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RESEARCH PAPER · Advanced Science · 2021

Fluorine‐Driven Enhancement of Birefringence in the Fluorooxosulfate: A Deep Evaluation from a Joint Experimental and Computational Study

Wenqi Jin, Wenyao Zhang, Abudukadi Tudi, Liying Wang, Xin Hua Zhou, Zhihua Yang, Shilie Pan

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Fluorine‐Driven Enhancement of Birefringence in the Fluorooxosulfate: A Deep Evaluation from a Joint Experimental and Computational StudyOriginalLi 5 Cs(SO 4 ) 3 : a potential zero-order wave plate material with short deep-ultraviolet cutoff edge20Two bismuth iodate sulfates with enhanced optical anisotropy17Toward the Enhancement of Critical Performance for Deep-Ultraviolet Frequency-Doubling Crystals Utilizing Covalent Tetrahedra137Tetrafluoroborate-Monofluorophosphate (NH4)3[PO3F][BF4]: First Member of Oxyfluoride with B–F and P–F Bonds16Non-π-Conjugated Deep-Ultraviolet Nonlinear Optical Crystal K2Zn3(SO4)(HSO4)2F437Achieving Short‐Wavelength Phase‐Matching Second Harmonic Generation in Boron‐Rich Borosulfate with Planar [BO3] Units102Achieving Short‐Wavelength Phase‐Matching Second Harmonic Generation in Boron‐Rich Borosulfate with Planar [BO3] Units9Pushing KTiOPO4-like Nonlinear Optical Sulfates into the Deep-Ultraviolet Spectral Region19AZn 2 (BO 3 )Si 2 O 5 (A = Rb, Cs): first examples of KBe 2 BO 3 F 2 structure type in the borosilicate family exhibiting a deep-ultraviolet cutoff edge25(N 2 H 6 )[HPO 3 F] 2 : maximizing the optical anisotropy of deep-ultraviolet fluorophosphates33Ba 2 Zn 2 B 6 O 13 : coplanar [B 2 O 5 ] in unnoted U-shaped [B 6 O 13 ] groups achieving large birefringence6Hg 2 (SeO 3 )(SO 4 ): the first sulfate selenite with large birefringence explored from d 10 transition metal compounds36Large optical anisotropy differentiation induced by the anion-directed regulation of structures29Large optical anisotropy-oriented construction of a carbonate-nitrate chloride compound as a potential ultraviolet birefringent material44Li 7 SrScB 12 O 24 and Li 7 Ba 0.6 Ca 0.4 ScB 12 O 24 : two new quaternary rare-earth borates with short UV cutoff edges4Linear unit BN 2 : a novel birefringence-enhanced fundamental module with sp orbital hybridization9LiSrSbS 3 : parallel configurations of lone pair electrons inducing a large birefringence16Performance of optical materials with the derivative of planar π-conjugated groups: Recent advances and future prospects37PNO: a promising deep-UV nonlinear optical material with the largest second harmonic generation effect17Variable dimensionality of the anion framework in four new borophosphates and fluoroborophosphates with short cutoff edges13First-principles study of the influence of lone pair electrons and molecular groups on the birefringence of phosphate and fluorophosphate13Review of Heteroleptic Tetrahedra as Birefringent or Nonlinear Optical Motifs17A microstructure engineered perovskite super anode with Li-storage life of exceeding 10,000 cycles42Potential optical functional crystals with large birefringence: Recent advances and future prospects322Explorations of New SHG Materials in Mercury Iodate Sulfate System**9“Removing Center”─An Effective Structure Design Strategy for Nonlinear Optical Crystals37Phosphogermanate Crystal: A New Ultraviolet–Infrared Nonlinear Optical Crystal with Excellent Optical Performances16Alkali metal sulfate: A new non-π-conjugated deep-ultraviolet quasi-phase matching crystal27An Optimized KBe2BO3F2‐Like Structure: The Unity of Deep‐Ultraviolet Transparency, Nonlinear Optical Property, and Ferroelectricity22NaBaBS3: A Promising Infrared Functional Material with Large Birefringence Induced by π-Conjugated [BS3] Units32Molecular Structure Design, Crystal Growth, and Characterization of New Types of Organic Nonlinear Optical Chalcone Crystals24Novel pull–push organic switches with D–π–A structural designs: computational design of star shape organic materials38[Ba2F2][Ge2O3S2]: An Unprecedented Heteroanionic Infrared Nonlinear Optical Material Containing Three Typical Anions47Designing a deep-UV nonlinear optical monofluorophosphate22From Phosphate Fluoride to Fluorophosphate: Design of Novel Ultraviolet/Deep-Ultraviolet Nonlinear Optical Materials for BePO3F with Optical Property Enhancement34Tailored Ordered Structures with Functional Units of Distorted [NbO6] and Antiparallel [GeO4] for Enhanced Birefringence in Germanate Crystal15SbHPO3F: 2D van der Waals Layered Phosphite Exhibiting Large Birefringence32Achieving effective balance between bandgap and birefringence by confining π-conjugation in an optically anisotropic crystal39A High‐Performance Nonlinear Optical Crystal with a Building Block Containing Expanded π‐Delocalization95A High‐Performance Nonlinear Optical Crystal with a Building Block Containing Expanded π‐Delocalization5Exploring Short-Wavelength Phase-Matching Nonlinear Optical Crystals by Employing KBe2BO3F2 as the Template95Li0.5Na0.5AlB2O4F2: Fluoroaluminoborate with Aligned 1∞[BO2] Chain Induced by Unprecedented [AlO3F3]6− Species Features Enhanced Birefringence30Local Polarity-Induced Assembly of Second-Order Nonlinear Optical Materials128Aluminoborates as Nonlinear Optical Materials79Aluminoborates as Nonlinear Optical Materials14Performance measurement technique for 193-nm depolarizer1Design of deep-ultraviolet nonlinear optical materials based on fundamental building blocks with excellent microscopic properties1Anisotropic structure building unit involving diverse chemical bonds: a new opportunity for high-performance second-order NLO materials181Dramatically improved optical anisotropy by realizing stereochemically active lone pairs in a sulfate system, K 2 SO 4 ·HIO 323Enhancement of birefringence and refractive index dispersion optimization from iodates to fluorooxoiodates1Enhancing birefringence of non-π-conjugated sulfate systems through rare-earth metal-centered polyhedra10From 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 birefringence50Linear π-conjugated units of the D ∞h point group as superior ultraviolet birefringent units1Mg 2 Pb 2 Si 2 O 7 F 2 : a new lead-containing alkali earth metal silicate fluoride with a short cutoff edge2Intense d‐p Hybridization in Nb3O15 Tripolymer Induced the Largest Second Harmonic Generation Response and Birefringence in Germanates51Intense d‐p Hybridization in Nb3O15 Tripolymer Induced the Largest Second Harmonic Generation Response and Birefringence in Germanates7Recent advances in non-π-conjugated nonlinear optical sulfates with deep-UV absorption edge53CaB2O2F4: A Novel [BOF2]∞-Based Structural Template with a Strong Second Harmonic Generation Response and Large Band Gap2The induced polarization enhanced birefringence in AlPS4 family: A first-principles investigation6Two Ultraviolet Optical Crystals K6B12O19F4 and K12B28O48: The Effects of Metal Cations Size and the F Ions on the Structure6“Cation Activation”: An Effective Strategy for the Enhancement of Birefringence36Mixed Alkali Metal and Alkaline Earth Metal Scandium Borate Birefringence Material with Layered Structure and Short Ultraviolet Cutoff Edge17SrCl2·6H2O: An Alkaline-Earth-Metal Chloride Hexahydrate as Deep-Ultraviolet Nonlinear-Optical Crystal with the {[Sr(H2O)6]2+}∞ Cationic Framework8Improved Birefringence Activated by Tetrahedra Decorated with a Single Linear Unit38Improved Birefringence Activated by Tetrahedra Decorated with a Single Linear Unit1From Monofluorophosphates A2PO3F to Difluorophosphates APO2F2 (A = alkali metal): Design of a Potential Deep-Ultraviolet Nonlinear Optical Materials System with a Shortened Phase-Matching Wavelength41The Strategy to Improve the Phase Matching Ability in Tetrahedron‐Based Deep‐Ultraviolet Nonlinear Optical Crystals21Li2RbSO4Cl with a Short Ultraviolet Absorption Edge and an Acentric Structure through Assembling Heteroleptic [LiO3Cl] Tetrahedra2YSO4F·H2O: A Deep-Ultraviolet Birefringent Rare-Earth Sulfate Fluoride with Enhanced Birefringence Induced by Fluorinated Y-Centered Polyhedra19Optically Anisotropic Mixed-Metal Fluoroiodate Ba2[GaF5(IO3F)] with a Wide Optical Transparent Window and a Moderate Birefringence6Designing Sulfate Crystals with Strong Optical Anisotropy through π‐Conjugated Tailoring51Designing Sulfate Crystals with Strong Optical Anisotropy through π‐Conjugated Tailoring11Na 10 Zn(NO 3 ) 4 (SO 3 S) 4 : a nonlinear optical crystal combining inorganic π-conjugated and non-π-conjugated heteroanion groups8New Organic Nonlinear Optical Pyridinium-Based Hydrate Crystals: Trimethoxy-Induced Noncentrosymmetric Alignment6Chiral amino acid-templated tin fluorides tailoring nonlinear optical properties, birefringence, and photoluminescence17A Sharp Improvement of Sulfate's Birefringence Induced by the Synergistic Effect of Heteroleptic and Dimeric Strategies14Achieving great optical anisotropy with the well-directed alignment of π-conjugated groups due to hydrogen bonds9Fluorination strategy toward chemical and functional modification65Exploration of antimony( iii ) oxyhalides via single-site substitution in quest of large birefringence10NaB(OH) 3 CH 3 : a deep-ultraviolet optical crystal with unprecedented methyl-modified [B(OH) 3 CH 3 ] units6Research progress in optical materials with cationic organic planar π-conjugated groups containing CN bonds34β -CsHg 2 I 5 , a compound with rare [Hg 2 I 5 ] dimers and large optical anisotropy2Screening Large Birefringent Materials via Halogen Regulation in Ternary d0-Transition Metal Oxyhalides8Synthesis, structures and properties of two new nitrate optical materials: Rb3ZnNO3Cl4 and Rb5Na(NO3)4Cl24The Birefringence Modulation in Short‐Wave Ultraviolet Sulfates with Functional π‐Conjugated Cations and Polymerized Heteroleptic Tetrahedral Anions18AYSO4F2 (A = K, Rb): [YO4F4] Polyhedra Enhancement of Birefringence in Non-π-Conjugated Sulfate Systems9KPO2(NHCONH2)2: A Promising Deep-Ultraviolet Nonlinear Optical Phosphate Containing Polar [PO2(NHCONH2)2]− Tetrahedra15Hg4(Te2O5)(SO4): A Giant Birefringent Sulfate Crystal Triggered by a Highly Selective Cation153Enhancement of Birefringence in π-Conjugated Oxyfluorides Achieved via van der Waals Layered Structural Optimization10A Universal Design Strategy Achieving Large Birefringence and Short Phase‐Matching Capability of Optical Materials via Dissimilating Non‐π‐Conjugated Units6Enhanced Birefringence in Phosphates via “Two Steps in One”: d0 Transition Metal Regulation and Fluorination Synergistic Strategy7Effect of synthesis conditions on the thermoluminescence of Li9Mg3[PO4]4F3 fluorophosphate6Breaking Boundaries: Giant Ultraviolet Birefringence in Dimension‐Reduced Zn‐Based Crystals66Breaking Boundaries: Giant Ultraviolet Birefringence in Dimension‐Reduced Zn‐Based Crystals8Fluorine-driven materials design of novel deep-ultraviolet nonlinear optical crystal materials: Research progress and challenges6NH4Y(SO4)2·H2O and NH4YSO4F2: Two New Ammonium‐Rare Earth Metal Sulfates with Enhanced Optical Anisotropy and Deep Ultraviolet Transmission3Promising Functional Structural Building Unit Trisulfimide (SO2N)33– and Its Contributions to Second Harmonic Generation and Birefringence1Sulfate 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 Ordering4The design of a non-centrosymmetric structure in sulfates by cation-induced symmetry breaking4The 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 Distribution14Looking Back the Nonlinear Optical Crystals in a Functionalized Unit's Perspective109A strongly birefringent sulfate crystal with a wide second-harmonic generation phase-matching range4Hydrogen bonding regulation-oriented design of pyridine sulfonate as a promising UV birefringent crystal characterized by enhanced structural anisotropy11K 2 SO 4 (NH 3 SO 3 ) 2 and Cs 2 SO 4 (NH 3 SO 3 ) 3 : two deep-UV transparent sulfamate-sulfates with moderate birefringence2Realizing large birefringence via S-substitution and anisotropic arrangement optimization4A HTO‐Type Nonlinear Optical Fluorophosphate with Ultrawide Bandgap16Birefringence Modulation by Phenyl and Acyl Groups in Urea-Based Crystals3Metal Cation Engineered UV Birefringent Crystals in π‐Conjugated Sulfonates with Record‐High Optical Anisotropy17Sb2(TeO4)(SO4): An Anhydrous Tellurite Sulfate with Large Birefringence and Enhanced Thermal Stability8Synthesis, characterization and theoretical calculations of a new rare-earth fluoride with a DUV cutoff edge1NH4PO3HCH3 and NH4PO3CH2NH3: Two Phosphate Derivatives with Deep-UV Cutoff Edges and Moderate Birefringence1[CON3H6BF4]: An Efficient Metal‐Free Borate with Optimized Birefringence Achieved by Structural Design Strategy15[C( NH2 )3] 2SiF6 : Design of Deep Ultraviolet Crystals with Large Birefringence Based on a Fluorination‐Oriented Strategy13The Layered Structure–Induced Enhanced Birefringence of LiMgPO 4 : A First‐Principles Investigation1Three-In-One: A Guanidinium-Containing Niobium Oxyfluoride with a Perovskite-like Structure Revealing Multifunctional Optical Properties2Reversal Enhancement of Birefringence by Stereochemically Active Lone Pairs in Sn(II)-Based Mixed Halides0K 2 GdB 3 O 6 F 2 : A Promising Short-Wave UV Birefringent Crystal via Optimized Assembly of π-Conjugated [B 3 O 6 ] Groups8Enhancement of Birefringence in Alkali Metal Sulfates Induced by Rare Earth Metal-Centered Polyhedra and Structure Regulation via Cations2Ba 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 Tetrahedra2A 2 Sb 2 SO 4 F 6 (A = NH 4 + , Na + ): two sulfate fluoride crystals exhibiting enhanced birefringence driven by stereochemically active antimony( iii )1A[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 ] − groups0Synergistic dual-modification strategy of π-conjugated cations and tetrahedra: rational design of ultraviolet high-birefringence monofluorophosphates0The condensation of π-conjugated units: a new paradigm for designing high-performance optical crystals4Ba 4 CdGa 2 S 6 F 4 : A Chalcohalide Birefringent Crystal with Large Band Gap Designed by the Cation and Anion Cosubstitution Strategy2LiK4B(SO4)4: a potential optical crystal for deep ultraviolet zero-order waveplates1Hydrogen‐Bond‐Directed Assembly of Urea Derivatives: Exceptional Birefringence Achieved by π ‐Conjugated Unit Alignment3Cation-sulfur-driven dimensional reduction engineering for tailoring sulfonate birefringent crystals with enhanced anisotropy2Accelerated Discovery of Fluorophosphates as Deep‐Ultraviolet Nonlinear Optical Materials in the Y–P–O–F System: Unveiling New Composition‐Structure‐Property Rules1Visible-light-driven photoswitching of donor-acceptor Stenhouse adducts: unlocking giant modulation of second-order nonlinear optical responses via π-conjugation engineering0A Strategy for Enhancing the Optical Anisotropy of Phosphates via Tetrahedral Unit Modification0Halogen-Substitution-Modulated Lone-Pair Orientation in Sb(H 2 PO 2 ) 2 X (X = Cl, F) for Enhanced UV Birefringence1Toward the vacuum-ultraviolet frontier in nonlinear optical frequency conversion: phase-matching mechanisms across dimensions and architectures2The Multi‐Scale Paradigm: An Integrated Design Logic for Nonlinear Optical Crystals1The Multi‐Scale Paradigm: An Integrated Design Logic for Nonlinear Optical Crystals0Assembly of dual π-conjugated units toward enhanced birefringence in a 2D organic sulfonate crystal0

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  1. Li 5 Cs(SO 4 ) 3 : a potential zero-order wave plate material with short deep-ultraviolet cutoff edge

    New Journal of Chemistry · 2021-01-01

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  2. Two bismuth iodate sulfates with enhanced optical anisotropy

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  3. Toward the Enhancement of Critical Performance for Deep-Ultraviolet Frequency-Doubling Crystals Utilizing Covalent Tetrahedra

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  4. Tetrafluoroborate-Monofluorophosphate (NH4)3[PO3F][BF4]: First Member of Oxyfluoride with B–F and P–F Bonds

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  5. Non-π-Conjugated Deep-Ultraviolet Nonlinear Optical Crystal K2Zn3(SO4)(HSO4)2F4

    The Journal of Physical Chemistry Letters · 2021-08-24

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  6. Achieving Short‐Wavelength Phase‐Matching Second Harmonic Generation in Boron‐Rich Borosulfate with Planar [BO3] Units

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  7. Achieving Short‐Wavelength Phase‐Matching Second Harmonic Generation in Boron‐Rich Borosulfate with Planar [BO3] Units

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  8. Pushing KTiOPO4-like Nonlinear Optical Sulfates into the Deep-Ultraviolet Spectral Region

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  9. AZn 2 (BO 3 )Si 2 O 5 (A = Rb, Cs): first examples of KBe 2 BO 3 F 2 structure type in the borosilicate family exhibiting a deep-ultraviolet cutoff edge

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  10. (N 2 H 6 )[HPO 3 F] 2 : maximizing the optical anisotropy of deep-ultraviolet fluorophosphates

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  11. Ba 2 Zn 2 B 6 O 13 : coplanar [B 2 O 5 ] in unnoted U-shaped [B 6 O 13 ] groups achieving large birefringence

    Chemical Communications · 2022-01-01

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  12. Hg 2 (SeO 3 )(SO 4 ): the first sulfate selenite with large birefringence explored from d 10 transition metal compounds

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  13. Large optical anisotropy differentiation induced by the anion-directed regulation of structures

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  14. Large optical anisotropy-oriented construction of a carbonate-nitrate chloride compound as a potential ultraviolet birefringent material

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  15. Li 7 SrScB 12 O 24 and Li 7 Ba 0.6 Ca 0.4 ScB 12 O 24 : two new quaternary rare-earth borates with short UV cutoff edges

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  16. Linear unit BN 2 : a novel birefringence-enhanced fundamental module with sp orbital hybridization

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  17. LiSrSbS 3 : parallel configurations of lone pair electrons inducing a large birefringence

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  18. Performance of optical materials with the derivative of planar π-conjugated groups: Recent advances and future prospects

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  19. PNO: a promising deep-UV nonlinear optical material with the largest second harmonic generation effect

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  20. Variable dimensionality of the anion framework in four new borophosphates and fluoroborophosphates with short cutoff edges

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  21. First-principles study of the influence of lone pair electrons and molecular groups on the birefringence of phosphate and fluorophosphate

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  22. Review of Heteroleptic Tetrahedra as Birefringent or Nonlinear Optical Motifs

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  23. A microstructure engineered perovskite super anode with Li-storage life of exceeding 10,000 cycles

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  24. Potential optical functional crystals with large birefringence: Recent advances and future prospects

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  25. Explorations of New SHG Materials in Mercury Iodate Sulfate System**

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  27. Phosphogermanate Crystal: A New Ultraviolet–Infrared Nonlinear Optical Crystal with Excellent Optical Performances

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  28. Alkali metal sulfate: A new non-π-conjugated deep-ultraviolet quasi-phase matching crystal

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  29. An Optimized KBe2BO3F2‐Like Structure: The Unity of Deep‐Ultraviolet Transparency, Nonlinear Optical Property, and Ferroelectricity

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  30. NaBaBS3: A Promising Infrared Functional Material with Large Birefringence Induced by π-Conjugated [BS3] Units

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  31. Molecular Structure Design, Crystal Growth, and Characterization of New Types of Organic Nonlinear Optical Chalcone Crystals

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  32. Novel pull–push organic switches with D–π–A structural designs: computational design of star shape organic materials

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  33. [Ba2F2][Ge2O3S2]: An Unprecedented Heteroanionic Infrared Nonlinear Optical Material Containing Three Typical Anions

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  34. Designing a deep-UV nonlinear optical monofluorophosphate

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  35. From Phosphate Fluoride to Fluorophosphate: Design of Novel Ultraviolet/Deep-Ultraviolet Nonlinear Optical Materials for BePO3F with Optical Property Enhancement

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  36. Tailored Ordered Structures with Functional Units of Distorted [NbO6] and Antiparallel [GeO4] for Enhanced Birefringence in Germanate Crystal

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  37. SbHPO3F: 2D van der Waals Layered Phosphite Exhibiting Large Birefringence

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  38. Achieving effective balance between bandgap and birefringence by confining π-conjugation in an optically anisotropic crystal

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  39. A High‐Performance Nonlinear Optical Crystal with a Building Block Containing Expanded π‐Delocalization

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  40. A High‐Performance Nonlinear Optical Crystal with a Building Block Containing Expanded π‐Delocalization

    Angewandte Chemie · 2022-11-07

    Yanqiang Li, Weiqi Huang, Zhou Yang, Xianyu Song, Jieyu Zheng, Han Wang, Yipeng Song, Minjuan Li, Junhua Luo, Sangen Zhao

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  41. Exploring Short-Wavelength Phase-Matching Nonlinear Optical Crystals by Employing KBe2BO3F2 as the Template

    ACS Central Science · 2022-11-11

    Zi‐Jian Li, Wenqi Jin, Fangfang Zhang, Zhihua Yang, Shilie Pan

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