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RESEARCH ARTICLE · Angewandte Chemie International Edition · 2020

CsZn2BO3X2 (X2=F2, Cl2, and FCl): A Series of Beryllium‐Free Deep‐Ultraviolet Nonlinear‐Optical Crystals with Excellent Properties

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CsZn2BO3X2 (X2=F2, Cl2, and FCl): A Series of Beryllium‐Free Deep‐Ultraviolet Nonlinear‐Optical Crystals with Excellent PropertiesOriginalA melamine-based organic–inorganic hybrid material revealing excellent optical performance and moderate thermal stability75Ba 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 -borate34BaZn 3 (BO 3 ) 2 F 2 : a new beryllium-free zincoborate with a KBBF-type structure11K 2 ZnMoP 2 O 10 : a novel nonlinear optical molybdophosphate with a strong second harmonic generation response and moderate birefringence24LaTeBO 5 : a new borotellurite with a large birefringence activated by the highly distorted [Te (iv) O 4 ] group16Recent advances of oxyfluorides for nonlinear optical applications69Prediction of Novel van der Waals Boron Oxides with Superior Deep‐Ultraviolet Nonlinear Optical Performance43Prediction of Novel van der Waals Boron Oxides with Superior Deep‐Ultraviolet Nonlinear Optical Performance6RbMT3(BO3)2O3 (M=Ba, Sr; T=Al, Ga): New Double‐Layered Oxyborates Constructed from [BO3] Triangles and [TO4] Tetrahedra13Discovery of First Magnesium Fluorooxoborate with Stable Fluorine Terminated Framework for Deep‐UV Nonlinear Optical Application167Discovery of First Magnesium Fluorooxoborate with Stable Fluorine Terminated Framework for Deep‐UV Nonlinear Optical Application18Polar polymorphism: β-Ca2[B5O8(OH)]2[B(OH)3]·H2O—synthesis, structure and nonlinear optical property11From Centrosymmetry to Noncentrosymmetry: Tailoring the Structural Arrangements of Carbonates with Strong Nonlinear Optical Response through Partial Anion Substitution33Sr2Pb(BeB5O10)(BO3): An Excellent Ultraviolet Nonlinear-Optical Beryllium Borate by the Pb-Modified Construction of a Conjugated System and Lone-Pair Effect14Finding 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] Units102Achieving Short‐Wavelength Phase‐Matching Second Harmonic Generation in Boron‐Rich Borosulfate with Planar [BO3] Units9La 3 Ga 3 Ge 2 S 3 O 10 : An Ultraviolet Nonlinear Optical Oxysulfide Designed by Anion‐Directed Band Gap Engineering63La3Ga3Ge2S3O10: An Ultraviolet Nonlinear Optical Oxysulfide Designed by Anion‐Directed Band Gap Engineering18Strong SHG Responses in a Beryllium‐Free Deep‐UV‐Transparent Hydroxyborate via Covalent Bond Modification89Strong SHG Responses in a Beryllium‐Free Deep‐UV‐Transparent Hydroxyborate via Covalent Bond Modification9From β‐Na2B6O10 to Na3AlB8O15 and Na3Al2B7O15: Structural Tuning of Anionic‐Group Architectures by Substitution of [BO4] by [AlO4] Covalent Tetrahedra10Ba2B13O19(OH)5·5H2O: A promising nonlinear optical material with a unique 2[B13O19(OH)5]∞ two-dimensional layer9A Lanthanum Ammonium Sulfate Double Salt with a Strong SHG Response and Wide Deep‐UV Transparency15A Lanthanum Ammonium Sulfate Double Salt with a Strong SHG Response and Wide Deep‐UV Transparency96Hybrid organic–inorganic triguanidine arsenate dihydrate for ultraviolet nonlinear optical application15Na4B8O9F10: 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(NH 2 ) 3 ]BiCl 2 SO 4 : an excellent birefringent material obtained by multifunctional group synergy40CsAB 8 O 12 F 2 ·CsI (A = K + , NH 4 + ): design of two fluorooxoborates with benign layered structures via a salt-inclusion strategy28KLi 2 CO 3 F: a beryllium-free KBBF-type deep-UV carbonate with an enhanced interlayer interaction and large birefringence20Li 6.58 Na 7.43 Sr 4 (B 9 O 18 )(B 12 O 24 )Cl: unprecedented combination of the largest two highly polymerized isolated B–O clusters with novel isolated B 9 O 18 FBB18Metal oxyhalides: an emerging family of nonlinear optical materials124Nain(C2o4)(Hpo4)(H2o)5: An Ultraviolet Transparent Nonlinear Optical Oxalate-Phosphate with Large Birefringence0Pb 4 SeBr 6 : A Congruently Melting Mid‐Infrared Nonlinear Optical Material with Excellent Comprehensive Performance39Revealing Electron–Phonon Coupling Dependence on the π-Conjugated Groups in Rare-Earth Borates6Strong Nonlinearity Induced by Coaxial Alignment of Polar Chain and Dense [BO3] Units in CaZn2(BO3)212Strong Nonlinearity Induced by Coaxial Alignment of Polar Chain and Dense [BO3] Units in CaZn2(BO3)2212The Kurtz-Perry powder technique revisited: A case study on the importance of reference quality and broadband nonlinear optical measurements using LiInSe232Two Metal Phosphate Nonlinear Optical Materials Simultaneously Exhibiting Ultraviolet Transparence and a Large Birefringence50Deep-ultraviolet nonlinear optical crystals: concept development and materials discovery181[C(NH2)3]2Zn(CO3)2: A Guanidinium-Templated Ultraviolet Nonlinear Optical Material20Difluoro(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 Li3Cs6Al2B14O28F4Deep Ultraviolet-Transparent Materials with Strong Second-Harmonic Response50NaK5Zn2(B5O10)2 and β-K3ZnB5O10: Two Zincoborates with Deep-UV Cutoff Edge9Enhancements of Second Harmonic Generation and Birefringence in Traditional RbTiOPO4‐Type Crystals by Aliovalent Substitution of Ti Site1Li2PbB2O5: A Pyroborate with Large Birefringence Induced by the Synergistic Effect of Stereochemical Active Lone Pair Cations and π-Conjugated [B2O5] Groups14Perfectly Encoding π‐Conjugated Anions in the RE5(C3N3O3)(OH)12 (RE=Y, Yb, Lu) Family with Strong Second Harmonic Generation Response and Balanced Birefringence91Perfectly Encoding π‐Conjugated Anions in the RE5(C3N3O3)(OH)12 (RE=Y, Yb, Lu) Family with Strong Second Harmonic Generation Response and Balanced Birefringence18Exploring Short-Wavelength Phase-Matching Nonlinear Optical Crystals by Employing KBe2BO3F2 as the Template95Second-order nonlinear optical properties of copper-based hybrid organic–inorganic perovskites induced by chiral amines30Noncentrosymmetric versus Centrosymmetric: Halogen Induced Variable Coordination Modes of Sn2+ and Structural Transition in Sn3B3O7X (X = Cl and Br)17Cs[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 configuration0Rational Design of the First Ammonium Magnesium Borate with Deep-Ultraviolet Cutoff Edge and Moderate Birefringence and Further Investigation into the Nature of Ammonium in the Borate System15The Kurtz–Perry Powder Technique Revisited: A Study of the Effect of Reference Selection on Powder Second-Harmonic Generation Response20Li3B8O13X (X = Cl and Br): Two New Noncentrosymmetric Crystals with Large Birefringence Induced by BO3 Units18Recent progress in ultraviolet and deep-ultraviolet nonlinear optical aluminoborates17Identifying Ordered OH/F Anions in Hydroxyfluorides by a Terahertz Spectroscopic Approach21The First UV Nonlinear Optical Selenite Material: Fluorination Control in CaYF(SeO 3 ) 2 and Y 3 F(SeO 3 ) 485The First UV Nonlinear Optical Selenite Material: Fluorination Control in CaYF(SeO3)2 and Y3F(SeO3)47Structural Motif Cosubstitution Strategy for Designing Fluoroaluminoborate with the Sr2Be2B2O7-Type Double-Layered Structure14Two Mixed-Alkali-Metal Selenates as Short-Wave Ultraviolet Nonlinear-Optical Materials10Unveiling the Superior Optical Properties of Novel Melamine‐Based Nonlinear Optical Material with Strong Second‐Harmonic Generation and Giant Optical Anisotropy74Chain‐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 Materials5Nonlinear optical crystals KPb3(3-C5H4NCOO)2Br5 and KPb3(3-C5H4NCOO)2Cl3Br2 with new Pb-centered nitrogen-halide polyhedrons obtained by the halide anionic substitution4“Cation Activation”: An Effective Strategy for the Enhancement of Birefringence36Advances in aliovalent substitution strategy for the design and synthesis of nonlinear optical materials: d0 transition metal/gallium iodates and selenites70KHC 2 O 4 · B ( OH ) 3 : A nonlinear optical crystal with large birefringence in the short‐wavelength ultraviolet region9Cs 3 [(BOP) 2 (B 3 O 7 ) 3 ]: A Deep-Ultraviolet Nonlinear Optical Crystal Designed by Optimizing Matching of Cation and Anion Groups169Cd2Nb2Te4O15: A Novel Pseudo‐Aurivillius‐Type Tellurite with Unprecedented Nonlinear Optical Properties and Excellent Stability40Quadruple‐Bidentate Nitrate‐Ligated A 2 Hg(NO 3 ) 4 (A=K, Rb): Strong Second‐Harmonic Generation and Sufficient Birefringence59Quadruple‐Bidentate Nitrate‐Ligated A 2 Hg(NO 3 ) 4 (A=K, Rb): Strong Second‐Harmonic Generation and Sufficient Birefringence2Giant Mid‐Infrared Second‐Harmonic Generation Response in a Densely‐Stacked Van Der Waals Transition‐Metal Oxychloride39Giant Mid‐Infrared Second‐Harmonic Generation Response in a Densely‐Stacked Van Der Waals Transition‐Metal Oxychloride8ASn(C10H12N2O8)Cl·H2O (A = K, Rb): Nonlinear optical crystals with new distorted Sn(IV)-centered nitrogen-oxygen-chloride polyhedron and wide band gaps6Unleashing Anion Chemical Adsorption with Pore-Confined Single Atom Zinc for Enabling High-Performance Lithium-Ion Capacitors9Enlargement of Bandgap and Birefringence in Nonlinear Optical Alkali‐Metal Sulfate Crystals by the Substitution of Asymmetrical Non‐π‐Conjugated Cation8Two UV organic-inorganic hybrid antimony-based materials with superior optical performance derived from cation-anion synergetic interactions30Ba 4 B 14 O 25 : A Deep Ultraviolet Transparent Nonlinear Optical Crystal with Strong Second Harmonic Generation Response Achieved by a Boron‐Rich Closed‐Loop Strategy12Synthesis, crystal and electronic structures, linear and nonlinear optical properties, and photocurrent response of oxyhalides CeHaVIO 4 (Ha = Cl, Br; VI = Mo, W)10(C(NH2)3)2(I2O5F)(IO3)(H2O) and C(NH2)3IO2F2: Two Guanidine Fluorooxoiodates with Wide Band Gap and Large Birefringence20K(NH4)Zn2(PO4)2: a Beryllium-Free Sr2Be2B2O7 Derivative with Enhanced Interlayer Connectivity7(C 2 H 10 N 2 )[Zn 2 (HPO 4 ) 2 Cl 2 ]: substitution-activated new short-wave ultraviolet phosphate with pivotal dual-property enhancement51D Cu( i )-based chiral organic–inorganic hybrid material with second harmonic generation and circular polarized luminescence10Chemical perspectives on heteroanionic compounds: a potential playground for multiferroics7Discovery of a new bimetallic borate with strong optical anisotropy activated by π-conjugated [B 2 O 5 ] units3Exploring 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 moieties37New ultraviolet transparent rare-earth borates with enhanced birefringence induced by cation chemical substitution15Recent advances in rational structure design for nonlinear optical crystals: leveraging advantageous templates153From ZnF2 to ZnF2(H2O)4: Partial Substitution Achieves Structural Transformation and Nonlinear Optical Activity while Keeping Short Ultraviolet Cutoff Edge19Toward the ultraviolet (UV) or deep-UV nonlinear optical crystals: The combination of π-conjugated planar [XY3] and tetrahedral [XY4]80The local state of hydrogen atoms and proton transfer in the crystal structure of natural berborite, Be2(BO3)(OH)‧H2O: Low-temperature single crystal X-ray analysis, IR and 1H NMR spectroscopy, and crystal chemistry and structural complexity of beryllium borates8An Unprecedented [BO2]‐Based Deep‐Ultraviolet Transparent Nonlinear Optical Crystal by Superhalogen Substitution33An Unprecedented [BO2]‐Based Deep‐Ultraviolet Transparent Nonlinear Optical Crystal by Superhalogen Substitution1Assembly of π‐Conjugated [B 3 O 6 ] Units by Mer‐Isomer [YO 3 F 3 ] Octahedra to Design a UV Nonlinear Optical Material, Cs 2 YB 3 O 6 F 211Assembly of π‐Conjugated [B3O6] Units by Mer‐Isomer [YO3F3] Octahedra to Design a UV Nonlinear Optical Material, Cs2YB3O6F297Enhanced UV Nonlinear Optical Properties in Layered Germanous Phosphites through Functional Group Sequential Construction11Enhanced UV Nonlinear Optical Properties in Layered Germanous Phosphites through Functional Group Sequential Construction116Breaking Boundaries: Giant Ultraviolet Birefringence in Dimension‐Reduced Zn‐Based Crystals66Breaking Boundaries: Giant Ultraviolet Birefringence in Dimension‐Reduced Zn‐Based Crystals8Breaking through the ‘‘200 nm deep-ultraviolet wall’’ of phase matching region by cation structural modulation27A2Cd(PO3)4 (A = K, Rb, Cs): Series of cadmium polyphosphates with infinite 1[(PO3)4]ꝏ chains and deep ultraviolet transparency windows2Birefringence Disparity Induced by Synergistic Effects of Stereochemically Active Lone Pairs19K 15 La 7 (BO 3 ) 12 : A KBBF-Like Nonlinear-Optical Material with a Short Cutoff Edge and a Strong Second-Harmonic-Generation Response10Designing a Heteroleptic Tetrahedral Group with an Ultrahigh Polarizability Anisotropy by Optimizing the Bonding Electrons Activity and Their Distribution14Structural modification of hydroxyborates by adjusting the number of shared oxygen atoms and hydroxyl groups for further performance enhancement1Unveiling Charge Dependent Law to Enhance Birefringence in 2‐Aminopyrimidine Family21Rational design of a series of non-centrosymmetric antiperovskite and double antiperovskite borate fluorides13Breaking Performance Barriers in KBe 2 BO 3 F 2 (KBBF) Analogs by Functional Group Self‐Polymerization5Breaking Performance Barriers in KBe 2 BO 3 F 2 (KBBF) Analogs by Functional Group Self‐Polymerization48Deep ultraviolet transparent borophosphates LiAB 2 P 2 O 9 (A = NH 4 , K) and LiNaB 2 P 2 O 8 (OH) 2 ·H 2 O exhibiting a moderate second-harmonic generation response4Deep-ultraviolet sulfamate halides with halogen-centered secondary building units for enhanced optical anisotropy4LiBa 3 Al 2 B 3 O 11 : a deep-ultraviolet transparent optical borate featuring a 2D [Al 2 B 3 O 11 ] ∞ layered structure0Design of rare earth borate short-wave UV nonlinear optical crystals with strengthened second harmonic generation activities via cationic modification strategy11(C6H10N2)ZnX4·H2O (X=Cl and Br): Excellent nonlinear optical properties and temperature induced photoluminescence for encryption23(3‐C6H10N2)ZnX4 (X = Cl and Br): Two Excellent UV Nonlinear Optical Crystals Designed by Combination of π‐conjugated and [ZnX4]2− Tetrahedral Units26Review of KBe2BO3F2-like second-order nonlinear optical materials and their structure-performance relationships13Designing a 3‐Hydroxypropane‐1‐Sulfonate Deep‐Ultraviolet Nonlinear Optical Crystal9Controllable Synthesis of a Strong Ultraviolet Nonlinear Optical Crystal by Tailoring the Lead Oxychloride Polyhedron3A Promising Short-Wave UV NLO Crystal with an Optimized KBBF-like Structure and Well-Balanced Properties Achieved via a Chemical Substitution Strategy6Anion-Ordered [B3O5(OH)2] Induced by Crystal Water with Deep Ultraviolet Transparency and Large Birefringence in Boron-Rich Borophosphates4Rational Design of a Deep-Ultraviolet Nonlinear Optical Crystal25Shape‐Topology‐Driven Design of Deep Ultraviolet Nonlinear Optical Crystals: Engineering [CH 3 PO 3 ]–Metal‐Oxo Layered Frameworks for Enhanced SHG, DUV Transparency3Nd-doped LYSB: A new multifunctional crystal for efficient multi-wavelength laser emission and frequency conversion0KCd(IO 3 ) 2 Cl: A New UV NLO Crystal with Balanced Optical Properties Engineering via Target‐Driven Multi‐Ion Substitution Strategy7Achieving record-high birefringence in a 3D fluorozincoborate via coplanar alignment of π-conjugated [BO 3 ] units0孤对电子效应羟基硼酸盐非线性光学研究进展(特邀)0Constructing Deep‐Ultraviolet Nonlinear Optical Crystals via Synergistic Combination of Fluorinated Polyhedra and Polymerized BO 3 Units15Zn 4 (BO 3 ) 2 (CO 2 CH 2 NH 2 ) 2 ·H 2 O: An Organic–Inorganic Hybridized KBe 2 BO 3 F 2 -like Ultraviolet Nonlinear Optical Crystal3Ba 5 Zn 4 (B 3 O 6 ) 2 (B 12 O 24 ): A Borate with Edge-Sharing [BO 4 ] Tetrahedral Connection by Introducing Zn into β-BaB 2 O 42CdY 2 Si 2 S 8 : A Wide Bandgap IR NLO Material with d 10 Metal-Induced Structure Transformation from CS to NCS1Reverse Weak Polarity‐Induced Ordered Layer Control for Enhanced Second‐Harmonic Generation in Ultraviolet Nonlinear Optical Crystals2The novel Zn-based ultraviolet birefringent crystals combined both large birefringence and wide bandgap2Covalent Interlayer Engineering Enables Ideal Birefringence and Strong SHG in Beryllium‐Free Deep‐UV NLO Borates2Cation-regulated orientational coherence in one-dimensional antimony fluoride selenate chains modulates ultraviolet second-Harmonic generation0Unlocking Hidden Potential via Reprogrammed Mineral Structures: How Anionic Transformation Achieves Ultraviolet Nonlinear Optical Performance0Beyond the bandgap bottleneck: structure–property design principles for infrared nonlinear optical phosphides0

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