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RESEARCH PAPER · Angewandte Chemie International Edition · 2021

Hydroxyfluorooxoborate Na[B3O3F2(OH)2]⋅[B(OH)3]: Optimizing the Optical Anisotropy with Heteroanionic Units for Deep Ultraviolet Birefringent Crystals

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Hydroxyfluorooxoborate Na[B3O3F2(OH)2]⋅[B(OH)3]: Optimizing the Optical Anisotropy with Heteroanionic Units for Deep Ultraviolet Birefringent CrystalsOriginalRbMo 2 P 3 O 14 with large birefringence mainly induced by highly distorted [MoO 6 ] in uncommon [Mo 2 P 3 O 14 ] ∞ layers9Two metal-free cyanurate crystals with a large optical birefringence resulting from the combination of π-conjugated units17Tetrafluoroborate-Monofluorophosphate (NH4)3[PO3F][BF4]: First Member of Oxyfluoride with B–F and P–F Bonds16Finding a Series of BaBOF3 Fluorooxoborate Polymorphs with Tunable Symmetries: A Simple but Flexible Case37Nonlinear optical properties of a new polar bismuth tellurium oxide fluoride, Bi3F(TeO3)(TeO2F2)315AAl3P6O20 (A = Rb, Cs): Two deep-ultraviolet transparent nonlinear optical materials designed by aliovalent substitution11K 3 V 2 O 3 F 4 (IO 3 ) 3 : a high-performance SHG crystal containing both five and six-coordinated V 5+ cations33Ba2B13O19(OH)5·5H2O: A promising nonlinear optical material with a unique 2[B13O19(OH)5]∞ two-dimensional layer9Na4B8O9F10: A Deep‐Ultraviolet Transparent Nonlinear Optical Fluorooxoborate with Unexpected Short Phase‐Matching Wavelength Induced by Optimized Chromatic Dispersion133Na4B8O9F10: A Deep‐Ultraviolet Transparent Nonlinear Optical Fluorooxoborate with Unexpected Short Phase‐Matching Wavelength Induced by Optimized Chromatic Dispersion13Guanidinium Fluorooxoborates as Efficient Metal-free Short-Wavelength Nonlinear Optical Crystals140(C 3 N 6 H 7 ) 2 SiF 6 ·H 2 O: an ultraviolet birefringent crystal exceeding the intrinsic energy gap of an organic reagent38(N 2 H 6 )[HPO 3 F] 2 : maximizing the optical anisotropy of deep-ultraviolet fluorophosphates33[C 3 N 6 H 7 ] 2 [B 3 O 3 F 4 (OH)]: a new hybrid birefringent crystal with strong optical anisotropy induced by mixed functional units85[C(NH 2 ) 3 ] 2 S 2 O 8 : combining delocalized and localized π-conjugate units to achieve strong optical anisotropy21Ba 2 Zn 2 B 6 O 13 : coplanar [B 2 O 5 ] in unnoted U-shaped [B 6 O 13 ] groups achieving large birefringence6BaI 3 O 9 H: a new alkaline-earth metal hydroxy iodate with two groups2CsB 3 O 4 (OH) 2 : a new deep-ultraviolet birefringent crystal with [B 3 O 4 (OH) 2 ] anionic group8Hg 2 (SeO 3 )(SO 4 ): the first sulfate selenite with large birefringence explored from d 10 transition metal compounds36Na 3 YB 8 O 15 : a new rare-earth borate with an infinite one-dimensional [B 8 O 15 ] ∞ chain and a short ultraviolet cutoff edge8Na 4 Ga 8 S 14 : a Ga-enriched wide band gap ternary alkali-metal sulfide with unique [Ga 12 S 42 ] 12-membered rings2Performance of optical materials with the derivative of planar π-conjugated groups: Recent advances and future prospects37Two porous-layered borates built by B 7 O 13 (OH) clusters and AlO 4 /GaO 4 tetrahedra7High‐Performance Sulfate Optical Materials Exhibiting Giant Second Harmonic Generation and Large Birefringence21High‐Performance Sulfate Optical Materials Exhibiting Giant Second Harmonic Generation and Large Birefringence199New Self-Organizing Optical Materials and Induced Polymorphic Phases of Their Mixtures Targeted for Energy Investigations17Chiral Ligand‐Driven Systematic Synthesis of Coordination Polymers with Non‐centrosymmetric Structures12Novel layered heterobimetallic fluorides with large optical band gaps3Two Indium Iodate–Nitrates with Large Birefringence Induced by Hybrid Anionic Functional Groups and Their Favorable Arrangements22LiB5O5F2(OH)4: A new deep-ultraviolet birefringent crystal with [B5O5F2(OH)4] anionic group28Promising Deep‐Ultraviolet Birefringent Materials via Rational Design and Assembly of Planar π‐Conjugated [B(OH)3] and [B3O3(OH)3] Functional Species6Promising Deep‐Ultraviolet Birefringent Materials via Rational Design and Assembly of Planar π‐Conjugated [B(OH)3] and [B3O3(OH)3] Functional Species83A Theoretical Perspective to Study the Optical Properties of Tetrafluoroborates4Structural Characterization and ORR Activity of a Copper Complex Borate and an Unexpected [Ni(atta)(SO4)0.5]+ Borate-Sulfate7Enhancement of Birefringence in Borophosphate Pushing Phase-Matching into the Short-Wavelength Region150NaBaBS3: A Promising Infrared Functional Material with Large Birefringence Induced by π-Conjugated [BS3] Units32Difluoro(oxalato)borates as Short-Wavelength Optical Crystals with Bifunctional [BF 2 C 2 O 4 ] Units38Rearrangement of [B2O5] Dimers within [B7O14] Clusters Enables Enhanced Optical Anisotropy in Li3Cs6Al2B14O28F4An Optically Anisotropic Crystal with Large Birefringence Arising from Cooperative π Orbitals81An Optically Anisotropic Crystal with Large Birefringence Arising from Cooperative π Orbitals22An excellent deep-ultraviolet birefringent material based on [BO2]∞ infinite chains185NaB3O4F(OH): A Hydroxyfluorooxoborate with One-Dimensional Chain Featuring Large Birefringence and Short Ultraviolet Cutoff Edge5Tailored Ordered Structures with Functional Units of Distorted [NbO6] and Antiparallel [GeO4] for Enhanced Birefringence in Germanate Crystal15Ag4SnGe2S7: A Noncentrosymmetric Chalcogenide in I4–II–IV2–VI7 System with Non-Diamond-Like Structure Featuring 1D ∞[SnGe2S8]6– Infinite Chain2BaSb(H2PO2)3Cl2: An excellent UV nonlinear optical hypophosphite exhibiting strong second-harmonic generation response32A new birefringent material, HfF2(IO3)2, with a large birefringence and improved overall performances achieved by the integration of functional groups19Cs2B4O5(OH)4: A new hydrated borate with a short UV cutoff edge2SbHPO3F: 2D van der Waals Layered Phosphite Exhibiting Large Birefringence32Finding a Deep‐UV Borate BaZnB4O8 with Edge‐sharing [BO4] Tetrahedra and Strong Optical Anisotropy20Achieving effective balance between bandgap and birefringence by confining π-conjugation in an optically anisotropic crystal39In Situ Kinetic Observations on Crystal Nucleation and Growth385LiKCuP2O7: Cation substitution application with mixed-alkaline copper-containing pyrophosphate and magnetic properties2A lithium–scandium sulfate with second-harmonic generation response and deep-ultraviolet transparency7Cs[B 3 O 3 F 2 (OH) 2 ]: discovery of a hydroxyfluorooxoborate guided by selective organic–inorganic transformation13Discovery of SrZn 2 B 6 O 12 with an unprecedented quadruple-layered configuration0Dramatically improved optical anisotropy by realizing stereochemically active lone pairs in a sulfate system, K 2 SO 4 ·HIO 323Enhancing birefringence of non-π-conjugated sulfate systems through rare-earth metal-centered polyhedra10Hg 3 O 2 (NO 3 )F: a mercury nitrate oxyfluoride with an unprecedented [(Hg 3 O 2 F) + ] ∞ cationic framework and excellent optical anisotropy21Hydroxyfluorooxoborate (NH 4 )[C(NH 2 ) 3 ][B 3 O 3 F 4 (OH)] for exploring the effects of cation substitution on structure and optical properties26K 5 [B 3 O 3 F 4 (OH)] 2 (NO 3 ): the first hydroxyfluorooxoborate-nitrate with a short ultraviolet cutoff edge and large birefringence18LiCs 3 AlB 7 O 14 : achieving enhanced optical anisotropy via [AlO 4 ] tetrahedron introduction to rearrange the anionic framework5Recent progress in borate-based short-wavelength nonlinear optical crystals with boron–oxygen skeleton modification28Recent progress on sulfide infrared nonlinear optical materials with large SHG response and wide band gap26Controlling the Nonlinear Optical Behavior and Structural Transformation with A‐Site Cation in α‐AZnPO4 (A = Li, K)20Identifying Ordered OH/F Anions in Hydroxyfluorides by a Terahertz Spectroscopic Approach21Recent Development of Sn II , Sb III ‐based Birefringent Material: Crystal Chemistry and Investigation of Birefringence130Recent Development of SnII, SbIII‐based Birefringent Material: Crystal Chemistry and Investigation of Birefringence6Na2BaB12O18F4: A Mixed Alkali/Alkaline-Earth Metal Fluorooxoborate with Two Unprecedented Interpenetrating Three-Dimensional B–O/F Anionic Networks and a Short Ultraviolet Cutoff Edge9Chain‐like [S x ] ( x =2–6) Units Realizing Giant Birefringence with Transparency in the Near‐Infrared for Optoelectronic Materials53Chain‐like [S x ] ( x =2–6) Units Realizing Giant Birefringence with Transparency in the Near‐Infrared for Optoelectronic Materials5Remarkable phase-matchable second-harmonic generation realized by strong polarities of [PbSe3] and [GaSe4] functional motifs in PbGa4Se718Stereochemically Active Tin(II)‐Induced Enhancement of Birefringence in SnIISnIV(PO4)2 and SrSn(PO4)PO2(OH)23“Cation Activation”: An Effective Strategy for the Enhancement of Birefringence36Na3SiS3F: A Wide Bandgap Fluorothiosilicate with Unique [SiS3F] Unit and High Laser‐Induced Damage Threshold39KHC 2 O 4 · B ( OH ) 3 : A nonlinear optical crystal with large birefringence in the short‐wavelength ultraviolet region9Target-Oriented Synthesis of Borate Derivatives Featuring Isolated [B3O3] Six-Membered Rings as Structural Features20Mixed Alkali Metal and Alkaline Earth Metal Scandium Borate Birefringence Material with Layered Structure and Short Ultraviolet Cutoff Edge17Improved Birefringence Activated by Tetrahedra Decorated with a Single Linear Unit38Improved Birefringence Activated by Tetrahedra Decorated with a Single Linear Unit1Fluorooxoborate Promoting the Exploration of Short-Wavelength Linear and Nonlinear Optical Crystals with Expected Properties and Versatile Structures27Introduction of the [B–O/F] Units Enhances the Band Gap and Birefringence from Na6Mg3B10O18F6 to K3NaB10O16F211Heterologous Isomorphic Substitution Induces Optical Property Enhancement for Deep-UV Crystals: a Case in Rb[B3O3F2(OH)2]10Improvement on Magnetocaloric Effect through Structural Evolution in Gadolinium Borate Halides Ba2Gd(BO3)2X (X = F, Cl)9The synthesis of novel lanthanum hydroxyborate at extreme conditions3Designing a Hybrid Perovskite with Enlarged Birefringence and Bandgap for Modulation of Light Polarization32Fluorination Strategy Towards Symmetry Breaking of Boron‐centered Tetrahedron for Poly‐fluorinated Optical Crystals15Fluorination Strategy Towards Symmetry Breaking of Boron‐centered Tetrahedron for Poly‐fluorinated Optical Crystals70Fluorination strategy toward chemical and functional modification65A borate [C 6 N 2 H 15 ]·[B 5 O 6 (OH) 4 ] ferroelectric crystal: synthesis, properties and film fabrication7C 8 H 6 IN 3 O 4 : a birefringent crystal induced by uniformly aligned hybrid groups10Designing excellent UV birefringent materials through the synergistic interaction of two highly distorted functional groups23Discovery of a new bimetallic borate with strong optical anisotropy activated by π-conjugated [B 2 O 5 ] units3Explorations of highly birefringent materials in the vanadium oxyfluoride–iodate system by fluoride ion modulation8HgBr 2 : an easily growing wide-spectrum birefringent crystal38NaB(OH) 3 CH 3 : a deep-ultraviolet optical crystal with unprecedented methyl-modified [B(OH) 3 CH 3 ] units6Where do the Fluorine Atoms Go in Inorganic‐Oxide Fluorinations? A Fluorooxoborate Illustration under Terahertz Light1Where do the Fluorine Atoms Go in Inorganic‐Oxide Fluorinations? A Fluorooxoborate Illustration under Terahertz Light33Two Hydroxyfluorooxoborates Achieving Deep‐Ultraviolet Cutoff Edges and Moderate Birefringence by Assembling Multi‐Anionic Groups6Tunable Optical Anisotropy in Rare‐Earth Borates with Flexible [BO3] Clusters7(C 8 H 7 N 2 O 2 ) 2 [Bi 2 Br 8 ]·2H 2 O and (C 8 H 7 N 2 O 2 ) 6 [Bi 2 Cl 10 ]Cl 2 ·2H 2 O: Exploring Birefringent Crystals in Hybrid Halide Systems5C9H7NBrX (X = Cl, Br, NO3): Three Excellent Birefringent Crystals with Distinct Optical Anisotropy Regulated by Anions34Deep-Ultraviolet Bialkali–Rare Earth Metal Anhydrous Sulfate Birefringent Crystal11Review on birefringence in borates based on birefringence-active functional groups and arrangements57Bi(SO4)F·H2O and Bi(SO4)(NO3)·3H2O: Chemical Substitution-Induced Birefringence Enhancement in Bismuth Sulfates6[B3O3F4(OH)]2–: A Versatile Hydroxyfluorooxoborate Heteroanion Producing Compounds with Highly Tunable Optical Anisotropy19A3Sc(SO4)3 (A = K, Rb, Cs): Three Deep‐Ultraviolet Transparent Alkali‐Scandium Sulfates with Strong Second‐Harmonic Generation Response and High Thermal Stability14NH4Y(SO4)2·H2O and NH4YSO4F2: Two New Ammonium‐Rare Earth Metal Sulfates with Enhanced Optical Anisotropy and Deep Ultraviolet Transmission3(C3N2H5)B3O3F2(OH)2: Realizing Large Birefringence via a Synergistic Effect between Anion F/OH‐Ratio Optimization and Cation Activation25CdInO(BO3): An oxyborate birefringent material explored from d10 metal compounds1Sulfate 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 Ordering4Ae3[TO3][SnOQ3] (Ae = Sr, Ba; T = Si, Ge; Q = S, Se) and Ba3[CO3][MQ4] (M = Ge, Sn; Q = S, Se): Design and Syntheses of a Series of Heteroanionic Antiperovskite-Type Oxychalcogenides29From B 3 O 3 (OH) 3 to B 3 O 3 F 3 : Uncovering Series of New Functional Units Based on [BO 2 F] Beneficial for Deep‐Ultraviolet Birefringence1Structural 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)12(CN 4 H 7 ) 2 SO 4 ·H 2 O: high-performance metal-free ultraviolet birefringent crystal with KBBF-like configuration5A remarkable solar-blind ultraviolet nonlinear optical crystal with comprehensive performance and enhanced thermal stability4A tri-alkali/alkaline-earth metal fluorophosphate deep-ultraviolet birefringent crystal with coexisting PO 3 F and PO 2 F 24An excellent ultraviolet nonlinear optical crystal derived from the polar methylphosphonate unit8CsBO(OH) 2 : a new hydroxyborate with the rare [BO(OH) 2 ] group and a deep ultraviolet cutoff edge3K 2 Na(I 3 O 8 ) 3 : a promising mid-infrared birefringent material with two different structures of octaoxotriiodate( v ) polyanions1NaCaGa 3 S 6 : a mixed alkali metal and alkaline earth metal sulfide with a distinctive [Ga 5 S 10 ] ∞ layered framework0RbB 7 O 10 (OH) 2 and NaB 11 O 16 (OH) 2 : alkali metal hydroxyborates with two-dimensional layered structures and large birefringence1Soft–Rigid Structural Integration in KMgBO3: A Pathway to Negative Thermo-optic Coefficient via Positive Thermal Expansion and Negative Temperature-Dependent Optical Absorption Edge2Na3Y2F3P2O8 and K4Y3F5P4O14: [YOF] Polyhedra Inducing Birefringence Enhancement in Non-π-Conjugated Phosphate Systems3Size effect of cations in the A2B3O4F3 family: Based on the new member Cs2B3O4F34Breaking the Natural Tendency of Deep‐UV Polyborate Anion Clusters to Inducing Strong Optical Anisotropy13Recent progress in structural design strategies of high-birefringence optical crystals54Non-equivalent terminating roles of hydroxyl and fluorine in hydroxy/fluorooxo-borate optical functional materials2CsICl 2 : A Record-Birefringent Inorganic Crystal with Ultrawide Infrared Transparency Enabled by Linear Interhalogen ICl 2 – Units36Borosilicates as deep-ultraviolet transparent nonlinear optical crystals: Structural motifs, performance limits and future directions9CsGaGe₃Se₈: Enhanced optical anisotropy and bandgap via cation-substitution-driven dimensionality reduction0Triple Integration of π‐Conjugated Building Blocks: Unprecedented Assembly for Large Optical Anisotropy11Sulfonated Module Aggregation for Ultrahigh Birefringence in Aqueous-Processable Crystals26Effect of Multiple Hydrogen Bonding on the π-Conjugated Groups and Optical Properties in Molecular Crystals5Heterocationic strategy to design a nonlinear optical crystal with a polar anti-perovskite structure7LiV 3 Se 2 O 12 : A Promising Giant‐Birefringent Crystal Enabled by Significant Structural Distortion3Design of borate-squarate hybrid crystals with large birefringence by synergistic assembly of planar π-conjugated groups0The condensation of π-conjugated units: a new paradigm for designing high-performance optical crystals4Noncovalent Assembly Engineering Achieves Excellent Birefringence in Crystals0F−/OH− terminal modification of [B3O6] clusters: Constructing deep-ultraviolet hydroxyfluorooxoborates with tunable optical performance0Steric hindrance and hydrogen-bond networks synergistically directing molecular alignment for high-performance ultraviolet birefringent1Halogen-Substitution-Modulated Lone-Pair Orientation in Sb(H 2 PO 2 ) 2 X (X = Cl, F) for Enhanced UV Birefringence1Parallel arrangement of functional building blocks: toward performance synergy in oxalate borate ultraviolet nonlinear optical crystals0From High Symmetry to High Symmetry: A Self‐Assembly Strategy for Synthesizing Large Birefringent Borates0Decoupling Contributions of Distinct Strategies for Enhancing Polarizability Anisotropy in Crystals Containing π-Conjugated Groups0Fluorination‐Driven Molecular Polarization Engineering in Hydroxyfluorooxoborates for Generating Strong Short‐Wavelength Nonlinear Optical Responses0

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  2. Two metal-free cyanurate crystals with a large optical birefringence resulting from the combination of π-conjugated units

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

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  4. Finding a Series of BaBOF3 Fluorooxoborate Polymorphs with Tunable Symmetries: A Simple but Flexible Case

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  5. Nonlinear optical properties of a new polar bismuth tellurium oxide fluoride, Bi3F(TeO3)(TeO2F2)3

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