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RESEARCH PAPER · Journal of the American Chemical Society · 2018

Assisting the Effective Design of Polar Iodates with Early Transition-Metal Oxide Fluoride Anions

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Assisting the Effective Design of Polar Iodates with Early Transition-Metal Oxide Fluoride AnionsOriginalIon-induced structural and optical performance evolution in LBO-like crystals: experimental and theoretical investigation13PbFePO 4 F 2 with a 1/6th bond depleted triangular lattice7Ce(IO3)2F2⋅H2O: The First Rare‐Earth‐Metal Iodate Fluoride with Large Second Harmonic Generation Response66A Facile Route to Nonlinear Optical Materials: Three‐Site Aliovalent Substitution Involving One Cation and Two Anions137A Facile Route to Nonlinear Optical Materials: Three‐Site Aliovalent Substitution Involving One Cation and Two Anions23(H 3 O)HCs 2 Nb(IO 3 ) 9 and SrNbO(IO 3 ) 5 : a facile synthetic method using hydrofluoric acid as a solubilizer19An energy band engineering design to enlarge the band gap of KTiOPO 4 (KTP)-type sulfates via aliovalent substitution66Cs 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 activity19KBi(IO 3 ) 3 (OH) and NaBi(IO 3 ) 4 : from the centrosymmetric chain to a noncentrosymmetric double layer18LiMg(IO 3 ) 3 : an excellent SHG material designed by single-site aliovalent substitution68M 2 (SeO 3 )F 2 (M = Zn, Cd): understanding the structure directing effect of [SeO 3 ] 2− groups on constructing ordered oxyfluorides14Sr[B(OH) 4 ](IO 3 ) and Li 4 Sr 5 [B 12 O 22 (OH) 4 ](IO 3 ) 2 : two unprecedented metal borate-iodates showing a subtle balance of enlarged band gap and birefringence34Synthesis and structure of a new mixed metal iodate Ba 3 Ga 2 (IO 3 ) 1218Three new phosphates, Cs8Pb4(P2O7)4, CsLi7(P2O7)2 and LiCa(PO3)3: structural comparison, characterization and theoretical calculation23Exploration of New Birefringent Crystals in Bismuth d0 Transition Metal Selenites35A Niobium Oxyiodate Sulfate with a Strong Second‐Harmonic‐Generation Response Built by Rational Multi‐Component Design114A Niobium Oxyiodate Sulfate with a Strong Second‐Harmonic‐Generation Response Built by Rational Multi‐Component Design25Variable Chains Found in Mixed Transition Metal Oxyfluorides with Heterocyclic Ligands9REI5O14 (RE=Y and Gd): Promising SHG Materials Featuring the Semicircle‐Shaped I5O143− Polyiodate Anion125REI5O14 (RE=Y and Gd): Promising SHG Materials Featuring the Semicircle‐Shaped I5O143− Polyiodate Anion62Mixed Transition Metal (Oxy)fluoride Paramagnet Chains: Synthesis, Structure, and Characterization11SrI3O9H: A new alkaline earth metal iodate with two different anionic units using mild aqua-solution method8Nontoxic KBBF Family Member Zn2BO3(OH): Balance between Beneficial Layered Structure and Layer Tendency82Cation Modulation on the Crystal Structure and Band Gap of Fluorooxoborates A3B3O3F6 (A = Alkali and Mixed Alkali Metal)17LiMII(IO3)3 (MII=Zn and Cd): Two Promising Nonlinear Optical Crystals Derived from a Tunable Structure Model of α‐LiIO398LiMII(IO3)3 (MII=Zn and Cd): Two Promising Nonlinear Optical Crystals Derived from a Tunable Structure Model of α‐LiIO337A x Ce 9 (IO 3 ) 36 (A = K, La): the effects of a change in the intermediate valence on the second-harmonic generation response7Ag4Hg(SeO3)2(SeO4): a novel SHG material created in mixed valent selenium oxides by in situ synthesis36K5(W3O9F4)(IO3): An Efficient Mid-Infrared Nonlinear Optical Compound with High Laser Damage Threshold114(NH4)Bi2(IO3)2F5: An Unusual Ammonium‐Containing Metal Iodate Fluoride Showing Strong Second Harmonic Generation Response and Thermochromic Behavior92(NH4)Bi2(IO3)2F5: An Unusual Ammonium‐Containing Metal Iodate Fluoride Showing Strong Second Harmonic Generation Response and Thermochromic Behavior11Ba(B 2 OF 3 (OH) 2 ) 2 with well-ordered OH/F anions and a unique B 2 OF 3 (OH) 2 dimer29From 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 material25Hexagonal tungsten oxides with large bandgaps synthesized by a chemical substitution method31In[Ba 3 Cl 3 F 6 ]: a novel infrared-transparent molecular sieve constructed by halides6Incorporating rare-earth cations with moderate electropositivity into iodates for the optimized second-order nonlinear optical performance17Influence of structure-directing polyhedra and heterocyclic ligands on the chain structures and O/F ordering in a series of zinc vanadium oxyfluorides1New polymorphism for BaTi(IO 3 ) 6 with two polymorphs crystallizing in the same space group11Two new ammonium/alkali-rare earth metal difluorophosphates ALa(PO 2 F 2 ) 4 (A = NH 4 and K) with moderate birefringence and short cutoff edges26Designing Sulfide Borate as a Novel Type of Second-Order Nonlinear-Optical Material91CsVO2F(IO3): An Excellent SHG Material Featuring an Unprecedented 3D [VO2F(IO3)]− Anionic Framework132CsVO2F(IO3): An Excellent SHG Material Featuring an Unprecedented 3D [VO2F(IO3)]− Anionic Framework22PbB5O7F3: A High-Performing Short-Wavelength Nonlinear Optical Material121Rational 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 Gap57Designing a Deep-UV Nonlinear Optical Fluorooxosilicophosphate127Hexagonal In2Se3: A Defect Wurtzite-Type Infrared Nonlinear Optical Material with Moderate Birefringence Contributed by Unique InSe5 Unit75A2SnS5: A Structural Incommensurate Modulation Exhibiting Strong Second‐Harmonic Generation and a High Laser‐Induced Damage Threshold (A=Ba, Sr)30A2SnS5: A Structural Incommensurate Modulation Exhibiting Strong Second‐Harmonic Generation and a High Laser‐Induced Damage Threshold (A=Ba, Sr)86BiGa(SeO3)3: A Phase Matchable SHG Material Achieved by Cation Substitution19Ba(IO3)F: An Alkaline-Earth-Metal Iodate Fluoride Crystal with Large Band Gap and Birefringence24New Alkaline-Earth Metal Fluoroiodates Exhibiting Large Birefringence and Short Ultraviolet Cutoff Edge with Highly Polarizable (IO 3 F) 2– Units63Multimodal Structure Solution with 19F NMR Crystallography of Spin Singlet Molybdenum Oxyfluorides15AGa 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 Gaps64Cs3B3O3F6 with a Deep-Ultraviolet Cutoff Edge and a Suitable Birefringence as the Potential Zero-Order Waveplate Material31Recent Advances in Oxide‐based Nonlinear Optical Materials with Wide Infrared Transparency Beyond 6 μm38From Ag2Zr(IO3)6 to LaZr(IO3)5F2: A Case of Constructing Wide‐band‐gap Birefringent Materials through Chemical Cosubstitution12A 3 BBi(P 2 O 7 ) 2 (A = Rb, Cs; B = Pb, Ba): Isovalent Cation Substitution to Sustain Large Second-Harmonic Generation Responses106Bi 32 Cd 3 P 10 O 76 : a new congruently melting nonlinear optical crystal with a large SHG response and a wide transparent region24Ba(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 Response69[GaF(H 2 O)][IO 3 F]: a promising NLO material obtained by anisotropic polycation substitution43Ba 2 [FeF 4 (IO 3 ) 2 ]IO 3 : a promising nonlinear optical material achieved by chemical-tailoring-induced structure evolution8Barium fluoroiodate crystals with a large band gap and birefringence23In situ hydrothermal synthesis of polar second-order nonlinear optical selenate Na 5 (SeO 4 )(HSeO 4 ) 3 (H 2 O) 219Na 7 (IO 3 )(SO 4 ) 3 : the first noncentrosymmetric alkaline-metal iodate-sulfate with isolated [IO 3 ] and [SO 4 ] units30NaGaI 3 O 9 F: a new alkali metal gallium iodate combined with IO 3 − and IO 3 F 2− units17Pb 2 TiFO(SeO 3 ) 2 Br: a new polar compound with the strongest second harmonic generation in the selenite bromide family29Recent advances of oxyfluorides for nonlinear optical applications69Zn(NH 3 )CO 3 : a “three-in-one” UV nonlinear optical crystal built by a polar molecule bonding strategy18New Polymorphism for Ba3Zn2(BO3)3F with Two Polymorphs Exhibiting Anomalous Phase Transition2Different mechanism of stereochemical activity and birefringence in post-transition metal halides: A first-principles investigation1A Polar Material with Facility of Crystal Growth and a Large Second-Harmonic Generation Response3A New Anhydrous Polar Rare-Earth Iodate Fluoride, Ce(IO3)2F2, Exhibiting a Large Second-Harmonic-Generation Effect and Improved Overall Performance36CsZrF4(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 Materials34Be2(BO3)(IO3): The First Anion‐mixed Van der Waals Member in the KBe2BO3F2 Family with a Very Strong Second Harmonic Generation Response130Be2(BO3)(IO3): The First Anion‐mixed Van der Waals Member in the KBe2BO3F2 Family with a Very Strong Second Harmonic Generation Response8High-Performance Second-Harmonic-Generation (SHG) Materials: New Developments and New Strategies323[ 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 Incorporation51Synthesis, 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 Generation23A Congruent‐Melting Mid‐Infrared Nonlinear Optical Vanadate Exhibiting Strong Second‐Harmonic Generation64An 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 Potassium Tungsten Oxyfluoride with Strong Second-Harmonic Generation Response Derived from Anion-Ordered Functional Motif18AMoO3(IO3) (A = Na and K): Two promising optical materials via properly assembling the Λ-shaped basic building units19Designing A New Infrared Nonlinear Optical Material, β‐BaGa 2 Se 4 Inspired by the Phase Transition of the BaB 2 O 4 (BBO) Crystal75Designing A New Infrared Nonlinear Optical Material, β‐BaGa2Se4 Inspired by the Phase Transition of the BaB2O4 (BBO) Crystal12Complex 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+ cations33A 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 Transparency96A 2 P 2 S 6 (A = Ba and Pb): a good platform to study the polymorph effect and lone pair effect to form an acentric structure30Ba 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 anions16Cd 2 (IO 3 )(PO 4 ) and Cd 1.62 Mg 0.38 (IO 3 )(PO 4 ): metal iodate-phosphates with large SHG responses and wide band gaps29Cs 2 VOF 4 (IO 2 F 2 ): Rationally designing a noncentrosymmetric early-transition-metal fluoroiodate25Metal oxyhalides: an emerging family of nonlinear optical materials125Mg(H 2 O) 6 [(IO 2 (OH)) 2 (IO 3 )] 2 : a new iodate with a very large band gap and optical anisotropy13The exploration of new infrared nonlinear optical crystals based on the polymorphism of BaGa 4 S 731Wide bandgaps and strong SHG responses of hetero-oxyfluorides by dual-fluorination-directed bandgap engineering27Novel layered heterobimetallic fluorides with large optical band gaps3Cd4InO(BO3)3: A New Nonlinear Optical Crystal Exhibiting Strong Second Harmonic Generation Effect and Moderate Birefringence2K3ZrF4(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 Material12Synthesis, Crystal and Electronic Structures, and Nonlinear Optical Properties of Y4Si3S1213One-Side Capping in Two-Dimensional WO 3 -Type Materials Leading to Strong Second-Harmonic Response29A Theoretical Perspective to Study the Optical Properties of Tetrafluoroborates4Additive‐Triggered Polar Polymorph Formation: β‐Sc(IO 3 ) 3 , a Promising Next‐Generation Mid‐Infrared Nonlinear Optical Material42Additive‐Triggered Polar Polymorph Formation: β‐Sc(IO3)3, a Promising Next‐Generation Mid‐Infrared Nonlinear Optical Material3NH4IO2F2 and (NH4)3(IO2F2)3·H2O: A Series of Ammonium-Containing Fluoroiodates with Wide Band Gaps12Enhancements of Second Harmonic Generation and Birefringence in Traditional RbTiOPO4‐Type Crystals by Aliovalent Substitution of Ti Site1Isoreticular Design of KTiOPO 4 -Like Deep-Ultraviolet Transparent Materials Exhibiting Strong Second-Harmonic Generation69MIO 3 F (M = Co and Ni): Magnetic Iodate Fluorides with Zigzag Chains16ZrF2(IO3)2 and RbGaF3(IO3): Two Promising Birefringent Crystals Featuring 1D Metal-Fluoride Cationic Chains and Wide Bandgaps23Synthesis and Crystal Structure of Fluoride K2(Ta0.9I0.1)F7 with the Micro-Isomorphic Substitution in the Ta Cationic Position0[M(OH) 2 ] 3 (IO 3 )(SeO 4 )·H 2 O (M = Ga and In): metal iodate–selenate nonlinear optical materials with a hexagonal tungsten oxide-type topology21A new stable polymorph of Li 2 TeMo 3 O 12 with wide mid-infrared transparency and a large Raman response17AIO3·H6TeO6 (A = NH4+, Rb+): Two telluric acid and iodate Co-crystalline compounds with second harmonic generation response4Ga(IO 3 ) 3 : a mid-IR nonlinear optical iodate with balanced performance between band gap and second harmonic generation response4Linear optical afterglow and nonlinear optical harmonic generation from chiral tin( iv ) halides: the role of lattice distortions37Na 7 (SeO 4 ) 3 (IO 3 ) and K 2 (SeO 4 )[IO 2 (OH)]: two new iodate-selenates with short-wave UV cutoff edge and large birefringence9Recent advances in F-containing iodate nonlinear optical materials6Toward Large Second-Harmonic Generation and Deep-UV Transparency in Strongly Electropositive Transition Metal Sulfates112Growth and Optical Properties of Large-Sized NaVO2(IO3)2(H2O) Crystals for Second-Harmonic Generation Applications11Noncentrosymmetric 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 Coordination8Alignment of Λ-Shaped Basic Building Units to Construct One New KMoO3(IO3) Polar Polymorph11Multi‐Stimuli Responsive Luminescence and Domino Phase Transition of Hybrid Copper Halides with Nonlinear Optical Switching Behavior19Multi‐Stimuli Responsive Luminescence and Domino Phase Transition of Hybrid Copper Halides with Nonlinear Optical Switching Behavior125Designing a Strong Second-Harmonic Generation Polar Iodate by the Structure-Directing Properties of the “Tumbler-like” [Zn(IO3)(I2O5(OH))] Polyanions20Advances in aliovalent substitution strategy for the design and synthesis of nonlinear optical materials: d0 transition metal/gallium iodates and selenites69A selenite containing unusual [Ga2F(Se2O5)4(HSeO3)2]5- clusters with the polarization ‘lighted’ by F− anions15Single-Crystalline Li2Sn(IO3)6 Microwires: Combining Optical-Waveguiding and Frequency-Doubling Functions5Beyond π–π Stacking: Understanding Inversion Symmetry Breaking in Crystalline Racemates27Quadruple‐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 Birefringence2α- and β-(C4H5N2O)(IO3)·HIO3: Two SHG Materials Based on Organic–Inorganic Hybrid Iodates14A survey of stereoactive oxysalts for linear and nonlinear optical applications40Heteroanionic LaBrVIO4 (VI = Mo, W): Excellence in Both Nonlinear Optical Properties and Photoluminescent Properties11

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