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RESEARCH PAPER · Angewandte Chemie International Edition · 2025

Double Sb‐N Coordination Enables Record‐High Birefringence in UV‐Transparent Crystals

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Double Sb‐N Coordination Enables Record‐High Birefringence in UV‐Transparent CrystalsOriginalEnhanced second-harmonic generation response in a chiral lead iodide induced by amino acid coordination8Exploring ultra-high optical anisotropy in polyiodides7Significant enhancement in the birefringence of metal phosphite halides via the introduction of π-conjugated cations17Structural chemistry of antimony( iii ) oxalates with lone pairs: polyhedral distortion [SbO 4 F 2 ], π-conjugation [C 2 O 4 ], and birefringence tuning1Ultra‐High Optical Anisotropy with UV Transmission Achieved by Rational Arrangement of Extended π‐Conjugated Groups46Halide Ion-Directed Symmetry Control in π-Conjugated Molecular Crystals6Dual Chemical Scissors Strategy Enables 1D Antimony Selenates with Ultraviolet Nonlinear Optical Properties35Dual Chemical Scissors Strategy Enables 1D Antimony Selenates with Ultraviolet Nonlinear Optical Properties6Designing High-Performance Short-Wave UV Tellurium-Based Mixed Halides Birefringent Crystals via Halogen Substitution Engineering4Breaking the Birefringence Barrier in B–O Crystals via B–C π-scaffolding36Dual‐Sided Multidentate Coordination Strategy Enables Record Birefringence in UV‐Transparent Antimony‐Based Hybrid Crystals37Dual‐Sided Multidentate Coordination Strategy Enables Record Birefringence in UV‐Transparent Antimony‐Based Hybrid Crystals11CsICl 2 : A Record-Birefringent Inorganic Crystal with Ultrawide Infrared Transparency Enabled by Linear Interhalogen ICl 2 – Units36Optimizing the Hydrogen-Bond Network Drives Cadmium Ce(IV) Fluoride Hydrate with Significantly Enhanced Optical Anisotropy8Modulation of Crystal Structure and Birefringence: Cation Size Effect in Alkali Metal Fluoroaluminoborates4Low‐Dimensional Organic–Inorganic Hybrid Metal Halide with Large Optical Anisotropy9Recent Progress in the Design and Synthesis of Nonlinear Optical Crystals with Stereochemically Active Lone Pairs8Enhanced Birefringence in Hybrid Antimony Halides via π-Conjugated Organic Cation Design10Enhancing Birefringence via a Planar‐Conformation‐Locking Strategy3[HgX 2 ] Linear Group Enabled Ultraviolet Birefringent Crystal RbHg 5 Br 11 with Strong Optical Anisotropy and Wide Bandgap12Five-Membered [C 5 O 5 ] 2 – Rings as Birefringence-Active Genes for Ultrabirefringent Crystals27From (C12H9N2)2TeBr6·2H2O to (C12H9N2)2TeBr6: Dehydration-Driven Crystal Reorganization for Birefringence Optimization6Exceptional Enhancement of Optical Anisotropy Achieved via the Strategy of Combining Rigid Groups with High Symmetry and π‐Conjugated Organic Groups in Hybrid Fluorides33[Pb(ptz)(OH)(H2O)]: A Hybrid Nonlinear Optical Crystal with Large Birefringence0Hydrogen-bond-driven noncentrosymmetric structure formation in π-conjugated (C3H7N6)(IO3): achieving both strong SHG response and wide bandgap5Remarkable Birefringence Enhancement Enabled by π-Conjugated Cyanoguanidine Group Based on Anisotropic Molecule Coordination Approach8Organic π-conjugated units as versatile building blocks for high-performance birefringent crystals6Dual-anion synergy drives remarkable birefringence in sulfate–nitrate crystals1Sb 2 (SeO 3 ) 2 SeO 4 : A Selenite–Selenate Crystal with Balanced Band Gap and Birefringence3A 2 Sb 2 SO 4 F 6 (A = NH 4 + , Na + ): two sulfate fluoride crystals exhibiting enhanced birefringence driven by stereochemically active antimony( iii )1Crystal structures and optical properties of two layered lead halide phosphites Pb 3 (HPO 3 )Cl 4 ·H 2 O and Pb 3 (HPO 3 ) 2 Cl 2 ·H 2 O0From Ba[Sn(IO 3 ) 6 ] to Ba[Sn(IO 3 ) 4 F 2 ]: fluoride-ion-driven enhancement of birefringence and band gap1Polymerization-enhanced optical anisotropy in selenites: a trimeric [H 2 Se 3 O 7 ] motif delivering large UV birefringence0Pyrazinamide–IBr: an organic–inorganic hybrid crystal exhibiting giant optical anisotropy0InO6X (X = Cl, Br): distinct functional motif family for nonlinear optical materials5[CdCl 2 (4-Aminopyridine) 2 ] n : Synergistic Enhancement of Second-Harmonic Generation and Birefringence Enabled by a π-Conjugated Ligand for UV Nonlinear Optics5Halogen‐Bond Coupled Halogenated‐π‐Conjugation Enables Giant Birefringence in Hydrogen‐Bonded Organic Frameworks13Unit Symmetry‐Breaking and Layered Linear Ordering Enabling Superior Short‐Wave Ultraviolet Birefringent Crystal8(C 6 H 7 N 2 O)NO 3 : π-Conjugation-Driven Synergistic Enhancement of Second-Harmonic Generation and Birefringence0Unveiling the Superior Birefringence Property of a Record‐Birefringent Crystal with Unique Building Block12Unveiling the Superior Birefringence Property of a Record‐Birefringent Crystal with Unique Building Block4Programmable Anisotropic in Diazapyrene Cocrystals With Birefringence Exceeding 1.27Programmable Anisotropic in Diazapyrene Cocrystals With Birefringence Exceeding 1.21Unlocking Strong SHG Response and Large Birefringence in Hybrid Antimony Halides via a Three-in-One Strategy7V-Shaped Pseudo-Chains Coupled with Lone-Pair-Distorted [GeX 3 ] − Units Enable Large Birefringence in Ge(II) Hybrid Halides2Significant Enhancement of Birefringence Resulting from the Introduction of [BO 2 (OH)] Groups into Borosulfates0Density-Compensated Polarizability Anisotropy for Record Birefringence in Short-Wavelength Ultraviolet Inorganic Crystals11Dual‐Functional Ultraviolet Nonlinear Optics and Bright Luminescence Achieved in the First Fluorine‐Containing Hybrid Lone‐Pair Metal Mixed Halides8NaNO 3 [(NH 2 ) 2 SO 2 ] 2 : A Halogen‐Free KBBF‐Type Nitrate Crystal with Record Birefringence for Ultraviolet Applications0Linear [ICl 2 ] Units Induced Giant Optical Anisotropy in AICl 2 (A = NH 4 , Rb): A Pathway to Advanced Birefringent Materials4Enhanced Birefringence in Organic–Inorganic Hybrid Antimony Halides via Partial Halogen Substitution1Lock‐and‐Key Assembly Enables Record Birefringence in Monocyclic π‐Conjugated Crystals via Spatial Confinement of Linear Polyhalide5K 2 ZrSi 2 O 7 with a Wide Transmission Range and Enhanced Birefringence Induced by the d 0 -TM Zr-Based Units2(C 2 N 4 H 7 S)(H 2 PO 3 ): Optical Properties Study of a Metal‐Free Amidinothiourea Phosphite0Bridging Motifs Induced Ordered Arrangement Contributing Large Birefringence for Hg 4 BiQ 2 Cl 5 (Q═S, Se)1Unlocking Structural Anisotropy by Guest-Symmetry Modulation Strategy to Achieve Giant Birefringence in Molecular Crystals0Interlayer Electronic Decoupling Unlocks Giant Birefringence in π‐Conjugated Metal‐Organic Frameworks0Unlocking Nonlinear Optics and Photoluminescence with Simultaneous Enhancement of Bandgap and Birefringence in Hybrid Sb-Based Halides2Peroxide‐Assisted Solvate Engineering Enables Record‐High Birefringence in a Solar‐Blind Transparent Crystal0Halogen-Substitution-Modulated Lone-Pair Orientation in Sb(H 2 PO 2 ) 2 X (X = Cl, F) for Enhanced UV Birefringence1K 3 Yb 2 (BO 3 ) 3 and Rb 3 Yb 2 (BO 3 ) 3 : Two Rare-Earth Borate Ultraviolet Nonlinear Optical Crystals1Bioinspired Subnanowire‐Based Optical Devices With Programmable Polarization Irisations Through Photocuring 3D Printing0Heavy‐Halide Coordination and Lattice‐Confined Molecular Alignment Enable Giant Birefringence in Hybrid Metal Halides0Lateral‐Site Unblocking Enables Bilateral π ‐Chromophore Organization for Giant Birefringence in One‐Dimensional Lead Hybrids0Steric‐Guided Coordination Engineering Enables Significantly Optimized Optical Anisotropy via Sulfur‐Driven [C 5 H 5 NS] Birefringence‐Active Groups0Local Aromatic Overlap Microregulation Enables Birefringence Enhancement in Isocompositional Hybrid Antimony Halides1Reversible Symmetry Switching, Giant Birefringence, and UV Second‐Harmonic Generation in Hybrid Niobium Oxyfluorides0Reversible Symmetry Switching, Giant Birefringence, and UV Second‐Harmonic Generation in Hybrid Niobium Oxyfluorides0A Dynamic Hydrogen‐Bonded Organic Framework With Giant OFF–ON Birefringence0Rational Construction of Fluoride Crystals With Record Birefringence via Water‐Regulated Hydrogen‐Bond Network Reconfiguration0Dual‐Role BF 3 Anchoring Enables Giant Birefringence in Short‐Wave UV‐Transparent Fluoroborates0

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  4. Structural chemistry of antimony( iii ) oxalates with lone pairs: polyhedral distortion [SbO 4 F 2 ], π-conjugation [C 2 O 4 ], and birefringence tuning

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  5. Ultra‐High Optical Anisotropy with UV Transmission Achieved by Rational Arrangement of Extended π‐Conjugated Groups

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  7. Dual Chemical Scissors Strategy Enables 1D Antimony Selenates with Ultraviolet Nonlinear Optical Properties

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  8. Dual Chemical Scissors Strategy Enables 1D Antimony Selenates with Ultraviolet Nonlinear Optical Properties

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  9. Designing High-Performance Short-Wave UV Tellurium-Based Mixed Halides Birefringent Crystals via Halogen Substitution Engineering

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  11. Dual‐Sided Multidentate Coordination Strategy Enables Record Birefringence in UV‐Transparent Antimony‐Based Hybrid Crystals

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  12. Dual‐Sided Multidentate Coordination Strategy Enables Record Birefringence in UV‐Transparent Antimony‐Based Hybrid Crystals

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  13. CsICl 2 : A Record-Birefringent Inorganic Crystal with Ultrawide Infrared Transparency Enabled by Linear Interhalogen ICl 2 – Units

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  14. Optimizing the Hydrogen-Bond Network Drives Cadmium Ce(IV) Fluoride Hydrate with Significantly Enhanced Optical Anisotropy

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  15. Modulation of Crystal Structure and Birefringence: Cation Size Effect in Alkali Metal Fluoroaluminoborates

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  16. Low‐Dimensional Organic–Inorganic Hybrid Metal Halide with Large Optical Anisotropy

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  17. Recent Progress in the Design and Synthesis of Nonlinear Optical Crystals with Stereochemically Active Lone Pairs

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  18. Enhanced Birefringence in Hybrid Antimony Halides via π-Conjugated Organic Cation Design

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  19. Enhancing Birefringence via a Planar‐Conformation‐Locking Strategy

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  20. [HgX 2 ] Linear Group Enabled Ultraviolet Birefringent Crystal RbHg 5 Br 11 with Strong Optical Anisotropy and Wide Bandgap

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  21. Five-Membered [C 5 O 5 ] 2 – Rings as Birefringence-Active Genes for Ultrabirefringent Crystals

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  22. From (C12H9N2)2TeBr6·2H2O to (C12H9N2)2TeBr6: Dehydration-Driven Crystal Reorganization for Birefringence Optimization

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  23. Exceptional Enhancement of Optical Anisotropy Achieved via the Strategy of Combining Rigid Groups with High Symmetry and π‐Conjugated Organic Groups in Hybrid Fluorides

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  24. [Pb(ptz)(OH)(H2O)]: A Hybrid Nonlinear Optical Crystal with Large Birefringence

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  25. Hydrogen-bond-driven noncentrosymmetric structure formation in π-conjugated (C3H7N6)(IO3): achieving both strong SHG response and wide bandgap

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  26. Remarkable Birefringence Enhancement Enabled by π-Conjugated Cyanoguanidine Group Based on Anisotropic Molecule Coordination Approach

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  44. Unlocking Strong SHG Response and Large Birefringence in Hybrid Antimony Halides via a Three-in-One Strategy

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  45. V-Shaped Pseudo-Chains Coupled with Lone-Pair-Distorted [GeX 3 ] − Units Enable Large Birefringence in Ge(II) Hybrid Halides

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  50. Linear [ICl 2 ] Units Induced Giant Optical Anisotropy in AICl 2 (A = NH 4 , Rb): A Pathway to Advanced Birefringent Materials

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