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RESEARCH PAPER · Journal of the American Chemical Society · 2020

BaF 2 TeF 2 (OH) 2 : A UV Nonlinear Optical Fluorotellurite Material Designed by Band-Gap Engineering

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BaF 2 TeF 2 (OH) 2 : A UV Nonlinear Optical Fluorotellurite Material Designed by Band-Gap EngineeringOriginalHexagonal tungsten oxides with large bandgaps synthesized by a chemical substitution method31Recent progress in selenite and tellurite based SHG materials32Dimensionality–Band Gap–Third-Harmonic Generation Property Relationship in Novel Main-Group Metal Iodates37CsZn2BO3X2 (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 Properties29Ba2[MoO3(OH)(IO3)2]IO3: A Promising SHG Material Featuring a Λ-Shaped Functional Motif Achieved by Universal Mono-Site Substitution50Y 2 (Te 4 O 10 )(SO 4 ): a new sulfate tellurite with a unique Te 4 O 10 polyanion and large birefringence36Ba(MoO 2 F) 2 (QO 3 ) 2 (Q = Se, Te): Partial Fluorination of MoO 6 Octahedra Enabling Two Polar Solids with Strong and Phase Matchable SHG Response69Giant Optical Anisotropy in the UV‐Transparent 2D Nonlinear Optical Material Sc(IO 3 ) 2 (NO 3 )212Giant Optical Anisotropy in the UV‐Transparent 2D Nonlinear Optical Material Sc(IO 3 ) 2 (NO 3 )57Applying band gap engineering to tune the linear optical and nonlinear optical properties of noncentrosymmetric chalcogenides La 4 Ge 3 Se x S 12− x ( x = 0, 2, 4, 6, 8, 10)21Breaking through the “3.0 eV wall” of energy band gap in mid-infrared nonlinear optical rare earth chalcogenides by charge-transfer engineering144From Ce(IO 3 ) 4 to CeF 2 (IO 3 ) 2 : fluorinated homovalent substitution simultaneously enhances SHG response and bandgap for mid-infrared nonlinear optics26Hg 3 (Te 3 O 8 )(SO 4 ): a new sulfate tellurite with a novel structure and large birefringence explored from d 10 metal compounds39LaTeBO 5 : a new borotellurite with a large birefringence activated by the highly distorted [Te (iv) O 4 ] group16Recent advances of oxyfluorides for nonlinear optical applications69Role of fluorine on the structure and second-harmonic-generation property of inorganic selenites and tellurites23Zn(NH 3 )CO 3 : a “three-in-one” UV nonlinear optical crystal built by a polar molecule bonding strategy18Order and Disorder: Toward the Thermodynamically Stable α-BaMoO2F4 from the Metastable Polymorph31Second-order nonlinear optical property of the ultraviolet transparent alkali metal-rare earth metal carbonate Na3Y(CO3)3.3H2O5Bi2[B2(SeO3)6]: A Metal Boroselenite with a Unique Zero-Dimensional [B2(SeO3)6]6– Anionic Group and Large Birefringence31A Deep‐UV Nonlinear Optical Borosulfate with Incommensurate Modulations71A Deep‐UV Nonlinear Optical Borosulfate with Incommensurate Modulations13UV Solar‐Blind‐Region Phase‐Matchable Optical Nonlinearity and Anisotropy in a π‐Conjugated Cation‐Containing Phosphate196UV Solar‐Blind‐Region Phase‐Matchable Optical Nonlinearity and Anisotropy in a π‐Conjugated Cation‐Containing Phosphate28Synthesis, crystal structure, linear and nonlinear optical properties of quaternary sulfides Ba6(Cu2X)Ge4S16 (X=Mg, Mn, Cd)23BaYOBO3: A deep-ultraviolet rare-earth oxy-borate with a large second harmonic generation response45Sr2Pb(BeB5O10)(BO3): An Excellent Ultraviolet Nonlinear-Optical Beryllium Borate by the Pb-Modified Construction of a Conjugated System and Lone-Pair Effect14Synthesis, Structure, Characterization, and Calculation of a Noncentrosymmetric Fluorine-Containing Indium Iodate, Ba[InF3(IO3)2]10Two Tellurium(IV)-Based Sulfates Exhibiting Strong Second Harmonic Generation and Moderate Birefringence as Promising Ultraviolet Nonlinear Optical Materials28Giant Second-Harmonic Generation Response and Large Band Gap in the Partially Fluorinated Mid-Infrared Oxide RbTeMo 2 O 8 F1492D van der Waals Layered [C(NH2)3]2SO3S Exhibits Desirable UV Nonlinear-Optical Trade-Off47An Effective Strategy for Designing Nonlinear Optical Crystals by Combining the Structure‐Directing Property of Oxyfluorides with Chemical Substitution73An Effective Strategy for Designing Nonlinear Optical Crystals by Combining the Structure‐Directing Property of Oxyfluorides with Chemical Substitution10A Lead Mixed Halide with Three Different Coordinated Anions and Strong Second‐Harmonic Generation Response10Synergistic Effect of π-Conjugated [C(NH 2 ) 3 ] Cation and Sb(III) Lone Pair Stereoactivity on Structural Transformation and Second Harmonic Generation58Fluorine: A Very Special Element and Its Very Special Impacts on Chemistry26Fluorine: A Very Special Element and Its Very Special Impacts on Chemistry40Fluorine: A Very Special Element and Its Very Special Impacts on Chemistry45Fluorine: A Very Special Element and Its Very Special Impacts on Chemistry5Two molybdenyl carbonates with different dimensional structures exhibiting huge differences in band gaps7β-BaGa 4 Se 7 : a promising IR nonlinear optical crystal designed by predictable structural rearrangement46(C 3 N 6 H 7 ) 2 SiF 6 ·H 2 O: an ultraviolet birefringent crystal exceeding the intrinsic energy gap of an organic reagent38An excellent lead oxyiodide with a strong second-harmonic generation response and a large birefringence induced by the oriented arrangement of highly distorted [PbO 4 I 2 ] polyhedra13APb 2 (C 7 H 3 NO 4 ) 2 I (A = K, Rb, Cs): rare stable nonlinear optical crystals with second-harmonic generation response and highly distorted lead core coordination polyhedra2Broad transparency and wide band gap achieved in a magnetic infrared nonlinear optical chalcogenide by suppressing d–d transitions41Cs 2 VOF 4 (IO 2 F 2 ): Rationally designing a noncentrosymmetric early-transition-metal fluoroiodate24First polar quaternary sulphide CsLiGa 6 S 10 with mixed ordered alkali cations displaying excellent infrared nonlinear optical properties16Hg 2 (SeO 3 )(SO 4 ): the first sulfate selenite with large birefringence explored from d 10 transition metal compounds36KLi 2 CO 3 F: a beryllium-free KBBF-type deep-UV carbonate with an enhanced interlayer interaction and large birefringence20NH 4 (B 6 PO 10 (OH) 4 )·H 2 O: exhibiting the largest birefringence in borophosphates43Unprecedented boat-shaped [Mo 2 O 5 (IO 3 ) 4 ] 2− polyanions induced a strong second harmonic generation response31Lead Tellurite Crystals BaPbTe2O6 and PbVTeO5F with Large Nonlinear-/Linear-Optical Responses due to Active Lone Pairs and Distorted Octahedra20HgTeO2F(OH): A Nonlinear Optical Oxyfluoride Constructed of Active [TeO2F(OH)]2– Pyramids and V-Shaped [HgO2]2– Groups36Intermolecular Energy Gap‐Induced Formation of High‐Valent Cobalt Species in CoOOH Surface Layer on Cobalt Sulfides for Efficient Water Oxidation255Intermolecular Energy Gap‐Induced Formation of High‐Valent Cobalt Species in CoOOH Surface Layer on Cobalt Sulfides for Efficient Water Oxidation58Pb 4 SeBr 6 : A Congruently Melting Mid‐Infrared Nonlinear Optical Material with Excellent Comprehensive Performance39Sr3[SnOSe3][CO3]: A Heteroanionic Nonlinear Optical Material Containing Planar π‐conjugated [CO3] and Heteroleptic [SnOSe3] Anionic Groups78Sr3[SnOSe3][CO3]: A Heteroanionic Nonlinear Optical Material Containing Planar π‐conjugated [CO3] and Heteroleptic [SnOSe3] Anionic Groups7K3ZrF4(SbF4)(SbF5) and K8(ZrF6)(Sb2Zr2F20): Two Zirconium Fluoroantimonites with Low Dimensional Structures and Wide Transparency Range12Ultrawide Bandgap and Outstanding Second‐Harmonic Generation Response by a Fluorine‐Enrichment Strategy at a Transition‐Metal Oxyfluoride Nonlinear Optical Material51Ultrawide Bandgap and Outstanding Second‐Harmonic Generation Response by a Fluorine‐Enrichment Strategy at a Transition‐Metal Oxyfluoride Nonlinear Optical Material12Negative Second Harmonic Response of Sn4+in the Fresnoite Oxysulfide Ba2SnSSi2O720[Ba2F2][Ge2O3S2]: An Unprecedented Heteroanionic Infrared Nonlinear Optical Material Containing Three Typical Anions47Deep Ultraviolet-Transparent Materials with Strong Second-Harmonic Response50(C3N6H7)2SbF5·H2O Exhibiting Strong Optical Anisotropy from the Optimal Arrangement of π-Conjugated (C3N6H7)+ Groups31Dual-Ligand-Oriented Design of Noncentrosymmetric Complexes with Nonlinear-Optical Activity11Isoreticular Design of KTiOPO 4 -Like Deep-Ultraviolet Transparent Materials Exhibiting Strong Second-Harmonic Generation68A 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 Template95From Ba3Nb2O2F12(H2O)2 to Ba0.5NbO2F2(H2O): Achieving Balanced Nonlinear Optical Performance by O/F Ratio Regulation18(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 cations56A UV solar-blind nonlinear optical crystal with confined π-conjugated groups13From AgTeO 2 F and Ag 2 (TeO 2 F 2 ) to Ag 3 F 3 (TeF 6 )(TeO 2 ) 12 : the first silver tellurite oxyfluorides with linear and nonlinear optical properties26From CdPb 8 (SeO 3 ) 4 Br 10 to Pb 3 (TeO 3 )Br 4 : the first tellurite bromide exhibiting an SHG response and mid-IR transparency21Shedding light on intrinsic characteristics and optical properties of novel selenite and tellurite crystals ZrSe 2 O 6 , HfSe 2 O 6 and HfTe 3 O 87The first polyanion-substitution-driven centrosymmetric-to-noncentrosymmetric structural transformation realizing an excellent nonlinear optical supramolecule [Cd 4 P 2 ][CdBr 4 ]17β-(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 groups35A Rare‐Earth Selenite with Unexpectedly Well‐Balanced Ultraviolet Nonlinear Optical Functionality, Sc(HSeO 3 ) 331Rational Design of a Rare‐Earth Oxychalcogenide Nd3[Ga3O3S3][Ge2O7] with Superior Infrared Nonlinear Optical Performance64K2(H2O)WO3F2: A new nonlinear optical material with remarkable second-harmonic generation response and enhanced laser damage threshold9Li3B8O13X (X = Cl and Br): Two New Noncentrosymmetric Crystals with Large Birefringence Induced by BO3 Units18Alignment of Λ-Shaped Basic Building Units to Construct One New KMoO3(IO3) Polar Polymorph11The 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)47Recent 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 Birefringence6Remarkable phase-matchable second-harmonic generation realized by strong polarities of [PbSe3] and [GaSe4] functional motifs in PbGa4Se718Theoretical Prediction‐Assisted Synthesis and Characterization of Infrared Nonlinear Optical Material NaSrBS324Designing a Strong Second-Harmonic Generation Polar Iodate by the Structure-Directing Properties of the “Tumbler-like” [Zn(IO3)(I2O5(OH))] Polyanions20AAl(Te 4 O 10 ) (A = Na, Ag) and K 2 Ga 2 (HTe 6 O 16 )(HTeO 3 ): Three Aluminum/Gallium Tellurites with Large Birefringence and Wide Band Gap21Cd2Nb2Te4O15: A Novel Pseudo‐Aurivillius‐Type Tellurite with Unprecedented Nonlinear Optical Properties and Excellent Stability40A selenite containing unusual [Ga2F(Se2O5)4(HSeO3)2]5- clusters with the polarization ‘lighted’ by F− anions15Halogen Bonding Assembles Anion⋅⋅⋅Anion Architectures in Non‐centrosymmetric Iodate and Bromate Crystals24Cs4Zn5P6S18I2: the Largest Birefringence in Chalcohalide Achieved by Highly Polarizable Nonlinear Optical Functional Motifs21Halide-Induced Band Gap Enhancement from Ba2SnSe4 to KBa2SnSe4Cl2Quadruple‐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 Birefringence2A survey of stereoactive oxysalts for linear and nonlinear optical applications40Excellent Nonlinear Optical M[M4Cl][Ga11S20] (M = A/Ba, A = K, Rb) Achieved by Unusual Cationic Substitution Strategy20A ll HgM IV S 4 (A ll = Sr, Ba, M IV = Si, Ge): A Series of Materials with Large Second Harmonic Generation Response and Wide Band Gaps27Enhanced stability and optoelectronic properties of double perovskite Cs2AgSbI6 by Br doping for solar cells22Stereochemically Active Lone-Pair Containing Metal Substitution in Polar Axis toward a Giant Phase-Matchable Optical Nonlinear Silicate Crystal Li 3 (OH)PbSiO 463Fluorination 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 modification65Ag 2 [TeO 2 (OH) 4 ]: a nonlinear optical tellurate with balanced comprehensive performance2Fully tricoordinated assembly unveils a pioneering nonlinear optical crystal (SbTeO 3 )(NO 3 )25New ultraviolet transparent rare-earth borates with enhanced birefringence induced by cation chemical substitution15Noncentrosymmetric tellurite halides created by a depolymerization strategy: toward strong SHG intensity and wide bandgap16Reticular chemistry-aided effective design of new second-order nonlinear optical selenites11Giant Optical Anisotropy in a Covalent Molybdenum Tellurite via Oxyanion Polymerization43Dual-Anion Strategy Induces Dual Enhancement Toward Ultrashort Phase-Matching Wavelength in Deep-UV Transparent d0 Transition Metal Oxyfluorides21[C(NH2)3][B(C2O2H4)2]: An Organic–Inorganic Hybrid Borate Containing Nonlinear-Optical Active Unit [B(C2O2H4)2]− with Solar-Blind-Region Optical Nonlinearity16Pb3[O10Pb20](SiO4)4X10 (X = Cl, Br): The First Pb-Containing Halogen Silicates with Mirror-Symmetric Pseudo-Aurivillius Bilayers3Hg16O12(NO3)6F2(H2O): A Mercury-Rich Nitrate Oxyfluoride with Diverse Triple-Coordinated Mercury-Based Units That Exhibits an Unparalleled [(Hg16O12F2(H2O))6+]∞ Cationic Framework and a Large Birefringence12Tunable Optical Anisotropy in Rare‐Earth Borates with Flexible [BO3] Clusters7Two Short-Wave UV Beryllium Selenites Exhibiting Diverse Optical Properties Stemming from Functional Group Arrangements8A Chlorinated Indolium‐Based Nonlinear Optical Crystal Achieving Effective Terahertz‐Wave Generation and Highly Sensitive Detection19EuSi7P10: An Inorganic Supramolecular Nonlinear Optical Crystal Exhibiting Strong Second-Harmonic Generation Response4From CaBaM2F12 to K2BaM2F12 (M = Zr, Hf): Heterovalent Cation-Substitution-Induced Symmetry Break and Nonlinear-Optical Activity11Old tree blossoms anew: Research progress on the structures and optical properties of ultraviolet selenites56Second Harmonic Generation in β-K2TeW3O12: An Acentric Crystal Designed from Centric Phase via Pressure Modulation4Halogen Bond Unlocks Ultra‐High Birefringence73Halogen Bond Unlocks Ultra‐High Birefringence14Lanthanide Contraction Eliminates Disorder while Holding Robust Second Harmonic Generation in a Series of Polyiodates13Toward Strong UV–Vis–NIR Second-Harmonic Generation by Dimensionality Engineering of Zinc Thiocyanates32Structure and optical properties of alkali rare-earth double phosphates of M3RE(PO4)2 (M = K, Rb; RE = Y, La, and Lu)4Recent progress in nonlinear optical molybdenum/tungsten tellurites: Structures, crystal growth and characterizations34(C 7 H 3 NO 4 ) 2 Sb 2 F 2 ·2H 2 O: a pyridine-based compound shows large optical anisotropy4CdF(C 6 H 4 NO 2 )(H 2 O): a UV nonlinear optical material with unprecedented SHG and birefringence via π-conjugated rings and a unique “Warren truss structure”11Hg 2 (SeO 3 )(TeO 3 ): a novel tellurite–selenite birefringent crystal achieved by assembling multiple functional groups11(NH 4 ) 2 Cd 2 Cl 3 F 3 and (NH 4 ) 2 Cd 2 Br 3 F 3 : The First Fluoride‐Containing d 10 Metal Mixed Halides Exhibiting Superior Ultraviolet Nonlinear Optical Properties28Enhanced Birefringence and Excellent Thermal Stability in Two Tellurium(IV) Vanadates: KTeOVO4 and Ca2TeV2O95LiAgCe2F10(H2O)2: Focusing on the Cation Size Effect to Reasonably Design a Nonlinear Optical Hydrated Cerium(IV) Fluoride10Sb2(TeO4)(SO4): An Anhydrous Tellurite Sulfate with Large Birefringence and Enhanced Thermal Stability8Designing High-Performance Short-Wave UV Tellurium-Based Mixed Halides Birefringent Crystals via Halogen Substitution Engineering4Designing an all-organic wide bandgap ultraviolet nonlinear optical crystal3Femtosecond Laser Breaks the Lattice Symmetry and Induces Broadband Second Harmonic Generation in 3D Halide Perovskites6Optimized growth and anisotropic physical properties of a promising mid-infrared nonlinear optical crystal Li2TiTeO63LnEuGa3OS6 (Ln = La, Pr, Nd): three dual rare earth metal-based oxychalcogenides with good IR nonlinear optical performances1BaAl2MS6 (M = Si and Ge): the rational construction of diamond-like structures with ultrawide band gap by group-optimization approach6Recent achievements of d0 transition-metal-based oxyfluorides: Crystal chemistry and application in second-order NLO materials10Unlocking Strong Second‐Harmonic Generation in Deep‐UV‐Transparent Polar Organic Sulfonates through Connectivity Regulation2Unlocking Strong Second‐Harmonic Generation in Deep‐UV‐Transparent Polar Organic Sulfonates through Connectivity Regulation6Stepwise Substitution Strategy for Beryllium-Based Selenites with Enhanced SHG Response, Moderate Birefringence, and Short UV Cutoff Edges6ZnGa(SeO 3 ) 2 F: a UV transparent birefringent crystal explored in M( ii )–IIIA–selenite–F systems2Syntheses, structures and optical properties of two new cadmium antimonites: Cs 4 Cd(SbF 5 ) 3 (H 2 O) 2 and Cd[Sb 7 O 10 (OH)](SO 4 )0Strategic Oxygen‐Substitution in Perfluorinated Ce(IV) Coordination Frameworks Triggers Dual‐Wavelength Nonlinear Optical Materials With Exceptional Performances3

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