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RESEARCH PAPER · Angewandte Chemie International Edition · 2023

Designing Sulfate Crystals with Strong Optical Anisotropy through π‐Conjugated Tailoring

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Designing Sulfate Crystals with Strong Optical Anisotropy through π‐Conjugated TailoringOriginalAdvancing 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)34Strategically designed metal-free deep-ultraviolet birefringent crystals with superior optical properties18Exceptional Optical Anisotropy Enhancement Achieved Through Dual‐Ions Cosubstitution Strategy in Novel Hybrid Bismuth Halides23Hg4(Te2O5)(SO4): A Giant Birefringent Sulfate Crystal Triggered by a Highly Selective Cation153Rational Combination of π‐Conjugated and Non‐π‐Conjugated Groups Achieving Strong Nonlinear Optical Response, Large Optical Anisotropy, and UV Light‐Switchable Fluorescence65Zn(C6H4NO2)2·4H2O: A Solar-Blind Birefringent Crystal5Deep-Ultraviolet Bialkali–Rare Earth Metal Anhydrous Sulfate Birefringent Crystal11A solution-processable natural crystal with giant optical anisotropy for efficient manipulation of light polarization161Breaking Boundaries: Giant Ultraviolet Birefringence in Dimension‐Reduced Zn‐Based Crystals66Breaking Boundaries: Giant Ultraviolet Birefringence in Dimension‐Reduced Zn‐Based Crystals8The Directional Design of the Quasi‐Phase‐Matching Short‐Wave Ultraviolet Nonlinear Optical Crystal25Li2NaB3S2O12: A Deep-UV Transparent Borosulfate with Moderate Birefringence Derived from the [B3S2O12]∞ Infinite Chain Designed by the High Boron-to-Sulfur Ratio Strategy6The New Paradigm of Ligand Substitution-Driven Enhancement of Anisotropy from SO4 Units in Short-Wavelength Region14Designing a Heteroleptic Tetrahedral Group with an Ultrahigh Polarizability Anisotropy by Optimizing the Bonding Electrons Activity and Their Distribution14(C 6 H 5 N 2 )HgCl 3 : Discovery of a Polar Hg‐Based Hybrid Halide as Preeminent Nonlinear Optical and Birefringent Material Activated by π‐Conjugated Organic Cation Substitution38(CN 4 H 7 ) 2 SO 4 ·H 2 O: high-performance metal-free ultraviolet birefringent crystal with KBBF-like configuration5Hg[CS(NH 2 ) 2 ] 4 (SiF 6 ): a fluorosilicate crystal with large birefringence achieved via multi-functional group modification6Hydrogen bonding regulation-oriented design of pyridine sulfonate as a promising UV birefringent crystal characterized by enhanced structural anisotropy11Structure modulation by cationic modification of sulfates using planar CS(NH 2 ) 25Synergistic engineering of ultraviolet metal-free crystals with exceptional birefringence via pyridine-derived dimers14Y(C 6 H 5 SO 3 ) 3 ·9H 2 O: strategic integration of ligand substitution and π-conjugated group linkage in sulfates for enhanced ultraviolet nonlinear optical properties4Hafnium-Based Chiral 2D Organic–Inorganic Hybrid Metal Halides: Engineering Polarity and Nonlinear Optical Properties via Para -Substituent Effects86SnHPO4: A Layered Tin(II) Phosphate with Enhanced Birefringence51From 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 Crystal28Polar [ NH ( CH2SO3 )2]2− Dimers Enable the First Promising Iminodimethanesulfonate with Nonlinear Optical Properties and Wide UV Transparency19Designed Metal‐Free Quasi‐1D Crystals with Giant Birefringence8Metal Cation Engineered UV Birefringent Crystals in π‐Conjugated Sulfonates with Record‐High Optical Anisotropy17Bridging 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 Crystals48Hydrogen‐Bonded Assembly of Functional Units for Constructing Linear and Nonlinear Optical Crystals10NH4PO3HCH3 and NH4PO3CH2NH3: Two Phosphate Derivatives with Deep-UV Cutoff Edges and Moderate Birefringence1Anionic Group Trimming Strategy: Oriented Fabrication of Sulfonate UV Birefringent Crystals with High Optical Anisotropy5Exceptional Enhancement of Optical Anisotropy Achieved via the Strategy of Combining Rigid Groups with High Symmetry and π‐Conjugated Organic Groups in Hybrid Fluorides33Sulfonated Module Aggregation for Ultrahigh Birefringence in Aqueous-Processable Crystals26LiBa 2 GaSi 2 O 8 : A Noncentrosymmetric Silicate Exhibiting Wide Transmission Range and Moderate Second Harmonic Generation Response2A[N(SO 2 NH 2 ) 2 ] (A = Na, K, Rb, and Cs): enhancing birefringence of non π-conjugated deep-ultraviolet crystals via novel dimeric disulfonamide [N(SO 2 NH 2 ) 2 ] − groups0Molecular pseudo-halogen engineering enables remarkable birefringence enhancement in hybrid perovskites0Truss bridge-like anhydrous stacking in hybrid crystals triggers ultra-high stability and robust birefringence0The modulation of structural polarity facilitating the gradient enhancement of second harmonic generation effects in hybrid metal halides5Halogen‐Bond Coupled Halogenated‐π‐Conjugation Enables Giant Birefringence in Hydrogen‐Bonded Organic Frameworks13Rigid‐Flexible Coupling Units Enable Robust Large Birefringence2Anion Size‐Dependent Conformational Folding of Guanidinopropionate: Enabling Tunable Birefringence and Balanced Second‐Harmonic Generation Performance3Noncovalent Assembly Engineering Achieves Excellent Birefringence in Crystals0Bio-inspired proton-conformation-coupled hydrogen-bond network reconfiguration for adaptive optical anisotropy0Designing Novel Solar‐Blind Ultraviolet Nonlinear Optical Crystals Based on Local Proton Distribution Complementary Effect0Decoupling Contributions of Distinct Strategies for Enhancing Polarizability Anisotropy in Crystals Containing π-Conjugated Groups0Two Rare Earth-Based Sulfates with Enhanced Birefringence and Broad Optical Transparency Window0Assembly of dual π-conjugated units toward enhanced birefringence in a 2D organic sulfonate crystal0A Hydrogen-Bonded Molecular Crystal with Strong Optical Anisotropy and Large Second-Harmonic Generation Response0

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  2. 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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  3. Strategically designed metal-free deep-ultraviolet birefringent crystals with superior optical properties

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  4. Exceptional Optical Anisotropy Enhancement Achieved Through Dual‐Ions Cosubstitution Strategy in Novel Hybrid Bismuth Halides

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

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  6. Rational Combination of π‐Conjugated and Non‐π‐Conjugated Groups Achieving Strong Nonlinear Optical Response, Large Optical Anisotropy, and UV Light‐Switchable Fluorescence

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  8. Deep-Ultraviolet Bialkali–Rare Earth Metal Anhydrous Sulfate Birefringent Crystal

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  9. A solution-processable natural crystal with giant optical anisotropy for efficient manipulation of light polarization

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

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

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  12. The Directional Design of the Quasi‐Phase‐Matching Short‐Wave Ultraviolet Nonlinear Optical Crystal

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  13. Li2NaB3S2O12: A Deep-UV Transparent Borosulfate with Moderate Birefringence Derived from the [B3S2O12]∞ Infinite Chain Designed by the High Boron-to-Sulfur Ratio Strategy

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  14. The New Paradigm of Ligand Substitution-Driven Enhancement of Anisotropy from SO4 Units in Short-Wavelength Region

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  15. Designing a Heteroleptic Tetrahedral Group with an Ultrahigh Polarizability Anisotropy by Optimizing the Bonding Electrons Activity and Their Distribution

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  16. (C 6 H 5 N 2 )HgCl 3 : Discovery of a Polar Hg‐Based Hybrid Halide as Preeminent Nonlinear Optical and Birefringent Material Activated by π‐Conjugated Organic Cation Substitution

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  17. (CN 4 H 7 ) 2 SO 4 ·H 2 O: high-performance metal-free ultraviolet birefringent crystal with KBBF-like configuration

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

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  19. Hydrogen bonding regulation-oriented design of pyridine sulfonate as a promising UV birefringent crystal characterized by enhanced structural anisotropy

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  20. Structure modulation by cationic modification of sulfates using planar CS(NH 2 ) 2

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

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  22. Y(C 6 H 5 SO 3 ) 3 ·9H 2 O: strategic integration of ligand substitution and π-conjugated group linkage in sulfates for enhanced ultraviolet nonlinear optical properties

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  24. SnHPO4: A Layered Tin(II) Phosphate with Enhanced Birefringence

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

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  27. Polar [ NH ( CH2SO3 )2]2− Dimers Enable the First Promising Iminodimethanesulfonate with Nonlinear Optical Properties and Wide UV Transparency

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  49. Two Rare Earth-Based Sulfates with Enhanced Birefringence and Broad Optical Transparency Window

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  50. Assembly of dual π-conjugated units toward enhanced birefringence in a 2D organic sulfonate crystal

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