Size11Increasing the Structural Rigidity and Quantum Yield of Highly Emissive Hybrid Antimony Chlorides Using a Diverse Set of Solvent Guests24Synthesis, Structure, and Optical Properties of a 0D Hybrid Organic–Inorganic Metal Halide (C 5 N 2 H 14 Cl)GeCl 317Boosted Second Harmonic Generation of a Chiral Hybrid Lead Halide Resonant to Charge Transfer Exciton from Metal Halide Octahedra to Ligand11Boosted Second Harmonic Generation of a Chiral Hybrid Lead Halide Resonant to Charge Transfer Exciton from Metal Halide Octahedra to Ligand48Room-Temperature Ferroelectric Epitaxial Nanowire Arrays with Photoluminescence11Regulating the Stereoisomerism of Diammonium Cations to Construct Polar Dion-Jacobson Hybrid Perovskites for Self-Powered X-ray Detection8Highly Stable MOF‐Type Lead Halide Luminescent Ferroelectrics26Highly Stable MOF‐Type Lead Halide Luminescent Ferroelectrics7Controlling the Orientation‐Dependent Second Harmonic Generation in Hybrid Germanium Perovskites2Controlling the Orientation‐Dependent Second Harmonic Generation in Hybrid Germanium Perovskites22Nonlinear Optical Effects of Hybrid Antimony(III) Halides Induced by Stereoactive 5s 2 Lone Pairs and Trimethylammonium Cations23Structural Evolution and Photoluminescence Quenching across the FASnI 3– x Br x ( x = 0–3) Perovskites29Noncollinear Electric Dipoles in a Polar Chiral Phase of CsSnBr3 Perovskite27Chiral Organic Cations and Distorted Inorganic Polyhedra Composing Metal Halide Nonlinear Optical Materials22Enhanced UV Nonlinear Optical Properties in Layered Germanous Phosphites through Functional Group Sequential Construction11Enhanced UV Nonlinear Optical Properties in Layered Germanous Phosphites through Functional Group Sequential Construction118Lead‐Free Halide Perovskite Nanoparticles for Up‐Conversion Lasing and Efficient Second Harmonic Generation11Photoluminescence Enhancement of 0D Organic–Inorganic Metal Halides via Aggregation‐Induced Emission and Halide Substitution14Stereo‐Active Lone Pairs Induced Second Harmonic Generation Responses and Electrocatalytic Activity in Hybrid Material1Unlocking the Potential of Organic‐Inorganic Hybrid Manganese Halides for Advanced Optoelectronic Applications171Vacancy Effect on the Luminescent and Water Responsive Properties of Vacancy‐Ordered Double Perovskite Derivatives4Vacancy Effect on the Luminescent and Water Responsive Properties of Vacancy‐Ordered Double Perovskite Derivatives21Histidine-based hybrid perovskites as promising materials for wide wavelength photodetection3A-Site Cation Chemistry in Halide Perovskites123Lead‐Free Perovskite Light‐Emitting Diodes46Chiral 0D hybrid lead-bromide perovskites with strong nonlinear chiroptical properties16Theoretical Studies on the Electronic Structures of Halide Perovskites: A Critical Review8Chiral Metal‐Free Anti‐Perovskite with Strong Chiroptical Nonlinearity13Chiral Metal‐Free Anti‐Perovskite with Strong Chiroptical Nonlinearity23A novel zero-dimensional germanium-based ferroelectric hybrid material with dual phase transitions6Dynamic control of halide perovskite structures for tailored ferroelectric and second-order nonlinear optical functionalities39From poor-active to high performance via heteroleptic tetrahedra engineering: rational design of non-π-conjugated hybrids for phase-matchable ultraviolet nonlinear optics12Ligand substitution in organic–inorganic hybrid zinc iodides for second-harmonic generation8Significant enhancement in the birefringence of metal phosphite halides via the introduction of π-conjugated cations18Strong second-harmonic generation response in an organic–inorganic hybrid antimony bromide1Thermo-mechanical control of second harmonic generation in a ferroelectric plastic crystal1Unprecedented Ultraviolet Circularly Polarized Light‐Dependent Anomalous Photovoltaics in Chiral Hybrid Perovskites12Design of organic crystals with lone pairs to study spin resonance and spin-lattice interactions3Self‐Powered Filterless Narrowband UV Photodetection Triggered by Asymmetric Charge Carrier Generation in a Wide‐Bandgap Halide Perovskite Ferroelectric18Two‐Dimensional Layered Germanium Iodide Perovskite Ferroelectric Semiconductors25Two‐Dimensional Layered Germanium Iodide Perovskite Ferroelectric Semiconductors2Additive engineering of nonlinear optical properties of all-inorganic halide perovskites2From (C6H5N2)2CdCl4 to (C6H5N2)2ZnCl4, Chirality Transformation to Realize a Nonlinear Optical Organic–Inorganic Hybrid Halide with Balanced Comprehensive Performance19Toward the Strongest Nonlinear Optical Response and Largest Birefringence in Solvent‐Free Organic–Inorganic Metal Halides by Hydrogen Bond Engineering39Syntheses, Structures, and Characterization of Alkali-Metal Molybdates, A3Cl[Mo2O7] (A = K, Rb and Cs)3Chiral Ligand-Induced Second-Harmonic Generation Response in Helical One-Dimensional Hybrid Lead Bromides9Small Cations for Engineering 3D Hybrid Perovskites7Femtosecond Laser Breaks the Lattice Symmetry and Induces Broadband Second Harmonic Generation in 3D Halide Perovskites6Alkaline Earth Metal‐Based Hybrid Organic‐Inorganic Perovskite‐Like Ferroelectrics11Alkaline Earth Metal‐Based Hybrid Organic‐Inorganic Perovskite‐Like Ferroelectrics3Lone pair expression in fluorinated two-dimensional hybrid perovskite enables multiaxial ferroelectricity and nonlinear optical response24Recent Progress in the Design and Synthesis of Nonlinear Optical Crystals with Stereochemically Active Lone Pairs8Record Second‐Harmonic Generation in a Lead‐Free 2D Hybrid Halide Perovskite13KF·[SO 2 (NH 2 ) 2 ]: the First Deep‐Ultraviolet Transparent Sulfonamide Fluoride Nonlinear Optical Crystal with Novel Cairo Pentagonal Structure13KF·[SO 2 (NH 2 ) 2 ]: the First Deep‐Ultraviolet Transparent Sulfonamide Fluoride Nonlinear Optical Crystal with Novel Cairo Pentagonal Structure5Tuning optical properties and local lone-pair off-centering in “hollow” FA 1− x { en } x Pb η − y Sn y Br 3 perovskites3Theoretical investigation of noncentrosymmetric Ruddlesden-Popper germanium perovskites Cs 2 Ge X 4 ( X = Cl , Br, and I) for second harmonic generation0Hydrogen‐Bond‐Directed Assembly of Steric Networks in Two‐Dimensional Germanium, Tin, and Lead Halide Perovskites: Highly Efficient, Ultranarrow Emission and Nonlinear Optical Properties4High‐Performance Second‐Harmonic Generation in Hybrid Ge Perovskite Ferroelectrics Enabled by Confinement Engineering8Exploring the Polaron Landscape in Germanium Halide Perovskites: CsGeCl 3 , CsGeBr 3 , and CsGeI 33A novel 0D germanium-based organic–inorganic hybrid material (C 12 H 28 N)GeCl 3 showing reversible phase transition, dielectric anomaly and SHG response1An organic–inorganic hybrid piezoelectric exhibiting high-temperature structural phase transition and moderate second harmonic generation response0Cation-dominated second-harmonic generation in chiral tetrahydro-1-naphthylammonium halides0Chiral calcium thiocyanate hybrids: amino acid-enabled structural diversity and second-harmonic generation0Computational Screening and Discovery of Silver–Indium Halide Double Salts0Internally and externally induced chiral hybrid metal halide materials for advanced chiroptoelectronic applications23Isomeric organic–inorganic indium bromide single crystals with delayed and dual colour emission0The modulation of structural polarity facilitating the gradient enhancement of second harmonic generation effects in hybrid metal halides5Perovskite solar cells with integrated photocatalysis: materials innovations and application potentials3Simultaneously Achieving Efficient Narrow‐Band Emission and Large Emission Dissymmetry Factor in an Achiral Hybrid Indium Chloride2Facile Synthesis and Structural, Morphological, and Optical Properties of Lead‐Free Layered Ruddlesden–Popper EA 2 CuCl 4 Hybrid Perovskite0Unlocking Strong SHG Response and Large Birefringence in Hybrid Antimony Halides via a Three-in-One Strategy7Halogen Anion-Mediated Substitution of Nitrate: Toward Polar Materials with Intense Second-Harmonic Generation Effects3Large-Area Three-Dimensional Displaced Overlapping Wing Perovskite Metamaterials with Giant Optical Chirality1Exploring Hybrid Metal Halide Materials beyond Halide Perovskites7Temperature-Dependent Structural and Optical Properties of CsGeI 30Record-high Glass coefficient in the shift current response of a ferroelectric halide perovskite0Narrow-Line Width Emission and Room Temperature Amplified Spontaneous Emission in Three-Dimensional Ge Halide Perovskites0Mutual Amplification of Chirality Driven by Interfacial Interactions in In Situ Synthesized Perovskite/Polymer Composites0Kinetic Trapping of Pressure‐Induced Symmetry Breaking in Hybrid Metal Halides via Fluorine‐Mediated Molecular Locking0Conjugated Molecules as Multifunctional Architects: Boosting Water Stability and Radiance of Mn-Based Metal Halides for Flexible X-ray Scintillation Imaging0Transcending the Speed‐Detectivity Trade‐Off via Self‐Powered, Lead‐Free Pyroelectric Germanium Perovskite Photodetectors0Record Second-Harmonic Generation and Exceptional Optical Anisotropy in High-Symmetry 1D Polar Perovskites1Dynamic Lone Pair Expression‐Driven Strong Light Emission in a Zero‐Dimensional Ge(II)‐Based Perovskite0Pressure‐Induced Ultra‐Red‐Shift From Visible to Near‐Infrared and Enhanced Emission in Inorganic Halide Perovskite CsGeBr 31Copper(I) Photocatalytic Three-Component Acylative Germylation of Unactivated Olefins with Aroyl Chlorides and CsGeBr30Chiral Trigonal Pyramidal Germanium Halides for Enhanced Second Harmonic Generation0Mixed‐Valence Engineering in Ge 2+ Chalcogenides: Structural Modulation for Balanced Infrared Nonlinear Optics0Deep-Red-Emissive Organic–Inorganic Hybrid Crystal with Multifunctional Nonlinear Optical Responses0

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  2. Effect of Pd( ii ) uptake on high-temperature phase transitions in a hybrid organic–inorganic perovskite semiconductor

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  3. From H 12 C 4 N 2 CdI 4 to H 11 C 4 N 2 CdI 3 : a highly polarizable CdNI 3 tetrahedron induced a sharp enhancement of second harmonic generation response and birefringence

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  4. Second harmonic generation from symmetry breaking stimulated by mixed organic cations in zero-dimensional hybrid metal halides

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  5. Achieving Near‐unity Photoluminescence Quantum Yields in Organic‐Inorganic Hybrid Antimony (III) Chlorides with the [SbCl 5 ] Geometry

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  7. Halogen Engineering To Realize Regulable Multipolar Axes, Nonlinear Optical Response, and Piezoelectricity in Plastic Ferroelectrics

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  8. Two-Dimensional Hybrid Dion–Jacobson Germanium Halide Perovskites

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  9. Mono‐ and Bi‐Dentate Chiral Ligands Lead to Efficient Circularly Polarized Luminescence in 0D and 3D Semiconducting Copper(I) Iodides

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  10. Recent Progress of Low‐Toxicity Poor‐Lead All‐Inorganic Perovskite Solar Cells

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  11. Chiral Hybrid Germanium(II) Halide with Strong Nonlinear Chiroptical Properties

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  12. Chiral Hybrid Germanium(II) Halide with Strong Nonlinear Chiroptical Properties

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  13. A review of the relationship between the structure and nonlinear optical properties of organic-inorganic hybrid materials

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  14. Lone-Pair Stereochemistry Induces Ferroelectric Distortion and the Rashba Effect in Inorganic Halide Perovskites

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  15. 0D Pyramid‐intercalated 2D Bimetallic Halides with Tunable Electronic Structures and Enhanced Emission under Pressure

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  16. 0D Pyramid‐intercalated 2D Bimetallic Halides with Tunable Electronic Structures and Enhanced Emission under Pressure

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  17. Stereo‐Active Lone Pairs Induced Giant Polarization in a 2D Ge‐Based Halide Perovskite Antiferroelectric

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  18. Tuning Structure and Excitonic Properties of 2D Ruddlesden–Popper Germanium, Tin, and Lead Iodide Perovskites via Interplay between Cations

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  19. Rational Design of the Alkali Metal Sn‐Based Mixed Halides with Large Birefringence and Wide Transparent Range

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  20. Optical bandgap anomaly with tuning dimensionality in germanium perovskites: Interplay between quantum confinement and lone pair expression

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  21. In Situ Chiral Template Approach to Synthesize Homochiral Lead Iodides for Second‐Harmonic Generation

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  22. In Situ Chiral Template Approach to Synthesize Homochiral Lead Iodides for Second‐Harmonic Generation

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  23. Hybrid perovskite shows temperature-dependent photoluminescence and dielectric response triggered by halogen substitution

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  24. (C 13 N 3 H 14 ) 2 MBr 4 (M = Zn, Cd): two novel hybrid metal halides with balanced integrated nonlinear optical performance

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  28. Halide-driven polarity tuning and optimized SHG-bandgap balance in (C 4 H 11 N 2 )ZnX 3 (X = Cl, Br, I)

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  29. High-entropy alloy screening for halide perovskites

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  30. High-throughput calculation for the screening of formamidinium halide perovskite for solar cells

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  31. N 2 H 4 Zn(HC 3 N 3 O 3 ): exceptionally strong second harmonic generation and ultra-long phosphorescence

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  32. Off‐Centering of Ge Atoms in GeBi 2 Te 4 and Impact on Thermoelectric Performance

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  33. Bright Circularly Polarized Mechanoluminescence from 0D Hybrid Manganese Halides

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  34. From C4H7N2Ge0.4Sn0.6Br3 to C6H11N2Ge0.4Sn0.6Br3: Effective Modulation of the Second Harmonic Generation Effect and Optical Band Gap by Planar π-Conjugated Organic Cation Size

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  35. Increasing the Structural Rigidity and Quantum Yield of Highly Emissive Hybrid Antimony Chlorides Using a Diverse Set of Solvent Guests

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  36. Synthesis, Structure, and Optical Properties of a 0D Hybrid Organic–Inorganic Metal Halide (C 5 N 2 H 14 Cl)GeCl 3

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  37. Boosted Second Harmonic Generation of a Chiral Hybrid Lead Halide Resonant to Charge Transfer Exciton from Metal Halide Octahedra to Ligand

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  38. Boosted Second Harmonic Generation of a Chiral Hybrid Lead Halide Resonant to Charge Transfer Exciton from Metal Halide Octahedra to Ligand

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  39. Room-Temperature Ferroelectric Epitaxial Nanowire Arrays with Photoluminescence

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  40. Regulating the Stereoisomerism of Diammonium Cations to Construct Polar Dion-Jacobson Hybrid Perovskites for Self-Powered X-ray Detection

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  41. Highly Stable MOF‐Type Lead Halide Luminescent Ferroelectrics

    Angewandte Chemie International Edition · 2024-05-15

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  42. Highly Stable MOF‐Type Lead Halide Luminescent Ferroelectrics

    Angewandte Chemie · 2024-05-15

    Chen Sun, Yukong Li, Jinlin Yin, Dongyang Li, Chao Wu, Chi Zhang, Honghan Fei

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

    Angewandte Chemie · 2024-05-21

    Zhu Guo, Ding‐Chong Han, Huan Liu, Yaoqiao Hu, Wei‐Xiong Zhang, Rui Chen, Lingling Mao

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

    Angewandte Chemie International Edition · 2024-05-21

    Zhu Guo, Ding‐Chong Han, Huan Liu, Yaoqiao Hu, Wei‐Xiong Zhang, Rui Chen, Lingling Mao

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  45. Nonlinear Optical Effects of Hybrid Antimony(III) Halides Induced by Stereoactive 5s 2 Lone Pairs and Trimethylammonium Cations

    Inorganic Chemistry · 2024-05-23

    Danping Chen, Zhexin Song, Can Yang, Yaoyao Wei, Guokui Liu, Lingqiang Meng, Qi Wu, Yangyang Dang

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