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RESEARCH PAPER · Angewandte Chemie International Edition · 2018

Pb2BO3I: A Borate Iodide with the Largest Second‐Harmonic Generation (SHG) Response in the KBe2BO3F2 (KBBF) Family of Nonlinear Optical (NLO) Materials

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Pb2BO3I: A Borate Iodide with the Largest Second‐Harmonic Generation (SHG) Response in the KBe2BO3F2 (KBBF) Family of Nonlinear Optical (NLO) MaterialsOriginalBa 3 B 10 O 17 Br 2 : a new barium borate halide with B–O layered structure4BaLiZn 3 (BO 3 ) 3 : a new member of the KBe 2 BO 3 F 2 family possessing dense BO 3 triangles and the smallest interlayer distance16Cation-tuned synthesis of the A 2 SO 4 ·SbF 3 (A = Na + , NH 4 + , K + , Rb + ) family with nonlinear optical properties78Rational Design of the First Lead/Tin Fluorooxoborates MB2O3F2 (M = Pb, Sn), Containing Flexible Two-Dimensional [B6O12F6]∞ Single Layers with Widely Divergent Second Harmonic Generation Effects211Second-order nonlinear optical crystals with mixed anions250The First Examples of Lithium‐Containing Mixed‐Alkali Strontium Borates with Different Dimensional Anionic Architectures and Short Cutoff Edges16Centrosymmetric (NH4)2SbCl(SO4)2 and Non-centrosymmetric (NH4)SbCl2(SO4): Synergistic Effect of Hydrogen-Bonding Interactions and Lone-Pair Cations on the Framework Structures and Macroscopic Centricities89Li2BaSc(BO3)2F and LiBa2Pb(BO3)2F with Layered Structures featuring Special Li−O/F Configurations11The linear and nonlinear optical response of CsGeX3 (X=Cl, Br, and I): The finite field and first-principles investigation26Two Lanthanide Borate Chlorides LnB4O6(OH)2Cl (Ln = La, Ce) with Wide Ultraviolet Transmission Windows and Large Second-Harmonic Generation Responses25N‐Doped C@Zn3B2O6 as a Low Cost and Environmentally Friendly Anode Material for Na‐Ion Batteries: High Performance and New Reaction Mechanism91An energy band engineering design to enlarge the band gap of KTiOPO 4 (KTP)-type sulfates via aliovalent substitution66Centrosymmetric K 2 SO 4 ·(SbF 3 ) 2 and noncentrosymmetric Rb 2 SO 4 ·(SbF 3 ) 2 resulting from cooperative effects of lone pair and cation size63Cs 2 CdV 2 O 6 Cl 2 and Cs 3 CdV 4 O 12 Br: two new non-centrosymmetric oxyhalides containing d 0 and d 10 cations and exhibiting second harmonic generation activity19Exploration of the deep-ultraviolet nonlinear optical materials in the derivatives of KBe2BO3F27From centrosymmetric to noncentrosymmetric: cation-directed structural evolution in X 3 ZnB 5 O 10 (X = Na, K, Rb) and Cs 12 Zn 4 (B 5 O 10 ) 4 crystals26K 2 [B 4 O 5 (OH) 4 ]·H 2 O and K 2 [B 4 O 5 (OH) 4 ]: two new hydrated potassium borates with isolated [B 4 O 5 (OH) 4 ] 2− units and different structural frameworks8Pb 10 O 4 (BO 3 ) 3 I 3 : a new noncentrosymmetric oxyborate iodide synthesized by the straightforward hydrothermal method6RbSbSO 4 Cl 2 : an excellent sulfate nonlinear optical material generated due to the synergistic effect of three asymmetric chromophores79Two alkali calcium borates exhibiting second harmonic generation and deep-UV cutoff edges3Two new tin( iv )-containing phosphate fluorides with two types of Sn( iv )–P–O–F frameworks and short cutoff edges0Li2CsB7O10(OH)4: A Deep-Ultraviolet Nonlinear-Optical Mixed-Alkaline Borate Constructed by Unusual Heptaborate Anions98Formation Mechanism of a Polyanonic Framework from Layer to Chain Explored by Adjusting Time, Temperature, and pH: Preparation and Characterization of Metal-Complex-Templated 1D Borate and 2D Nickel Borate13Crystallographic Investigations into the Polar Polymorphism of BaTeW2O9: Phase Transformation, Controlled Crystallization, and Linear and Nonlinear Optical Properties26Zeolitic Open-Framework Borates with Noncentrosymmetric Structures and Nonlinear Optical Properties24CsSbF 2 SO 4 : An Excellent Ultraviolet Nonlinear Optical Sulfate with a KTiOPO 4 (KTP)‐type Structure87CsSbF2SO4: An Excellent Ultraviolet Nonlinear Optical Sulfate with a KTiOPO4 (KTP)‐type Structure432Cs3Na(H2C3N3O3)4·3H2O: A Mixed Alkali‐Metal Hydroisocyanurate Nonlinear Optical Material Containing π‐Conjugated Six‐Membered‐Ring Units68Synthesis and Characterization of the Tin Iodide Borate Sn3[B3O7]I14K9[B4O5(OH)4]3(CO3)X·7H2O (X = Cl, Br): Syntheses, Characterizations, and Theoretical Studies of Noncentrosymmetric Halogen Borate–Carbonates with Short UV Cutoff Edges16[Ln6O8] Cluster‐Encapsulating Polyplumbites as New Polyoxometalate Members and Record Inorganic Anion‐Exchange Materials for ReO4− Sequestration21β‐CsB9O14: A Triple‐Layered Borate with Edge‐Sharing BO4 Tetrahedra Exhibiting a Short Cutoff Edge and a Large Birefringence30Rb7SrY2(B5O10)3: A Rare-Earth Pentaborate with Moderate Second-Harmonic Response and Interesting Phase-Matching Behavior29Research and Development of Zincoborates: Crystal Growth, Structural Chemistry and Physicochemical Properties20Structure and Properties of the Non‐Centrosymmetric Manganese(II) Borate Mn5(BO3)3OH3Nontoxic KBBF Family Member Zn2BO3(OH): Balance between Beneficial Layered Structure and Layer Tendency81Ag4Hg(SeO3)2(SeO4): a novel SHG material created in mixed valent selenium oxides by in situ synthesis36A new iodate-phosphate Pb 2 (IO 3 )(PO 4 ) achieving great improvement in birefringence activated by (IO 3 ) − groups53[O 2 Pb 3 ] 2 (BO 3 )I: a new lead borate iodide with 1∞[O 2 Pb 3 ] double chains6Gd(NO 3 )(Se 2 O 5 )·3H 2 O: a nitrate–selenite nonlinear optical material with a short ultraviolet cutoff edge28Inorganic planar π-conjugated groups in nonlinear optical crystals: review and outlook145Li 3 CaB 2 O 5 F: a unique sandwich-like structure with diverse and wide Li ion diffusion pathways5Novel ultraviolet (UV) nonlinear optical (NLO) materials discovered by chemical substitution-oriented design302RbB 3 O 4 F 2 : a rubidium fluorooxoborate with an unprecedented [B 3 O 5 F 2 ] 3− functionalized unit and a large birefringence37Synthesis, characterization and crystal structure of a new mixed alkali and alkaline-earth metal borate Rb 9 Ba 24 (BO 3 ) 196Two-stage evolution from phosphate to sulfate of new KTP-type family members as UV nonlinear optical materials through chemical cosubstitution-oriented design51A Promising Fluorooxoborate Framework with Flexibile Capability for Diverse Cations to Enhance the Second Harmonic Generation14PbB5O7F3: A High-Performing Short-Wavelength Nonlinear Optical Material120Bridging the Salt-Inclusion and Open-Framework Structures: The Case of Acentric Ag 4 B 4 O 7 X 2 (X = Br, I) Borate Halides21An Unprecedented Antimony(III) Borate with Strong Linear and Nonlinear Optical Responses224An Unprecedented Antimony(III) Borate with Strong Linear and Nonlinear Optical Responses42Pb6O5(NO3)2: A Nonlinear Optical Oxynitrate Structurally Based on Lead Oxide Framework4The Non-Concentration-Quenching Phosphor Ca3Eu2B4O12 for WLED Application176Rational Design of the Nonlinear Optical Response in a Tin Iodate Fluoride Sn(IO3)2F290Enhancement of Second-Order Optical Nonlinearity in a Lutetium Selenite by Monodentate Anion Partial Substitution58K4Sb(SO4)3Cl: The first apatite-type sulfate ultraviolet nonlinear optical material with sharply enlarged birefringence61Hydrogen-Bond-Assisted Reinforcement of Interlayer Connections in Zn2BO3X·H2O (X = Cl, Br): Two UV Nonlinear Optical Crystals with KBBF-Type Structure9Resource‐Efficient Low‐Temperature Synthesis of Microcrystalline Pb2B5O9X (X = Cl, Br) for Surfaces Studies by Optical Second Harmonic Generation10A6Sb4F12(SO4)3 (A = Rb, Cs): Two Novel Antimony Fluoride Sulfates with Unique Crown-like Clusters50A review on phase transition and structure-performance relationship of second-order nonlinear optical polymorphs107Li4Ca2B8O16: A Borate with a Unique Fundamental Building Block and a Short Cutoff Edge14Nanostructured Borate Halides for Optical Second Harmonic Generation at Surfaces7Rational Design of the Metal‐Free KBe 2 BO 3 F 2 ⋅(KBBF) Family Member C(NH 2 ) 3 SO 3 F with Ultraviolet Optical Nonlinearity201Rational Design of the Metal‐Free KBe2BO3F2⋅(KBBF) Family Member C(NH2)3SO3F with Ultraviolet Optical Nonlinearity31CsZn2BO3X2 (X2=F2, Cl2, and FCl): A Series of Beryllium‐Free Deep‐Ultraviolet Nonlinear‐Optical Crystals with Excellent Properties142CsZn2BO3X2 (X2=F2, Cl2, and FCl): A Series of Beryllium‐Free Deep‐Ultraviolet Nonlinear‐Optical Crystals with Excellent Properties29CsHgNO3Cl2: A New Nitrate UV Birefringent Material Exhibiting an Optimized Layered Structure49Nonlinear-Optical Crystal Rb3YB6O12 with Condensed B5O10 Blocks That Exhibits an Intriguing Structural Arrangement and a Short Ultraviolet Absorption Edge26Different mechanism of response of asymmetric lone pair electrons around ns2 cations to birefringence and second harmonic generation7Cs 3 Pb 2 (CH 3 COO) 2 X 5 (X=I, Br): Halides with Strong Second‐Harmonic Generation Response Induced by Acetate Groups75Cs3Pb2(CH3COO)2X5 (X=I, Br): Halides with Strong Second‐Harmonic Generation Response Induced by Acetate Groups22The first bismuth borate oxyiodide, Bi4BO7I: commensurate or incommensurate?3A new nonlinear optical sulfate of layered structure: Cs2Zn2(SO4)319Borates: A Rich Source for Optical Materials1089KNa2ZrF7: A Mixed-Metal Fluoride Exhibits Phase-Matchable Second-Harmonic-Generation Effect and High Laser-Induced Damage Threshold42Sn2B5O9Br as an Outstanding Bifunctional Material with Strong Second‐Harmonic Generation Effect and Large Birefringence84Sb6O7(SO4)2: A Promising Ultraviolet Nonlinear Optical Material with an Enhanced Second‐Harmonic‐Generation Response Activated by SbIII Lone‐Pair Stereoactivity62Ba 2.5 Pb 1.5 B 12 O 22 : structural transformation from a centrosymmetric to a noncentrosymmetric space group by introducing Pb into Ba 2 B 6 O 117Centrosymmetric RbSnF 2 NO 3 vs. noncentrosymmetric Rb 2 SbF 3 (NO 3 ) 254Pb 2 TiFO(SeO 3 ) 2 Br: a new polar compound with the strongest second harmonic generation in the selenite bromide family29Potassium L-ascorbate monohydrate: a new metal–organic nonlinear optical crystal6Sn 14 O 11 Br 6 : a promising birefringent material with a [Sn 14 O 11 Br 6 ] layer26Different mechanism of stereochemical activity and birefringence in post-transition metal halides: A first-principles investigation1Nonlinear Optical Thermometry—A Novel Temperature Sensing Strategy via Second Harmonic Generation (SHG) and Upconversion Luminescence in BaTiO 3 :Ho 3+ ,Yb 3+ Perovskite62Tin Chloride Sulfates A3Sn2(SO4)3–xCl1+2x (A = K, Rb, Cs; x = 0, 1) as Multifunctional Optical Materials33Sr2Pb(BeB5O10)(BO3): An Excellent Ultraviolet Nonlinear-Optical Beryllium Borate by the Pb-Modified Construction of a Conjugated System and Lone-Pair Effect14Zintl based superatom P7M2 (M=Li, Na, K & Be, Mg, Ca) clusters with excellent second and third-order nonlinear optical response24KCs2[Pb2Br5(HCOO)2]: A Polar 3D Lead‐Bromide Framework Exhibiting Strong Second‐Harmonic Generation Response10Strain-Driven Polarized Electric Field-Promoted Photocatalytic Activity in Borate-Based CsCdBO3 Bulk Materials30Linear and Nonlinear Optical Properties of Centrosymmetric Sb 4 O 5 SO 4 and Noncentrosymmetric Sb 4 O 4 (SO 4 )(OH) 2 Induced by Lone Pair Stereoactivity55Two Tellurium(IV)-Based Sulfates Exhibiting Strong Second Harmonic Generation and Moderate Birefringence as Promising Ultraviolet Nonlinear Optical Materials28Sn2PO4I: An Excellent Birefringent Material with Giant Optical Anisotropy in Non π‐Conjugated Phosphate212Sn2PO4I: An Excellent Birefringent Material with Giant Optical Anisotropy in Non π‐Conjugated Phosphate22Synthesis, Crystal Structure, and Nonlinear Optical Property of an Anhydrous Sulfate KTb(SO4)216Noncentrosymmetric Rb3(COOH)3(H3BO3)2 vs Centrosymmetric Cs3(COOH)3(H3BO3)214Strong 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 Modification9LiB9O15·H2dap·H2O: A Cotemplated Acentric Layer-Pillared Borate Built by Mixed Oxoboron Clusters12Chemical substitution – oriented design of a new polar PbFIO3 achieving a balance between large second-harmonic generation response and wide band gap16Structure and Origin of the Second-Harmonic Generation Response of Nonlinear Optical Material Sr2Be2B2O713M4O(IO3)3(I3O7F3)BF4 (M = Pb, Sr): Promising Nonlinear Optical Materials Featuring the Unprecedented Windmill-Shaped [I3O7F3]2– Polyfluoroiodate Anion12From CeF2(SO4)·H2O to Ce(IO3)2(SO4): Defluorinated Homovalent Substitution for Strong Second-Harmonic-Generation Effect and Sufficient Birefringence53NH4Sb2(C2O4)F5: A novel UV nonlinear optical material synthesized in deep eutectic solvents38Complex coordinated functional groups: A great genes for nonlinear optical materials64Ba2B13O19(OH)5·5H2O: A promising nonlinear optical material with a unique 2[B13O19(OH)5]∞ two-dimensional layer9NaSb3O2(SO4)3·H2O: A New Alkali-Metal Antimony(III) Sulfate with a Unique Sb6O20H4 Unit and Moderate Birefringence19Anion-Tuned Synthesis of Ag Coordination Compounds: Approaches for Optimizing Second-Harmonic-Generation (SHG) Response5Germanium-based superatom clusters as excess electron compounds with significant static and dynamic NLO response; a DFT study22AZn 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(C 3 N 6 H 7 ) 2 SiF 6 ·H 2 O: an ultraviolet birefringent crystal exceeding the intrinsic energy gap of an organic reagent38Biological Determination, Molecular Docking and Hirshfeld Surface Analysis of Rhoduim(I)-N-Heterocyclic Carbene Complex: Synthesis, Crystal Structure, DFT Calculations, Optical and Non Linear Optical Properties12KF·B(OH) 3 : a KBBF-type material with large birefringence and remarkable deep-ultraviolet transparency33KLi 2 CO 3 F: a beryllium-free KBBF-type deep-UV carbonate with an enhanced interlayer interaction and large birefringence20KSb(BeF 3 )F 3 : a totally fluorine strategy for achieving wide bandgap and large birefringence23Large optical anisotropy differentiation induced by the anion-directed regulation of structures29Metal oxyhalides: an emerging family of nonlinear optical materials124Na 3 B 6 O 10 (HCOO): an ultraviolet nonlinear optical sodium borate-formate33Where the extraordinaries meet: a cascade of isosymmetrical superionic phase transitions and negative thermal expansion in a novel silver salt-inclusion borate halide15Layered Perovskite-like Nitrate Cs2Pb(NO3)2Br2 as a Multifunctional Optical Material40Inorganic nonlinear optical materials7Noncentrosymmetric Rare-Earth Borate Fluoride La2B5O9F3: A New Ultraviolet Nonlinear Optical Crystal with Enhanced Linear and Nonlinear Performance48Novel Dy incorporated Ca3Y2B4O12 phosphor: Insights into the structure, broadband emission, photoluminescence and cathodoluminescence characteristics21Enhanced Interlayer Interaction and Second-Harmonic-Generation Response in a KBe 2 BO 3 F 2 -Type Inorganic–Organic Hybrid Zinc Borate33Self-Assembled Nonlinear Optical Crystals Based on an Asymmetric Fluorenone Derivative17Highly transparent Pb8O7I2, a novel lead oxyiodide5The strong alternating built-in electric field sourced by ball milling on Pb2BO3X (X Cl, Br, I) piezoelectric materials contributes to high catalytic activity50Theoretical investigation of lithium-based clusters Lin (where n = 3, 5, 7) with remarkable electronic and frequency-dependent NLO properties6Crystal Growth of K2HCO3F·H2O with a Very Short Cutoff Edge and Large Birefringence17(C3N6H7)2SbF5·H2O Exhibiting Strong Optical Anisotropy from the Optimal Arrangement of π-Conjugated (C3N6H7)+ Groups31Design of a new ultraviolet nonlinear optical material KNO3SO3NH3 exhibiting an unexpected strong second harmonic generation response44BaSb(H2PO2)3Cl2: An excellent UV nonlinear optical hypophosphite exhibiting strong second-harmonic generation response32SbHPO3F: 2D van der Waals Layered Phosphite Exhibiting Large Birefringence32Achieving Large Second Harmonic Generation Effects via Optimal Planar Alignment of Triangular Units64Solvothermal and hydrothermal methods for preparative solid-state chemistry5Explorations of Second-Order Nonlinear Optical Materials in the Monovalent Trithiocyanurate System18Trade-Off for Better Balanced Nonlinear Optical Performance with Disordered Si in ZnGeP217Cd(NH 2 SO 3 ) 2 · x H 2 O ( x = 0, 2): new sulfamates with a unique coordination environment and reversible phase transitions20Ag 4 B 7 O 12 X (X = Cl, Br, I) Heptaborate Family: Comprehensive Crystal Chemistry, Thermal Stability Trends, Topology, and Vibrational Anharmonicity13Noncentrosymmetric versus Centrosymmetric: Halogen Induced Variable Coordination Modes of Sn2+ and Structural Transition in Sn3B3O7X (X = Cl and Br)17A Cation-Driven Approach toward Deep-Ultraviolet Nonlinear Optical Materials17Ce 3 F 4 (SO 4 ) 4 : cationic framework assembly for designing polar nonlinear optical material through fluorination degree modulation23KMB 4 O 6 F 3 (M = Co, Fe): two-dimensional magnetic fluorooxoborates with triangular lattices directed by triangular BO 3 units16Low temperature molten salt synthesis of noncentrosymmetric (NH 4 ) 3 SbF 3 (NO 3 ) 3 and centrosymmetric (NH 4 ) 3 SbF 4 (NO 3 ) 234New Ultraviolet Nonlinear Optical Crystal Rb3Hg2(SO4)3Cl3Self-assembled organic nonlinear optical crystals based on pyridine derived fluorenone20Synthesis and characterization of a new rare earth borate nonlinear optical crystal K 7 PbLu 2 B 15 O 308Three-dimensional porous borocarbonitride composed of pentagonal motifs as a high-performance pyroelectric material0β-(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 groups35SbI3·3S8: A Novel Promising Inorganic Adducts Crystal for Second Harmonic Generation5Two Mixed-Alkali-Metal Selenates as Short-Wave Ultraviolet Nonlinear-Optical Materials10

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  1. Ba 3 B 10 O 17 Br 2 : a new barium borate halide with B–O layered structure

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  2. BaLiZn 3 (BO 3 ) 3 : a new member of the KBe 2 BO 3 F 2 family possessing dense BO 3 triangles and the smallest interlayer distance

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  4. Rational Design of the First Lead/Tin Fluorooxoborates MB2O3F2 (M = Pb, Sn), Containing Flexible Two-Dimensional [B6O12F6]∞ Single Layers with Widely Divergent Second Harmonic Generation Effects

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  10. Two Lanthanide Borate Chlorides LnB4O6(OH)2Cl (Ln = La, Ce) with Wide Ultraviolet Transmission Windows and Large Second-Harmonic Generation Responses

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  22. Li2CsB7O10(OH)4: A Deep-Ultraviolet Nonlinear-Optical Mixed-Alkaline Borate Constructed by Unusual Heptaborate Anions

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  29. Synthesis and Characterization of the Tin Iodide Borate Sn3[B3O7]I

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  30. K9[B4O5(OH)4]3(CO3)X·7H2O (X = Cl, Br): Syntheses, Characterizations, and Theoretical Studies of Noncentrosymmetric Halogen Borate–Carbonates with Short UV Cutoff Edges

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