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RESEARCH ARTICLE · Chemistry of Materials · 2019

K5(W3O9F4)(IO3): An Efficient Mid-Infrared Nonlinear Optical Compound with High Laser Damage Threshold

Chao Wu, Lin Lin, Xingxing Jiang, Zheshuai Lin, Zhipeng Huang, Mark Graeme Humphrey, P. Shiv Halasyamani, Chi Zhang

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K5(W3O9F4)(IO3): An Efficient Mid-Infrared Nonlinear Optical Compound with High Laser Damage ThresholdOriginalFrom centrosymmetric to noncentrosymmetric: intriguing structure evolution in d 10 -transition metal iodate fluorides36Gd(NO 3 )(Se 2 O 5 )·3H 2 O: a nitrate–selenite nonlinear optical material with a short ultraviolet cutoff edge28Helix-constructed polar rare-earth iodate fluoride as a laser nonlinear optical multifunctional material25Incorporating rare-earth cations with moderate electropositivity into iodates for the optimized second-order nonlinear optical performance17On Prediction of a Novel Chiral Material Y2H3O(OH): A Hydroxyhydride Holding Hydridic and Protonic Hydrogens4Rational 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 Substitution58ZnIO3F: Zinc Iodate Fluoride with Large Birefringence and Wide Band Gap57Polar Molecule-Based Material with Optic–Electric Switching Constructed by Polar Anions21Volume Modulation of Nonlinear Optical Properties by Cation Substitution8Synthesis, crystal structures and optical properties of open-framework gallium phosphates: NaGa3F4(PO4)2(H2O)2 and AGa2P2O7(OH)3(H2O) (A = K, Rb)1New Alkaline-Earth Metal Fluoroiodates Exhibiting Large Birefringence and Short Ultraviolet Cutoff Edge with Highly Polarizable (IO 3 F) 2– Units63AGa 3 F 6 (SeO 3 ) 2 (A = Rb, Cs): A New Type of Phase-Matchable Hexagonal Tungsten Oxide Material with Strong Second-Harmonic Generation Responses63High Coordinate Metal Iodate Chlorides with Diverse Structural Motifs and Tunable Birefringence10Ba2[MoO3(OH)(IO3)2]IO3: A Promising SHG Material Featuring a Λ-Shaped Functional Motif Achieved by Universal Mono-Site Substitution50A 2 Bi 2 (SeO 3 ) 3 F 2 (A = K and Rb): Excellent Mid-Infrared Nonlinear Optical Materials with Both Strong SHG Responses and Large Band Gaps64From Ag2Zr(IO3)6 to LaZr(IO3)5F2: A Case of Constructing Wide‐band‐gap Birefringent Materials through Chemical Cosubstitution11Synthesis, Structure, and Characterization of d0 Transition-Metal Iodate: BaTi(IO3)6·0.5H2O12Ba(MoO2F)2(XO3)2 (X = Se and Te): First Cases of Noncentrosymmetric Fluorinated Molybdenum Oxide Selenite/Tellurite Through Unary Substitution for Enlarging Band Gaps and Second Harmonic Generation34Ba(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 )57Recent Achievements in Lone-Pair Cation-Based Infrared Second-Order Nonlinear Optical Materials95[GaF(H 2 O)][IO 3 F]: a promising NLO material obtained by anisotropic polycation substitution42Ba 2 [FeF 4 (IO 3 ) 2 ]IO 3 : a promising nonlinear optical material achieved by chemical-tailoring-induced structure evolution8Facile syntheses of silver thioantimonates exhibiting second-harmonic generation responses and large birefringence18First chiral fluorinated lead vanadate selenite Pb 2 (V 2 O 4 F)(VO 2 )(SeO 3 ) 3 with five asymmetric motifs and large optical properties24From Ce(IO 3 ) 4 to CeF 2 (IO 3 ) 2 : fluorinated homovalent substitution simultaneously enhances SHG response and bandgap for mid-infrared nonlinear optics26In situ hydrothermal synthesis of polar second-order nonlinear optical selenate Na 5 (SeO 4 )(HSeO 4 ) 3 (H 2 O) 219LaTeBO 5 : a new borotellurite with a large birefringence activated by the highly distorted [Te (iv) O 4 ] group16Na 7 (IO 3 )(SO 4 ) 3 : the first noncentrosymmetric alkaline-metal iodate-sulfate with isolated [IO 3 ] and [SO 4 ] units28Rb3In(SO4)3: a defluorinated mixed main-group metal sulfate for ultraviolet transparent nonlinear optical materials with a large optical band gap26Recent advances of oxyfluorides for nonlinear optical applications69A Polar Material with Facility of Crystal Growth and a Large Second-Harmonic Generation Response3Large Second-Harmonic Response and Giant Birefringence of CeF 2 (SO 4 ) Induced by Highly Polarizable Polyhedra248Second-order nonlinear optical property of the ultraviolet transparent alkali metal-rare earth metal carbonate Na3Y(CO3)3.3H2O5UV 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 Phosphate28A New Anhydrous Polar Rare-Earth Iodate Fluoride, Ce(IO3)2F2, Exhibiting a Large Second-Harmonic-Generation Effect and Improved Overall Performance35Discovery 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 Application18CsZrF4(IO3): The First Polar Zirconium Iodate with cis-[ZrO2F6] Polyhedra Inducing Optimized Balance of Large Band Gap and Second Harmonic Generation47Tin Chloride Sulfates A3Sn2(SO4)3–xCl1+2x (A = K, Rb, Cs; x = 0, 1) as Multifunctional Optical Materials33[ o ‐C 5 H 4 NHOH] 2 [I 7 O 18 (OH)]⋅3 H 2 O: An Organic–Inorganic Hybrid SHG Material Featuring an [I 7 O 18 (OH)] Branched Polyiodate Chain86[o‐C5H4NHOH]2[I7O18(OH)]⋅3 H2O: An Organic–Inorganic Hybrid SHG Material Featuring an [I7O18(OH)] Branched Polyiodate Chain21A2MoO2F3(IO2F2) (A = Rb, Cs): Strong Nonlinear Optical Responses and Enlarged Band Gaps through Fluorine Incorporation50Synthesis, Structure, Characterization, and Calculation of a Noncentrosymmetric Fluorine-Containing Indium Iodate, Ba[InF3(IO3)2]10Solvothermal Syntheses of Three-Dimensional Open-Framework Thioantimonates Displaying Nonlinear Optical Responses5A Congruent‐Melting Mid‐Infrared Nonlinear Optical Vanadate Exhibiting Strong Second‐Harmonic Generation22A Congruent‐Melting Mid‐Infrared Nonlinear Optical Vanadate Exhibiting Strong Second‐Harmonic Generation63Giant Second-Harmonic Generation Response and Large Band Gap in the Partially Fluorinated Mid-Infrared Oxide RbTeMo 2 O 8 F149An 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 Substitution10Structural, Electronic, Mechanical, Linear and Nonlinear Optical, and Piezoelectric Properties of CsIO\(_3\) Materials from Ab Initio Study0Ca3(TeO3)2(MO4) (M = Mo, W): Mid-Infrared Nonlinear Optical Tellurates with Ultrawide Transparency Ranges and Superhigh Laser-Induced Damage Thresholds46From CeF2(SO4)·H2O to Ce(IO3)2(SO4): Defluorinated Homovalent Substitution for Strong Second-Harmonic-Generation Effect and Sufficient Birefringence53Complex coordinated functional groups: A great genes for nonlinear optical materials64K 3 V 2 O 3 F 4 (IO 3 ) 3 : a high-performance SHG crystal containing both five and six-coordinated V 5+ cations33Ba 2 [WO 3 F(IO 3 )][WO 3 F 2 ]: the first polar fluorinated tungsten iodate featuring a direct W–O–I bond7Ba 4 Ag 5 (IO 3 ) 6 (I 3 O 8 ) 3 (I 4 O 11 ) 2 : a nonlinear optical crystal containing two types of polyiodate anions16Cs 2 VOF 4 (IO 2 F 2 ): Rationally designing a noncentrosymmetric early-transition-metal fluoroiodate24Metal oxyhalides: an emerging family of nonlinear optical materials124Methylpiperazine based 0D chiral hybrid lead halides for second harmonic generation21Nain(C2o4)(Hpo4)(H2o)5: An Ultraviolet Transparent Nonlinear Optical Oxalate-Phosphate with Large Birefringence0Wide bandgaps and strong SHG responses of hetero-oxyfluorides by dual-fluorination-directed bandgap engineering28HgSO4: An excellent mid-infrared sulfate nonlinear optical crystal with wide band gap and strong second harmonic generation response19Polar lanthanide copper iodates LnCu(IO3)5 (Ln = La, Ce, Pr, and Nd): Synthesis, crystal structure and characterization6Ultrawide 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 Material12One-Side Capping in Two-Dimensional WO 3 -Type Materials Leading to Strong Second-Harmonic Response29Remarkable Infrared Nonlinear Optical, Dielectric, and Strong Diamagnetic Characteristics of Semiconducting K3[BiS3]5A Hybrid Antiperovskite with Strong Linear and Second‐Order Nonlinear Optical Responses15A Hybrid Antiperovskite with Strong Linear and Second‐Order Nonlinear Optical Responses96Isoreticular Design of KTiOPO 4 -Like Deep-Ultraviolet Transparent Materials Exhibiting Strong Second-Harmonic Generation68MIO 3 F (M = Co and Ni): Magnetic Iodate Fluorides with Zigzag Chains16Predicting Diamond-like Nitrides as Infrared Nonlinear Optical Materials with High Thermal Conductivity20From Ba3Nb2O2F12(H2O)2 to Ba0.5NbO2F2(H2O): Achieving Balanced Nonlinear Optical Performance by O/F Ratio Regulation18Recent Advances in Infrared Nonlinear Optical Crystal7Ce 3 F 4 (SO 4 ) 4 : cationic framework assembly for designing polar nonlinear optical material through fluorination degree modulation23Recent advances in F-containing iodate nonlinear optical materials6Structure and optical property evolution in PbM(PO 4 )X (M = Zn, Sn; X = halogen): SHG effect and birefringence21Noncentrosymmetric γ-Cs2I4O11 Obtained from IO4 Polyhedral Rearrangements in the Centrosymmetric β-Phase16CsHfF4(IO3): A Hafnium Iodate Exhibiting a Strong Second-Harmonic-Generation Effect and a Wide Band Gap Achieved by Mixed-Ligand Acentric Coordination8A selenite containing unusual [Ga2F(Se2O5)4(HSeO3)2]5- clusters with the polarization ‘lighted’ by F− anions15Beyond π–π Stacking: Understanding Inversion Symmetry Breaking in Crystalline Racemates26A survey of stereoactive oxysalts for linear and nonlinear optical applications40Heteroanionic LaBrVIO4 (VI = Mo, W): Excellence in Both Nonlinear Optical Properties and Photoluminescent Properties11Ultrashort Phase‐Matching Wavelength and Strong Second‐Harmonic Generation in Deep‐UV‐Transparent Oxyfluorides by Covalency Reduction33Ultrashort Phase‐Matching Wavelength and Strong Second‐Harmonic Generation in Deep‐UV‐Transparent Oxyfluorides by Covalency Reduction3Secondary‐Bond‐Driven Construction of a Polar Material Exhibiting Strong Broad‐Spectrum Second‐Harmonic Generation and Large Birefringence9Secondary‐Bond‐Driven Construction of a Polar Material Exhibiting Strong Broad‐Spectrum Second‐Harmonic Generation and Large Birefringence41Ba 2 Ga 2 F 6 (IO 3 )(PO 4 ): the first fluoride-containing iodate-phosphate with a 1D [Ga 2 F 6 (IO 3 )(PO 4 )] 4− helix chain2Novel Laser Crystal Nd:LiY(MoO4)2: Crystal Growth, Characterization, and Orthogonally Polarized Dual-Wavelength Laser13Enhancement of Birefringence in π-Conjugated Oxyfluorides Achieved via van der Waals Layered Structural Optimization10Designing Strong Polarity and High Configurational Entropy Flexible Units toward Excellent Ultraviolet Nonlinear Optical Materials42Diversity of [M(IO3)6] Building Blocks in Iodate Families and the New Trigonal Polymorph of Cs2HIn(IO3)64Diversity of fundamental building blocks [M(IO3)6] in iodate families and new trigonal polymorph of Cs2HIn(IO3)60SbO(OH)2(IO3): The First Polar Sb5+‐Iodate with a Strong Second‐Harmonic Generation Response and a Wide Bandgap8Emergent Mid‐Infrared Nonlinear Optical Candidates With Targeted Balance Performances17Design and Synthesis of Vanadium-Based Infrared Nlo Crystal K4cdv5o15br Through Aliovalent Substitution with Strongly Polarized Active Units0Multifactorial Directed Regulation Of the [Io 3 ] − Units in Praseodymium-Contained Iodates0Enhanced 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) Fluoride10Potassium Tetraiodatoiodate(III) Iodate(V): A Nonlinear Optical Crystal with Exceptional Second‐Harmonic Generation and Full‐Wavelength Phase Matching19Potassium Tetraiodatoiodate(III) Iodate(V): A Nonlinear Optical Crystal with Exceptional Second‐Harmonic Generation and Full‐Wavelength Phase Matching0Nonlinear Optical Series A(VO2)3(SeO3)2 (A = NH4+, K+, and H3O+) with Large Birefringence Derived from High-Anisotropic VO6 Octahedra and SeO3 Pyramids8Three-In-One: A Guanidinium-Containing Niobium Oxyfluoride with a Perovskite-like Structure Revealing Multifunctional Optical Properties2Multifactorial directed regulation of anionic units in praseodymium-contained iodates1A Band‐Orientation Co‐Anchoring Strategy for the Design of a High‐Performance Mid‐Infrared Nonlinear Optical Crystal2A Band‐Orientation Co‐Anchoring Strategy for the Design of a High‐Performance Mid‐Infrared Nonlinear Optical Crystal12Hydrogen-bond-driven noncentrosymmetric structure formation in π-conjugated (C3H7N6)(IO3): achieving both strong SHG response and wide bandgap5Recent achievements of d0 transition-metal-based oxyfluorides: Crystal chemistry and application in second-order NLO materials10Polar Antiperovskite Oxides: Promising Mid-Infrared Nonlinear Optical Materials with Strong Second-Harmonic Generation2

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  2. Gd(NO 3 )(Se 2 O 5 )·3H 2 O: a nitrate–selenite nonlinear optical material with a short ultraviolet cutoff edge

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  4. Incorporating rare-earth cations with moderate electropositivity into iodates for the optimized second-order nonlinear optical performance

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  5. On Prediction of a Novel Chiral Material Y2H3O(OH): A Hydroxyhydride Holding Hydridic and Protonic Hydrogens

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  6. Rational Design of the Nonlinear Optical Response in a Tin Iodate Fluoride Sn(IO3)2F2

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  7. Enhancement of Second-Order Optical Nonlinearity in a Lutetium Selenite by Monodentate Anion Partial Substitution

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  11. Synthesis, crystal structures and optical properties of open-framework gallium phosphates: NaGa3F4(PO4)2(H2O)2 and AGa2P2O7(OH)3(H2O) (A = K, Rb)

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  12. New Alkaline-Earth Metal Fluoroiodates Exhibiting Large Birefringence and Short Ultraviolet Cutoff Edge with Highly Polarizable (IO 3 F) 2– Units

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  14. High Coordinate Metal Iodate Chlorides with Diverse Structural Motifs and Tunable Birefringence

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  15. Ba2[MoO3(OH)(IO3)2]IO3: A Promising SHG Material Featuring a Λ-Shaped Functional Motif Achieved by Universal Mono-Site Substitution

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  17. From Ag2Zr(IO3)6 to LaZr(IO3)5F2: A Case of Constructing Wide‐band‐gap Birefringent Materials through Chemical Cosubstitution

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  18. Synthesis, Structure, and Characterization of d0 Transition-Metal Iodate: BaTi(IO3)6·0.5H2O

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  21. Giant Optical Anisotropy in the UV‐Transparent 2D Nonlinear Optical Material Sc(IO 3 ) 2 (NO 3 )

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  22. Giant Optical Anisotropy in the UV‐Transparent 2D Nonlinear Optical Material Sc(IO 3 ) 2 (NO 3 )

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  23. Recent Achievements in Lone-Pair Cation-Based Infrared Second-Order Nonlinear Optical Materials

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  30. LaTeBO 5 : a new borotellurite with a large birefringence activated by the highly distorted [Te (iv) O 4 ] group

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  31. Na 7 (IO 3 )(SO 4 ) 3 : the first noncentrosymmetric alkaline-metal iodate-sulfate with isolated [IO 3 ] and [SO 4 ] units

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  32. Rb3In(SO4)3: a defluorinated mixed main-group metal sulfate for ultraviolet transparent nonlinear optical materials with a large optical band gap

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  33. Recent advances of oxyfluorides for nonlinear optical applications

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  34. A Polar Material with Facility of Crystal Growth and a Large Second-Harmonic Generation Response

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  35. Large Second-Harmonic Response and Giant Birefringence of CeF 2 (SO 4 ) Induced by Highly Polarizable Polyhedra

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  36. Second-order nonlinear optical property of the ultraviolet transparent alkali metal-rare earth metal carbonate Na3Y(CO3)3.3H2O

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  37. UV Solar‐Blind‐Region Phase‐Matchable Optical Nonlinearity and Anisotropy in a π‐Conjugated Cation‐Containing Phosphate

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  38. UV Solar‐Blind‐Region Phase‐Matchable Optical Nonlinearity and Anisotropy in a π‐Conjugated Cation‐Containing Phosphate

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  39. A New Anhydrous Polar Rare-Earth Iodate Fluoride, Ce(IO3)2F2, Exhibiting a Large Second-Harmonic-Generation Effect and Improved Overall Performance

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

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

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  42. CsZrF4(IO3): The First Polar Zirconium Iodate with cis-[ZrO2F6] Polyhedra Inducing Optimized Balance of Large Band Gap and Second Harmonic Generation

    Chemistry of Materials · 2021

    Lin Lin, Xingxing Jiang, Chao Wu, Zheshuai Lin, Zhipeng Huang, Mark Graeme Humphrey, Chi Zhang

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  43. Tin Chloride Sulfates A3Sn2(SO4)3–xCl1+2x (A = K, Rb, Cs; x = 0, 1) as Multifunctional Optical Materials

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  44. [ o ‐C 5 H 4 NHOH] 2 [I 7 O 18 (OH)]⋅3 H 2 O: An Organic–Inorganic Hybrid SHG Material Featuring an [I 7 O 18 (OH)] Branched Polyiodate Chain

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