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RESEARCH PAPER · Chemical Reviews · 2020

Borates: A Rich Source for Optical Materials

Miriding Mutailipu, Kenneth Reinhard Poeppelmeier, Shilie Pan

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Borates: A Rich Source for Optical MaterialsOriginal[GaF(H 2 O)][IO 3 F]: a promising NLO material obtained by anisotropic polycation substitution43Aliovalent-cation-substitution-induced structure transformation: a new path toward high-performance IR nonlinear optical materials47Ba 4 Ca(B 2 O 5 ) 2 F 2 : π-conjugation of B 2 O 5 in the planar pentagonal layer achieving large second harmonic generation of pyro -borate34Recent progress in oxychalcogenides as IR nonlinear optical materials79Finding Short-Wavelength Birefringent Crystals with Large Optical Anisotropy Activated by π-Conjugated [C(NH2)3] Units44Large Second-Harmonic Response and Giant Birefringence of CeF 2 (SO 4 ) Induced by Highly Polarizable Polyhedra247Discovery of NLO Semiorganic (C 5 H 6 ON) + (H 2 PO 4 ) − : Dipole Moment Modulation and Superior Synergy in Solar-Blind UV Region270Toward the Enhancement of Critical Performance for Deep-Ultraviolet Frequency-Doubling Crystals Utilizing Covalent Tetrahedra137Cyanurates consisting of intrinsic planar π-conjugated 6-membered rings: An emerging source of optical functional materials111Discovery of First Magnesium Fluorooxoborate with Stable Fluorine Terminated Framework for Deep‐UV Nonlinear Optical Application168Expanding the chemistry of borates with functional [BO2]− anions200ASb5S8 (A = K, Rb, and Cs): Thermal Switching of Infrared Nonlinear Optical Properties across the Crystal/Glass Transformation39K5Mg2La3(BO3)6: An Efficient, Deep-Ultraviolet Nonlinear Optical Material70Be2(BO3)(IO3): The First Anion‐mixed Van der Waals Member in the KBe2BO3F2 Family with a Very Strong Second Harmonic Generation Response130High-Performance Second-Harmonic-Generation (SHG) Materials: New Developments and New Strategies323LiB2O3F: A Beryllium-Free Deep-Ultraviolet Nonlinear Optical Material Designed Based on a Boron-Rich Strategy62AZn4Ga5Se12 (A = K, Rb, or Cs): Infrared Nonlinear Optical Materials with Simultaneous Large Second Harmonic Generation Responses and High Laser-Induced Damage Thresholds34Hydroxyfluorooxoborate Na[B3O3F2(OH)2]⋅[B(OH)3]: Optimizing the Optical Anisotropy with Heteroanionic Units for Deep Ultraviolet Birefringent Crystals147A2MoO2F3(IO2F2) (A = Rb, Cs): Strong Nonlinear Optical Responses and Enlarged Band Gaps through Fluorine Incorporation51Exploring Deep-UV Nonlinear Optical Materials with Enhanced Second Harmonic Generation Response and Birefringence in Fluoroaluminoborate Crystals69CsBaB9O15: a high performance ultraviolet nonlinear optical material activated by the peculiar double layered configuration80Prediction and Understanding: Quantum Chemical Framework of Transition Metals Enclosed in a B12N12 Inorganic Nanocluster for Adsorption and Removal of DDT from the Environment67Theoretical Understanding and Role of Guest π-Bridges in Triphenylamine-Based Donor Materials for High-Performance Solar Cells67Li 4 MgGe 2 S 7 : The First Alkali and Alkaline‐Earth Diamond‐Like Infrared Nonlinear Optical Material with Exceptional Large Band Gap214A Congruent‐Melting Mid‐Infrared Nonlinear Optical Vanadate Exhibiting Strong Second‐Harmonic Generation64Hg 3 P 2 S 8 : A New Promising Infrared Nonlinear Optical Material with a Large Second-Harmonic Generation and a High Laser-Induced Damage Threshold111Giant Second-Harmonic Generation Response and Large Band Gap in the Partially Fluorinated Mid-Infrared Oxide RbTeMo 2 O 8 F150Transition-metal-based chalcogenides: A rich source of infrared nonlinear optical materials185Hydrogen as an energy currency: Encapsulation of inorganic Ga12N12 with alkali metals for efficient H2 adsorption as hydrogen storage materials61SnPQ3 (Q = S, Se, S/Se): A Series of Lone-Pair Cationic Chalcogenophosphates Exhibiting Balanced NLO Activity Originating from SnQ8 Units50The Rise of Infrared Nonlinear Optical Pnictides: Advances and Outlooks36Finding a Series of BaBOF3 Fluorooxoborate Polymorphs with Tunable Symmetries: A Simple but Flexible Case37Achieving Short‐Wavelength Phase‐Matching Second Harmonic Generation in Boron‐Rich Borosulfate with Planar [BO3] Units102La 3 Ga 3 Ge 2 S 3 O 10 : An Ultraviolet Nonlinear Optical Oxysulfide Designed by Anion‐Directed Band Gap Engineering63Ca3(TeO3)2(MO4) (M = Mo, W): Mid-Infrared Nonlinear Optical Tellurates with Ultrawide Transparency Ranges and Superhigh Laser-Induced Damage Thresholds46β-BaGa 4 Se 7 : a promising IR nonlinear optical crystal designed by predictable structural rearrangement46Complex coordinated functional groups: A great genes for nonlinear optical materials64Hg-based chalcogenides: An intriguing class of infrared nonlinear optical materials130LiNbTeO5: A High-Performance Multifunctional Crystal Material with a Very Large Second-Harmonic Generation Response and Piezoelectric Coefficient52Na4B8O9F10: A Deep‐Ultraviolet Transparent Nonlinear Optical Fluorooxoborate with Unexpected Short Phase‐Matching Wavelength Induced by Optimized Chromatic Dispersion133Guanidinium 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[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 units85K 3 Sr 3 Li 2 Al 4 B 6 O 20 F: a competitive nonlinear optical crystal for generation of a 266 nm laser35Metal oxyhalides: an emerging family of nonlinear optical materials125Performance of optical materials with the derivative of planar π-conjugated groups: Recent advances and future prospects36Sc 2 F 2 (B 2 O 5 ): a deep ultraviolet scandium borate fluoride exhibiting large birefringence induced by the synergistic effect of B 2 O 5 and ScO n F 2 groups38HgTeO2F(OH): A Nonlinear Optical Oxyfluoride Constructed of Active [TeO2F(OH)]2– Pyramids and V-Shaped [HgO2]2– Groups36“Removing Center”─An Effective Structure Design Strategy for Nonlinear Optical Crystals37Ba2B10O16(OH)2·(H3BO3)(H2O): A Possible Deep-Ultraviolet Nonlinear-Optical Barium Borate36Strong Nonlinearity Induced by Coaxial Alignment of Polar Chain and Dense [BO3] Units in CaZn2(BO3)2215Rb5Ba2(B10O17)2(BO2): The formation of unusual functional [BO2]− in borates with deep-ultraviolet transmission window62Highly efficient and stable deep-blue room temperature phosphorescence via through-space conjugation68The Combination of Structure Prediction and Experiment for the Exploration of Alkali‐Earth Metal‐Contained Chalcopyrite‐Like IR Nonlinear Optical Material105Noncentrosymmetric Rare-Earth Borate Fluoride La2B5O9F3: A New Ultraviolet Nonlinear Optical Crystal with Enhanced Linear and Nonlinear Performance48Promising Deep‐Ultraviolet Birefringent Materials via Rational Design and Assembly of Planar π‐Conjugated [B(OH)3] and [B3O3(OH)3] Functional Species82Double‐Modification Oriented Design of a Deep‐UV Birefringent Crystal Functionalized by [B12O16F4(OH)4] Clusters138Eu 2 P 2 S 6 : The First Rare‐Earth Chalcogenophosphate Exhibiting Large Second‐Harmonic Generation Response and High Laser‐Induced Damage Threshold143(NH4)3B11PO19F3: a deep-UV nonlinear optical crystal with unique [B5PO10F]∞ layers142Borate particulate photocatalysts for photocatalytic applications: A review127Computation Assisted Design and Prediction of Alkali-Metal-Centered B12N12 Nanoclusters for Efficient H2 Adsorption: New Hydrogen Storage Materials54Two Metal Phosphate Nonlinear Optical Materials Simultaneously Exhibiting Ultraviolet Transparence and a Large Birefringence49Boric Acid‐Activated Room‐Temperature Phosphorescence and Thermally Activated Delayed Fluorescence for Efficient Solid‐State Photoluminescence Materials54AgGaSe2-Inspired Nonlinear Optical Materials: Tetrel Selenides of Alkali Metals and Mercury34A comprehensive review on metal chalcogenides with three-dimensional frameworks for infrared nonlinear optical applications115Difluoro(oxalato)borates as Short-Wavelength Optical Crystals with Bifunctional [BF 2 C 2 O 4 ] Units37Mixed-Anion-Oriented Design of LnMGa3S6O (Ln = La, Pr, and Nd; M = Ca and Sr) Nonlinear Optical Oxysulfides with Targeted Property Balance57An excellent deep-ultraviolet birefringent material based on [BO2]∞ infinite chains186From Phosphate Fluoride to Fluorophosphate: Design of Novel Ultraviolet/Deep-Ultraviolet Nonlinear Optical Materials for BePO3F with Optical Property Enhancement34A Hybrid Antiperovskite with Strong Linear and Second‐Order Nonlinear Optical Responses96Ternary AGa5S8 (A = K, Rb, Cs): Promising infrared nonlinear optical materials rationally realized by “one-for-multiple substitution” strategy37Strategies for Enhancement Luminance of Sub‐Micrometer Phosphor: A Sub‐Micrometer Narrow‐Band Red Phosphor with Ultrahigh Thermal Stability50Isoreticular Design of KTiOPO 4 -Like Deep-Ultraviolet Transparent Materials Exhibiting Strong Second-Harmonic Generation69Achieving Large Second Harmonic Generation Effects via Optimal Planar Alignment of Triangular Units63A High‐Performance Nonlinear Optical Crystal with a Building Block Containing Expanded π‐Delocalization94In Situ Kinetic Observations on Crystal Nucleation and Growth386Perfectly Encoding π‐Conjugated Anions in the RE5(C3N3O3)(OH)12 (RE=Y, Yb, Lu) Family with Strong Second Harmonic Generation Response and Balanced Birefringence91Emerging Chalcohalide Materials for Energy Applications164Rb 2 CdSi 4 S 10 : novel [Si 4 S 10 ] T2-supertetrahedra-contained infrared nonlinear optical material with large band gap79Ag-based chalcogenides and derivatives as promising infrared nonlinear optical materials92KREP2Se6 (RE = Sm, Gd, Tb): The First Rare‐Earth Selenophosphates with Remarkable Nonlinear Optical Activities Realized by Synergistic Effect of RE‐ and P‐Based Motifs39Aluminoborates as Nonlinear Optical Materials77(C 5 H 6.16 N 2 Cl 0.84 )(IO 2 Cl 2 ): a birefringent crystal featuring unprecedented (IO 2 Cl 2 ) − anions and π-conjugated organic cations56From 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 birefringence50β-(C 3 H 7 N 6 ) 2 Cl 2 ·H 2 O and (C 3 H 7 N 6 )F·H 2 O: two UV birefringent crystals induced by uniformly aligned structural groups35Intense d‐p Hybridization in Nb3O15 Tripolymer Induced the Largest Second Harmonic Generation Response and Birefringence in Germanates51Toward Large Second-Harmonic Generation and Deep-UV Transparency in Strongly Electropositive Transition Metal Sulfates112Nanoencapsulation-Induced Second Harmonic Generation in Pillararene-Based Host–Guest Complex Cocrystals46Recent progress in the design of IR nonlinear optical materials by partial chemical substitution: Structural evolution and performance optimization133Rational Design of a Rare‐Earth Oxychalcogenide Nd3[Ga3O3S3][Ge2O7] with Superior Infrared Nonlinear Optical Performance64NaRb 6 (B 4 O 5 (OH) 4 ) 3 (BO 2 ) Featuring Noncentrosymmetry, Chirality, and the Linear Anionic Group BO 2 –101[K2PbX][Ga7S12] (X = Cl, Br, I): The First Lead‐Containing Cationic Moieties with Ultrahigh Second‐Harmonic Generation and Band Gaps Exceeding the Criterion of 2.33 eV46Clamping effect driven design and fabrication of new infrared birefringent materials with large optical anisotropy44Target‐Driven Design of Deep‐UV Nonlinear Optical Materials via Interpretable Machine Learning125Modulating Emission of Boric Acid into Highly Efficient and Color‐Tunable Afterglow via Dehydration‐Induced Through‐Space Conjugation67Na3SiS3F: A Wide Bandgap Fluorothiosilicate with Unique [SiS3F] Unit and High Laser‐Induced Damage Threshold39Advances in aliovalent substitution strategy for the design and synthesis of nonlinear optical materials: d0 transition metal/gallium iodates and selenites69Achieving the full-wavelength phase-matching for efficient nonlinear optical frequency conversion in C(NH2)3BF4515Improved Birefringence Activated by Tetrahedra Decorated with a Single Linear Unit38Impact of symmetry breaking on the performance of non-fullerene acceptors (NFAs) for photo and thermally stable organic solar cells (OSCs): A DFT-based interrogation and investigation37From Monofluorophosphates A2PO3F to Difluorophosphates APO2F2 (A = alkali metal): Design of a Potential Deep-Ultraviolet Nonlinear Optical Materials System with a Shortened Phase-Matching Wavelength41Zn 2 HgP 2 S 8 : A Wide Bandgap Hg‐Based Infrared Nonlinear Optical Material with Large Second‐Harmonic Generation Response75Nonlinear optical inorganic sulfates: The improvement of the phase matching ability driven by the structural modulation41Quadruple‐Bidentate Nitrate‐Ligated A 2 Hg(NO 3 ) 4 (A=K, Rb): Strong Second‐Harmonic Generation and Sufficient Birefringence59A survey of stereoactive oxysalts for linear and nonlinear optical applications40Photophysics of corroles and closely related systems for emergent solar energy, medicinal, and materials science applications38Enhanced ammonia gas sensing by cost-effective SnO2 gas sensor: Influence of effective Mo doping39Breaking Through the Trade‐Off Between Wide Band Gap and Large SHG Coefficient in Mercury‐Based Chalcogenides for IR Nonlinear Optical Application49Structural diversity and complexity of antiperovskites38A prediction-driven database to enable rapid discovery of nonlinear optical materials46Breaking the Inherent Interarrangement of [B3O6] Clusters for Nonlinear Optics with Orbital Hybridization Enhancement143Highly Birefringent d 0 Transition Metal Fluoroantimonite in the Mid Infrared Band: Order–Disorder Regulation by Cationic Size84Fluorination Strategy Towards Symmetry Breaking of Boron‐centered Tetrahedron for Poly‐fluorinated Optical Crystals70Advances in Solid-State Nonlinear Optical Materials: From Fundamentals to Applications61Fluorination strategy toward chemical and functional modification65“Three‐in‐One”: A New Hg‐Based Selenide Hg 7 P 2 Se 12 Exhibiting Wide Infrared Transparency Range and Strong Nonlinear Optical Effect80Exploring a new short-wavelength nonlinear optical fluoride material featuring unprecedented polar cis -[Zr 6 F 34 ] 10− clusters48KBa 3 M 2 F 14 Cl (M = Zr, Hf): novel short-wavelength mixed metal halides with the largest second-harmonic generation responses contributed by mixed functional moieties37Large second harmonic generation and birefringence from extended octupolar π-conjugated structures35Rare-earth-based chalcogenides and their derivatives: an encouraging IR nonlinear optical material candidate71Recent advances in rational structure design for nonlinear optical crystals: leveraging advantageous templates153Giant Low-Field Cryogenic Magnetocaloric Effect in a Polycrystalline EuB 4 O 7 Compound71Cs 3 In(In 4 Se 7 )(P 2 Se 6 ): A Multi‐Chromophore Chalcogenide with Excellent Nonlinear Optical Property Designed by Group Grafting55Toward the ultraviolet (UV) or deep-UV nonlinear optical crystals: The combination of π-conjugated planar [XY3] and tetrahedral [XY4]801D Tin(II)‐Based Chiral Hybrid Perovskite Single Crystals with Extremely Distorted Inorganic Chains for Second Harmonic Generation38Record Second-Harmonic Generation and Birefringence in an Ultraviolet Antimonate by Bond Engineering157Temperature-dependent photoluminescence of novel Eu3+, Tb3+, and Dy3+ doped LaCa4O(BO3)3: Insights at low and room temperatures35Assembly of π‐Conjugated [B3O6] Units by Mer‐Isomer [YO3F3] Octahedra to Design a UV Nonlinear Optical Material, Cs2YB3O6F296Enhanced UV Nonlinear Optical Properties in Layered Germanous Phosphites through Functional Group Sequential Construction116Review on birefringence in borates based on birefringence-active functional groups and arrangements57Old tree blossoms anew: Research progress on the structures and optical properties of ultraviolet selenites56Recent advances and future perspectives on rare-earth-based nonlinear optical materials with π-conjugated [XO3] (X = B, C, N) units67Halogen Bond Unlocks Ultra‐High Birefringence72Sulfate Derivatives with Heteroleptic Tetrahedra: New Deep‐Ultraviolet Birefringent Materials in which Weak Interactions Modulate Functional Module Ordering61Exploiting Deep‐Ultraviolet Nonlinear Optical Material Rb 2 ScB 3 O 6 F 2 Originated from Congruously Oriented [B 3 O 6 ] Groups61Crystal Chemistry and Design Principles of Altermagnets47Computer‐Aided Development of New Nonlinear Optical Materials38Rational Design and Controlled Synthesis of High-Performance Inorganic Short-Wave UV Nonlinear Optical Materials150Looking Back the Nonlinear Optical Crystals in a Functionalized Unit's Perspective109A review of recent developments in rare earth-doped nanophosphors for emerging technological applications78[C 2 N 4 H 7 O][NH 2 SO 3 ]: High‐Performance Ultraviolet Nonlinear Optical Crystal with Ditrigon Coupled Guanylurea Group48Chalcophosphates: A plentiful source of infrared nonlinear optical materials42Synergically Assembling Advantageous Groups toward High‐Performance Infrared Nonlinear Optical Materials A II CdSiSe 4 (A II = Sr, Ba)40Ultra‐High Optical Anisotropy with UV Transmission Achieved by Rational Arrangement of Extended π‐Conjugated Groups45Bridging the Interlayer Binding to Ordered π‐Conjugated Units for Constructing High‐Performing Light Polarization Crystals48Recent progress in structural design strategies of high-birefringence optical crystals53Decoupling the SHG‐Birefringence Trade‐off in UV NLO Materials via Triple‐Control Coordination Engineering: Achieving Synergistic Performance Optimization88Breaking the Birefringence Barrier in B–O Crystals via B–C π-scaffolding35A review of recent advances in Ce3+-activated garnet phosphors for blue-chip-pumped pc-WLEDs81Engineered Integration of Diverse Functional Units Induces Multifunctionality in Malonate‐Borate Hybrids44

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  38. RbMT3(BO3)2O3 (M=Ba, Sr; T=Al, Ga): New Double‐Layered Oxyborates Constructed from [BO3] Triangles and [TO4] Tetrahedra

    Chemistry - A European Journal · 2021-04-08

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  39. Large Magnetocaloric Effect in Li3K9Gd3(BO3)7 Crystal Featuring Sandwich-Like Three-Dimensional Framework

    Inorganic Chemistry · 2021-04-12

    Wang Liu, Fei Liang, Yuwei Chen, Huimin Song, Jingcheng Feng, Jun Shen, Zheshuai Lin, Heng Tu, Guochun Zhang

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  40. Cyanurates consisting of intrinsic planar π-conjugated 6-membered rings: An emerging source of optical functional materials

    Coordination Chemistry Reviews · 2021-04-14

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  41. Discovery of First Magnesium Fluorooxoborate with Stable Fluorine Terminated Framework for Deep‐UV Nonlinear Optical Application

    Angewandte Chemie International Edition · 2021-04-19

    Ming Xia, Fuming Li, Miriding Mutailipu, Shujuan Han, Zhihua Yang, Shilie Pan

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  42. Discovery of First Magnesium Fluorooxoborate with Stable Fluorine Terminated Framework for Deep‐UV Nonlinear Optical Application

    Angewandte Chemie · 2021-04-19

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  43. Te(CS(NH2)2)4SO4·2H2O: A Three-in-One Semiorganic Nonlinear Optical Crystal with an Unusual Quadrilateral (TeS4)6– Chromophore

    Crystal Growth & Design · 2021-04-23

    Xiaoya Weng, Chensheng Lin, Guang Peng, Huixin Fan, Xin Lei Zhao, Kaichuang Chen, Min Luo, Ning Ye

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  44. Cs4B4O3F10: First Fluorooxoborate with [BF4] Involving Heteroanionic Units and Extremely Low Melting Point

    Chemistry - A European Journal · 2021-05-03

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  45. Expanding the chemistry of borates with functional [BO2]− anions

    Nature Communications · 2021-05-10

    Chunmei Huang, Miriding Mutailipu, Fangfang Zhang, Kent J. Griffith, Cong Hu, Zhihua Yang, John M. Griffin, Kenneth Reinhard Poeppelmeier, Shilie Pan

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  46. ASb5S8 (A = K, Rb, and Cs): Thermal Switching of Infrared Nonlinear Optical Properties across the Crystal/Glass Transformation

    Chemistry of Materials · 2021-05-11

    Wen‐Fa Chen, Bin‐Wen Liu, Shao‐Min Pei, Qiu-Nan Yan, Xiao‐Ming Jiang, Guo‐Cong Guo

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  47. K5Mg2La3(BO3)6: An Efficient, Deep-Ultraviolet Nonlinear Optical Material

    Chemistry of Materials · 2021-05-21

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  48. From Centrosymmetry to Noncentrosymmetry: Tailoring the Structural Arrangements of Carbonates with Strong Nonlinear Optical Response through Partial Anion Substitution

    Advanced Optical Materials · 2021-05-22

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  49. A photochromism induced dual-mode luminescence modulation in Sr2SnO4:xYb3+/Ho3+ ceramics

    Ceramics International · 2021-05-26

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  50. Be2(BO3)(IO3): The First Anion‐mixed Van der Waals Member in the KBe2BO3F2 Family with a Very Strong Second Harmonic Generation Response

    Angewandte Chemie International Edition · 2021-05-26

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