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RESEARCH PAPER · Angewandte Chemie International Edition · 2024

Breaking Boundaries: Giant Ultraviolet Birefringence in Dimension‐Reduced Zn‐Based Crystals

Yang Li, Kang Min Ok

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Breaking Boundaries: Giant Ultraviolet Birefringence in Dimension‐Reduced Zn‐Based CrystalsOriginalResearch progress in optical materials with cationic organic planar π-conjugated groups containing CN bonds34Tetrahedra Modification of Phosphates for Optical Anisotropy Enhancement13[C(NH 2 ) 3 ] 2 [C 2 H 5 (C 2 O 4 )]Cl: rational design of a metal-free UV birefringent crystal through the synergistic assembly of three distinct motifs5A π-conjugated organic molecule-modified strategy to achieve high-performance metal nitrate birefringent crystals9Hg 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 groups11Hg[CS(NH 2 ) 2 ] 4 (SiF 6 ): a fluorosilicate crystal with large birefringence achieved via multi-functional group modification6Significant enhancement in the birefringence of metal phosphite halides via the introduction of π-conjugated cations17Synergistic engineering of ultraviolet metal-free crystals with exceptional birefringence via pyridine-derived dimers14Designing Polar Covalent Hybrid Cadmium‐Based Chalcohalides Ultraviolet Nonlinear Optical Crystal with Strong Optical Anisotropy via Double‐Site Dual FBUs Tailoring25From (C6H5N2)2CdCl4 to (C6H5N2)2ZnCl4, Chirality Transformation to Realize a Nonlinear Optical Organic–Inorganic Hybrid Halide with Balanced Comprehensive Performance19From 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 Crystal28Tuning Birefringence in Supramolecular Mg-PDA Frameworks: Modulating Bonding and Layer Connectivity0Designed Metal‐Free Quasi‐1D Crystals with Giant Birefringence8Na[B3IO7(OH)] and Na2[B4IO9](IO3): Explorations of Boroiodates with Strong Second Harmonic Generation Response and Large Birefringence54Unearthing Hydrogen Bonded Metal‐Free Crystal with Remarkable Optical Anisotropy9Bridging 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 Crystals48La2Zn3(SeO3)6: A UV Selenite Crystal with Second-Harmonic Generation and Large Birefringence13Decoupling the SHG‐Birefringence Trade‐off in UV NLO Materials via Triple‐Control Coordination Engineering: Achieving Synergistic Performance Optimization88Decoupling the SHG‐Birefringence Trade‐off in UV NLO Materials via Triple‐Control Coordination Engineering: Achieving Synergistic Performance Optimization13Giant Birefringence and Solar‐Blind Ultraviolet Transmission by Coordination‐Induced Assembly of π‐Conjugated Pyridine–Carboxylate8Giant Birefringence and Solar‐Blind Ultraviolet Transmission by Coordination‐Induced Assembly of π‐Conjugated Pyridine–Carboxylate24[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-scaffolding36Controlling d10 Metal in Phenylthiourea‐Based Hybrid Metal Halides to Actualize Dimensional Transformation and Significantly Improve the Birefringence11CsICl 2 : A Record-Birefringent Inorganic Crystal with Ultrawide Infrared Transparency Enabled by Linear Interhalogen ICl 2 – Units36A strategy to achieve giant optical anisotropy via integrating linear pseudohalogen and stereochemical active lone pair cation6Giant Birefringence and Strong Third-Order Nonlinear Optical Response in a Hybrid Crystal Templated by a Push–Pull π-Conjugated System6Low‐Dimensional Organic–Inorganic Hybrid Metal Halide with Large Optical Anisotropy9Giant Birefringence Induced by Intermolecular Aromatic Interactions in Hydrogen‐Bonded Organic Frameworks37Enhancing Birefringence via a Planar‐Conformation‐Locking Strategy3Five-Membered [C 5 O 5 ] 2 – Rings as Birefringence-Active Genes for Ultrabirefringent Crystals27K 2 GdB 3 O 6 F 2 : A Promising Short-Wave UV Birefringent Crystal via Optimized Assembly of π-Conjugated [B 3 O 6 ] Groups8Sulfonated Module Aggregation for Ultrahigh Birefringence in Aqueous-Processable Crystals26Remarkable Birefringence Enhancement Enabled by π-Conjugated Cyanoguanidine Group Based on Anisotropic Molecule Coordination Approach8Effect of Multiple Hydrogen Bonding on the π-Conjugated Groups and Optical Properties in Molecular Crystals5Anomalous Refractive Index Modulation and Giant Birefringence in 2D Ferrielectric CuInP 2 S 62Organic π-conjugated units as versatile building blocks for high-performance birefringent crystals6Hybrid Zinc‒Based Halides with Giant Optical Anisotropy via Protonation‒Engineered π ‒Conjugated Organic Group24Hydrogen‐Bond‐Driven Metal‐Free Crystal (C 6 H 7 N 2 O)(NH 2 SO 3 ) with Giant Birefringence and Solar‐Blind Ultraviolet Transmission0Achieving Ultra‐High Optical Anisotropy via Structural Regulation and Coplanar Engineering of Extended π‐Conjugated [H 2–x C 3 N 3 S 3 ] (x = 1, 2) Groups3KTeOPO 4 and NH 4 SnClSO 4 : two new KTiOPO 4 derivatives as birefringent crystals featuring enhanced optical anisotropy0Molecular pseudo-halogen engineering enables remarkable birefringence enhancement in hybrid perovskites0Truss bridge-like anhydrous stacking in hybrid crystals triggers ultra-high stability and robust birefringence0Functional Unit Design of Deep‐UV NLO Crystals With Short Phase‐Matching and Large SHG Response22Unveiling 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 Block4V-Shaped Pseudo-Chains Coupled with Lone-Pair-Distorted [GeX 3 ] − Units Enable Large Birefringence in Ge(II) Hybrid Halides2Density-Compensated Polarizability Anisotropy for Record Birefringence in Short-Wavelength Ultraviolet Inorganic Crystals11The Achievement of a Strong Second Harmonic Generation Response and a Large Birefringence in Sulfates4Synergistic Enhancement of Birefringence in Metal Benzoxazolium Complexes by π-Conjugated [C 9 H 10 NO] + and Triangular [HgI 3 ] − Motifs3Ultrawide Bandgap and Record-High Birefringence in a Covalent Beryllium-Organic Framework7Electronegativity Adaption Approach for Solar‐Blind UV Birefringent Crystals With Ultrawide Bandgaps2Redox‐Driven Strategy Enabling Leapfrog Enhancement of Birefringence in Layered Tin‐Based Optical Crystals1Rb 2 ZnGe 3 Se 8 : A Large-Birefringence Layered Chalcogenide Enabled by Anisotropic Electrons in Tetrahedral Units0Peroxide‐Assisted Solvate Engineering Enables Record‐High Birefringence in a Solar‐Blind Transparent Crystal0Fluorine‐Driven Chemical Scissor Effect in Scandium Borates: Structural Evolution with Retained Optically Active Motifs0Designing Novel Solar‐Blind Ultraviolet Nonlinear Optical Crystals Based on Local Proton Distribution Complementary Effect0Steric‐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 Halides1Decoupling Contributions of Distinct Strategies for Enhancing Polarizability Anisotropy in Crystals Containing π-Conjugated Groups0Cation-Modulated Activation of Linear Units in an Ordered Arrangement Achieves the Largest Optical Anisotropy in Wide-Bandgap Metal Chalcogenides0A Hydrogen-Bonded Molecular Crystal with Strong Optical Anisotropy and Large Second-Harmonic Generation Response0

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  2. Tetrahedra Modification of Phosphates for Optical Anisotropy Enhancement

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  3. [C(NH 2 ) 3 ] 2 [C 2 H 5 (C 2 O 4 )]Cl: rational design of a metal-free UV birefringent crystal through the synergistic assembly of three distinct motifs

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  4. A π-conjugated organic molecule-modified strategy to achieve high-performance metal nitrate birefringent crystals

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  5. Hg 2 (HTe 2 O 5 )(PO 4 ): a novel phosphate crystal with enhanced birefringence enabled by the synergistic modification of multiple functional groups

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  6. Hg 2 (SeO 3 )(TeO 3 ): a novel tellurite–selenite birefringent crystal achieved by assembling multiple functional groups

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  7. Hg[CS(NH 2 ) 2 ] 4 (SiF 6 ): a fluorosilicate crystal with large birefringence achieved via multi-functional group modification

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  8. Significant enhancement in the birefringence of metal phosphite halides via the introduction of π-conjugated cations

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  9. Synergistic engineering of ultraviolet metal-free crystals with exceptional birefringence via pyridine-derived dimers

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  10. Designing Polar Covalent Hybrid Cadmium‐Based Chalcohalides Ultraviolet Nonlinear Optical Crystal with Strong Optical Anisotropy via Double‐Site Dual FBUs Tailoring

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  11. From (C6H5N2)2CdCl4 to (C6H5N2)2ZnCl4, Chirality Transformation to Realize a Nonlinear Optical Organic–Inorganic Hybrid Halide with Balanced Comprehensive Performance

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  12. From Holodirected to Hemidirected Coordination Activated by Oxygenation Strategy: A Facile Route to Long Wave Infrared Birefringent Crystal

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  14. Tuning Birefringence in Supramolecular Mg-PDA Frameworks: Modulating Bonding and Layer Connectivity

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  15. Designed Metal‐Free Quasi‐1D Crystals with Giant Birefringence

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  16. Na[B3IO7(OH)] and Na2[B4IO9](IO3): Explorations of Boroiodates with Strong Second Harmonic Generation Response and Large Birefringence

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  17. Unearthing Hydrogen Bonded Metal‐Free Crystal with Remarkable Optical Anisotropy

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  18. Bridging the Interlayer Binding to Ordered π‐Conjugated Units for Constructing High‐Performing Light Polarization Crystals

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  19. Bridging the Interlayer Binding to Ordered π‐Conjugated Units for Constructing High‐Performing Light Polarization Crystals

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  20. La2Zn3(SeO3)6: A UV Selenite Crystal with Second-Harmonic Generation and Large Birefringence

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  46. Molecular pseudo-halogen engineering enables remarkable birefringence enhancement in hybrid perovskites

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  47. Truss bridge-like anhydrous stacking in hybrid crystals triggers ultra-high stability and robust birefringence

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  49. Unveiling the Superior Birefringence Property of a Record‐Birefringent Crystal with Unique Building Block

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  50. Unveiling the Superior Birefringence Property of a Record‐Birefringent Crystal with Unique Building Block

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