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RESEARCH PAPER · Journal of the American Chemical Society · 2023

Highly Birefringent d 0 Transition Metal Fluoroantimonite in the Mid Infrared Band: Order–Disorder Regulation by Cationic Size

Jia-Hang Wu, Chun‐Li Hu, Ting-Kun Jiang, Jiang‐Gao Mao, Fang Kong

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Highly Birefringent d 0 Transition Metal Fluoroantimonite in the Mid Infrared Band: Order–Disorder Regulation by Cationic SizeOriginal[(C 5 H 6 N 2 ) 2 H](Sb 4 F 13 ): a polyfluoroantimonite with a strong second harmonic generation effect601D Cu( i )-based chiral organic–inorganic hybrid material with second harmonic generation and circular polarized luminescence10A UV non-hydrogen pure selenite nonlinear optical material for achieving balanced properties through framework-optimized structural transformation41Designing excellent UV birefringent materials through the synergistic interaction of two highly distorted functional groups23Designing promising ultraviolet (UV) birefringent crystals with different hydrogen-bonded phosphate frameworks18Explorations of highly birefringent materials in the vanadium oxyfluoride–iodate system by fluoride ion modulation8From (NH 4 ) 3 [Zr(PO 4 ) 2 F] to (NH 4 ) 3 [Sn 2 (PO 4 ) 2 ]Cl: the rational design of a tin-based short-wave ultraviolet phosphate with large optical anisotropy14Halide-driven polarity tuning and optimized SHG-bandgap balance in (C 4 H 11 N 2 )ZnX 3 (X = Cl, Br, I)34HgBr 2 : an easily growing wide-spectrum birefringent crystal38Large second harmonic generation and birefringence from extended octupolar π-conjugated structures35Hg3Se(SeO3)(SO4): A Mixed-Valent Selenium Compound with Mid-Infrared Transmittance Obtained by In Situ Reaction26Dual-Anion Strategy Induces Dual Enhancement Toward Ultrashort Phase-Matching Wavelength in Deep-UV Transparent d0 Transition Metal Oxyfluorides21Hg4(Te2O5)(SO4): A Giant Birefringent Sulfate Crystal Triggered by a Highly Selective Cation153Mixed-anion square-pyramid [SbS3I2] units causing strong second-harmonic generation intensity and large birefringence8Record Second-Harmonic Generation and Birefringence in an Ultraviolet Antimonate by Bond Engineering157UV-Transparent SHG Material Explored in an Alkali Metal Sulfate Selenite System16Cadmium Hydroxyl Chloride with Balanced Band Gap and Second-Harmonic-Generation Response2Highly Stable MOF‐Type Lead Halide Luminescent Ferroelectrics26Highly Stable MOF‐Type Lead Halide Luminescent Ferroelectrics7Old tree blossoms anew: Research progress on the structures and optical properties of ultraviolet selenites56Halogen Bond Unlocks Ultra‐High Birefringence73Halogen Bond Unlocks Ultra‐High Birefringence14The centrosymmetric to non-centrosymmetric transformation induced by alkaline-earth cations producing infrared nonlinear optical AeMn6Ga6S16 (Ae = Ca, Sr)13β-Pb3P2S8: A new optical crystal with exceptional birefringence effect11Cs2Pb(CO3)2: a novel mixed-metal carbonate with rare Pb-C-O one-dimensional chain0Sulfate Derivatives with Heteroleptic Tetrahedra: New Deep‐Ultraviolet Birefringent Materials in which Weak Interactions Modulate Functional Module Ordering61Sulfate Derivatives with Heteroleptic Tetrahedra: New Deep‐Ultraviolet Birefringent Materials in which Weak Interactions Modulate Functional Module Ordering4Hybrid metal halide family with color-time-dual-resolved phosphorescence for multiplexed information security applications18Unprecedented Silver‐Based Hybrid Pyroelectric Enabling Wide Spectral Photo‐Pyroelectricity for Birefringence Photomodulation7Unprecedented Silver‐Based Hybrid Pyroelectric Enabling Wide Spectral Photo‐Pyroelectricity for Birefringence Photomodulation1A Giant Optically Anisotropic Phosphate Driven by Mixed Valence Mercury Units22Structural Evolution and Optical Properties of Hydroxyfluorooxoborates MM′2n-1[B3O3F4(OH)]n (M = K, Cs, and Rb; M′ = K, NH4, and Cs; n = 1, 2, and 3)12Birefringence Disparity Induced by Synergistic Effects of Stereochemically Active Lone Pairs19Rare‐Earth Substitution Induced Symmetry Breaking for The First Sc‐Based Nonlinear Optical Chalcogenide with High‐Performance30(CN 4 H 7 ) 2 SO 4 ·H 2 O: high-performance metal-free ultraviolet birefringent crystal with KBBF-like configuration5Hg 2 (HTe 2 O 5 )(PO 4 ): a novel phosphate crystal with enhanced birefringence enabled by the synergistic modification of multiple functional groups12Hg 2 (SeO 3 )(TeO 3 ): a novel tellurite–selenite birefringent crystal achieved by assembling multiple functional groups11K 2 Na(I 3 O 8 ) 3 : a promising mid-infrared birefringent material with two different structures of octaoxotriiodate( v ) polyanions1BaFS: Birefringence Enhanced by the Transformation from Optical Isotropy to Anisotropy via Interlayer Anion Substitution8Design and Synthesis of Two Sn-Centered Mixed Halide Crystals with Enhanced Birefringence8From Holodirected to Hemidirected Coordination Activated by Oxygenation Strategy: A Facile Route to Long Wave Infrared Birefringent Crystal4From Holodirected to Hemidirected Coordination Activated by Oxygenation Strategy: A Facile Route to Long Wave Infrared Birefringent Crystal28Double Sb‐N Coordination Enables Record‐High Birefringence in UV‐Transparent Crystals71Double Sb‐N Coordination Enables Record‐High Birefringence in UV‐Transparent Crystals8Bridging the Interlayer Binding to Ordered π‐Conjugated Units for Constructing High‐Performing Light Polarization Crystals8Bridging the Interlayer Binding to Ordered π‐Conjugated Units for Constructing High‐Performing Light Polarization Crystals48Recent progress in structural design strategies of high-birefringence optical crystals54[TeSeS 2 ] 2− : The First Heterotriple‐Chalcogenide Motifs Decode Giant Mid‐Far Infrared Birefringence18[TeSeS 2 ] 2− : The First Heterotriple‐Chalcogenide Motifs Decode Giant Mid‐Far Infrared Birefringence4Breaking the Birefringence Barrier in B–O Crystals via B–C π-scaffolding36A novel metal-free crystal demonstrating superior birefringence attributed to the synergistic interaction of dual π-conjugated units8Dual‐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 – Units36Hydrogen Bond-Assisted Structural Regulation Enables Large Birefringence in Two Antimony Oxalofluoride Crystals5(CN4H7)H2C3N3S3: Trithiocyanurate Exhibiting Giant Optical Anisotropy via Weak Interaction-Mediated Functional Module Alignment3Giant Birefringence Induced by Intermolecular Aromatic Interactions in Hydrogen‐Bonded Organic Frameworks37Exceptional Enhancement of Optical Anisotropy Achieved via the Strategy of Combining Rigid Groups with High Symmetry and π‐Conjugated Organic Groups in Hybrid Fluorides33Ba 3 (MoO 2 F 3 )PO 4 F 2 : Rational Design and Synthesis of an Alkaline-Earth Phosphate Fluoride as a Birefringent Crystal1[C(NH 2 ) 3 ] 2 PO 3 (OH): A Deep-Ultraviolet Birefringent Crystal Enabled by Synergy of π-Conjugated Cations and Heteroleptic Tetrahedra2LiV 3 Se 2 O 12 : A Promising Giant‐Birefringent Crystal Enabled by Significant Structural Distortion3[Al(H 2 O) 6 ](NO 3 )Cl 2 : achieving parallel arrangement of functional units and birefringence enhancement through free halogen-mediated structural regulation0Achieving record birefringence in metal-free semiorganic sulfate crystals via tetrahedral anionic group substitution0From Ba[Sn(IO 3 ) 6 ] to Ba[Sn(IO 3 ) 4 F 2 ]: fluoride-ion-driven enhancement of birefringence and band gap1KTeOPO 4 and NH 4 SnClSO 4 : two new KTiOPO 4 derivatives as birefringent crystals featuring enhanced optical anisotropy0Layered perovskite-like nitrates A 2 Ca(NO 3 ) 2 Cl 2 (A = Rb, Cs) as ultraviolet birefringent optical materials3Confinement-assembled ultraviolet nonlinear optical crystal from pyridine-expanded π-systems with exhibiting strong SHG and birefringence18Halogen‐Bond Coupled Halogenated‐π‐Conjugation Enables Giant Birefringence in Hydrogen‐Bonded Organic Frameworks13Programmable Anisotropic in Diazapyrene Cocrystals With Birefringence Exceeding 1.27Programmable Anisotropic in Diazapyrene Cocrystals With Birefringence Exceeding 1.21[C 3 N 2 H 5 ]B 7 O 10 F 2 : Demonstrating a New Hydrogen‐Bond‐Induced Intralayer Charge‐Balanced Structure Model with Large Birefringence3Ultrawide Bandgap and Record-High Birefringence in a Covalent Beryllium-Organic Framework7Breaking Inversion Symmetry via Vanadium Coordination Engineering in Bismuth Vanadium Selenites0Steric hindrance and hydrogen-bond networks synergistically directing molecular alignment for high-performance ultraviolet birefringent1Defect Diamond‐Like d 10 Metal Indium Selenium With Strong Second‐Harmonic Generation and Enhanced Laser‐Induced Damage Threshold2Record‐High Birefringence with Ultralow Dichroic Loss Realized by Cation‐Templated Engineering Ordered Assembly of Linear Birefringent‐Active Unit6K 2 ZrSi 2 O 7 with a Wide Transmission Range and Enhanced Birefringence Induced by the d 0 -TM Zr-Based Units2Peroxide‐Assisted Solvate Engineering Enables Record‐High Birefringence in a Solar‐Blind Transparent Crystal0Peroxide‐Assisted Solvate Engineering Enables Record‐High Birefringence in a Solar‐Blind Transparent Crystal0Reversed Quantum‐Well Engineering Unlocks Large Ultraviolet Chiral Nonlinear Optical Response in a Water‐Resistant 2D Hybrid Fluorozirconate0Reversed Quantum‐Well Engineering Unlocks Large Ultraviolet Chiral Nonlinear Optical Response in a Water‐Resistant 2D Hybrid Fluorozirconate0Domino‐Effect Amplification via Covalent‐Chain Engineering for Giant Birefringence in NaAsQ 2 (Q = S, Se) Crystals0Coordination chemistry of Sb(III)-based optical crystals: from lone-pair-induced distortion to birefringence and second-harmonic generation0

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  2. 1D Cu( i )-based chiral organic–inorganic hybrid material with second harmonic generation and circular polarized luminescence

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  3. A UV non-hydrogen pure selenite nonlinear optical material for achieving balanced properties through framework-optimized structural transformation

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  4. Designing excellent UV birefringent materials through the synergistic interaction of two highly distorted functional groups

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  6. Explorations of highly birefringent materials in the vanadium oxyfluoride–iodate system by fluoride ion modulation

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  7. From (NH 4 ) 3 [Zr(PO 4 ) 2 F] to (NH 4 ) 3 [Sn 2 (PO 4 ) 2 ]Cl: the rational design of a tin-based short-wave ultraviolet phosphate with large optical anisotropy

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  8. 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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  11. Hg3Se(SeO3)(SO4): A Mixed-Valent Selenium Compound with Mid-Infrared Transmittance Obtained by In Situ Reaction

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  12. Dual-Anion Strategy Induces Dual Enhancement Toward Ultrashort Phase-Matching Wavelength in Deep-UV Transparent d0 Transition Metal Oxyfluorides

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  13. Hg4(Te2O5)(SO4): A Giant Birefringent Sulfate Crystal Triggered by a Highly Selective Cation

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  14. Mixed-anion square-pyramid [SbS3I2] units causing strong second-harmonic generation intensity and large birefringence

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  15. Record Second-Harmonic Generation and Birefringence in an Ultraviolet Antimonate by Bond Engineering

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  16. UV-Transparent SHG Material Explored in an Alkali Metal Sulfate Selenite System

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  17. Cadmium Hydroxyl Chloride with Balanced Band Gap and Second-Harmonic-Generation Response

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  20. Old tree blossoms anew: Research progress on the structures and optical properties of ultraviolet selenites

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  21. Halogen Bond Unlocks Ultra‐High Birefringence

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  48. [TeSeS 2 ] 2− : The First Heterotriple‐Chalcogenide Motifs Decode Giant Mid‐Far Infrared Birefringence

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  49. [TeSeS 2 ] 2− : The First Heterotriple‐Chalcogenide Motifs Decode Giant Mid‐Far Infrared Birefringence

    Angewandte Chemie · 2025-06-17

    Bo Zhang, Wei‐Qi Huang, Jiaxiang Zhang, Xintao Wu, Hua Lin, Qi‐Long Zhu

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  50. Breaking the Birefringence Barrier in B–O Crystals via B–C π-scaffolding

    Journal of the American Chemical Society · 2025-07-04

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