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RESEARCH PAPER · Angewandte Chemie International Edition · 2019

LiMII(IO3)3 (MII=Zn and Cd): Two Promising Nonlinear Optical Crystals Derived from a Tunable Structure Model of α‐LiIO3

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LiMII(IO3)3 (MII=Zn and Cd): Two Promising Nonlinear Optical Crystals Derived from a Tunable Structure Model of α‐LiIO3OriginalEmergent Deep‐Ultraviolet Nonlinear Optical Candidates324Neue Kandidaten für die nichtlineare Optik im Tief‐UV‐Bereich43From centrosymmetric to noncentrosymmetric: intriguing structure evolution in d 10 -transition metal iodate fluorides36Large nonlinear optical effect in tungsten bronze structures via Li/Na cross-substitutions4M 4 LiBe 4 P 7 O 24 and M 4 Li(Li 3 P)P 7 O 24 (M = Cs, Rb): deep-ultraviolet nonlinear-optical phosphates with a tetrahedra-substituted paracelsian-like framework9Rational Design of the Nonlinear Optical Response in a Tin Iodate Fluoride Sn(IO3)2F290K2Na(IO3)2(I3O8) with Strong Second Harmonic Generation Response Activated by Two Types of Isolated Iodate Anions46High 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 Substitution50Fluorine Substitution in Ethylamine Triggers Second Harmonic Generation in Noncentrosymmetric Crystalline [NH3CH2CH2F]3BiCl632Enhanced Proton Conductivity by Aliovalent Substitution of Cadmium for Indium in Dimethylaminium-Templated Metal Anilicates29Recent 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 Cosubstitution11An inherently kidney-targeting near-infrared fluorophore based probe for early detection of acute kidney injury59Methylation Design Strategy to Trigger a Dual Dielectric Switch and Improve the Phase Transition Temperature13Bi 32 Cd 3 P 10 O 76 : a new congruently melting nonlinear optical crystal with a large SHG response and a wide transparent region24Simple New Method for the Preparation of La(IO3)3 Nanoparticles6A new nonlinear optical sulfate of layered structure: Cs2Zn2(SO4)319Chiral Template‐Driven Macroscopic Chirality Control: Structure‐Second‐Harmonic Generation Properties Relationship24High-Pressure Spectroscopy Study of Zn(IO3)2 Using Far-Infrared Synchrotron Radiation12[GaF(H 2 O)][IO 3 F]: a promising NLO material obtained by anisotropic polycation substitution42Pressure-dependent modifications in the optical and electronic properties of Fe(IO 3 ) 3 : the role of Fe 3d and I 5p lone–pair electrons15SrTi(IO 3 ) 6 ·2H 2 O and SrSn(IO 3 ) 6 : distinct arrangements of lone pair electrons leading to large birefringences11Na3Bi(IO3)6: An Alkali-Metal Bismuth Iodate with Intriguing One-Dimensional [BiI6O18] Chains and Pressure-Induced Structural Transition11Cd3(IO3)(IO4)F2·0.1CdO: A Nonlinear-Optical Crystal with the Introduction of Fluoride into Iodate Containing Both [IO3]− and [IO4]3– Groups18CsZrF4(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 Materials33Sr2Pb(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]10Ca-cluster-constructed deep-ultraviolet nonlinear-optical crystal Na2Ca17Al2(PO4)14 with strong NLO response11Synthesis and Characterization of Novel Nanoparticles of Lithium Aluminum Iodate LiAl(IO3)4, and DFT Calculations of the Crystal Structure and Physical Properties6KCs2Pb2(HCOO)2Cl5: A Lead Formate with Strong Second-Harmonic-Generation Response Obtained by an Anionic Substitution3BaI 3 O 9 H: a new alkaline-earth metal hydroxy iodate with two groups2Cd 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 gaps28From oxides to oxysulfides: the mixed-anion GeS 3 O unit induces huge improvement in the nonlinear optical effect and optical anisotropy for potential nonlinear optical materials19Piezoelectricity and related properties in orthorhombic cadmium diiodate4Unprecedented mid-infrared nonlinear optical materials achieved by crystal structure engineering, a case study of (KX)P 2 S 6 (X = Sb, Bi, Ba)59Lead Tellurite Crystals BaPbTe2O6 and PbVTeO5F with Large Nonlinear-/Linear-Optical Responses due to Active Lone Pairs and Distorted Octahedra20Polar lanthanide copper iodates LnCu(IO3)5 (Ln = La, Ce, Pr, and Nd): Synthesis, crystal structure and characterization6Explorations of New SHG Materials in Mercury Iodate Sulfate System**9General relationship between the band-gap energy and iodine-oxygen bond distance in metal iodates15AgGaSe2-Inspired Nonlinear Optical Materials: Tetrel Selenides of Alkali Metals and Mercury34Coordination metal effect on the nonlinear optical properties and biological activity of double selenates8Synthesis, characterization and theoretical calculations of four chiral schiff base materials for second harmonic generation applications7Mixed-Anion-Oriented Design of LnMGa3S6O (Ln = La, Pr, and Nd; M = Ca and Sr) Nonlinear Optical Oxysulfides with Targeted Property Balance56PbBi(SeO 3 ) 2 F and Pb 2 Bi(SeO 3 ) 2 Cl 3 : Coexistence of Three Kinds of Stereochemically Active Lone-Pair Cations Exhibiting Excellent Nonlinear Optical Properties57MIO 3 F (M = Co and Ni): Magnetic Iodate Fluorides with Zigzag Chains16[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 topology20A new stable polymorph of Li 2 TeMo 3 O 12 with wide mid-infrared transparency and a large Raman response17Ga(IO 3 ) 3 : a mid-IR nonlinear optical iodate with balanced performance between band gap and second harmonic generation response4LaAeAl 3 S 7 (Ae = Ca, Sr): Cairo pentagonal layered thioaluminates achieving a good balance between a strong second harmonic generation response and a wide bandgap23Na 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 birefringence8Recent advances in F-containing iodate nonlinear optical materials6Polar Bismuth Selenite Iodate Oxide BiSeIO6 with Three Types of Lone Pair Cations in One Structure6CsHfF4(IO3): A Hafnium Iodate Exhibiting a Strong Second-Harmonic-Generation Effect and a Wide Band Gap Achieved by Mixed-Ligand Acentric Coordination8A review on the advancements in the characterization of the high-pressure properties of iodates44Optimal Design of Mid-Infrared Nonlinear-Optical Crystals: From SrZnSnSe 4 to SrZnSiSe 422ε-La(IO3)3: A Polar Iodate with High Thermal Stability and a Large Second-Harmonic-Generation Response Obtained by a Supercritical Hydrothermal Method8Advances in aliovalent substitution strategy for the design and synthesis of nonlinear optical materials: d0 transition metal/gallium iodates and selenites70A selenite containing unusual [Ga2F(Se2O5)4(HSeO3)2]5- clusters with the polarization ‘lighted’ by F− anions15α- and β-(C4H5N2O)(IO3)·HIO3: Two SHG Materials Based on Organic–Inorganic Hybrid Iodates14Deep-ultraviolet (DUV) nonlinear optical (NLO) crystals: An application in photonic technologies29LiGa(IO3)4: An Excellent NLO Material with Unprecedented 2D [Ga(IO3)4]∞− Layer Synthesized by Aliovalent Substitution20Synthesis and Structure of a New Iodate Cs5[Sc2(IO3)9](IO3)2 with a Complex Framework Based on the Condensation of [Sc(IO3)6] Building Blocks4Enlargement of Bandgap and Birefringence in Nonlinear Optical Alkali‐Metal Sulfate Crystals by the Substitution of Asymmetrical Non‐π‐Conjugated Cation8K(NH4)Zn2(PO4)2: a Beryllium-Free Sr2Be2B2O7 Derivative with Enhanced Interlayer Connectivity71D Cu( i )-based chiral organic–inorganic hybrid material with second harmonic generation and circular polarized luminescence10Chromium iodate: the structure and origin of optical second harmonic generation1Explorations of highly birefringent materials in the vanadium oxyfluoride–iodate system by fluoride ion modulation8From NaGa(IO3)3F to NaGa(IO3)2F2 and NaGa(IO3)4: The Effects of Chemical Substitution between F– Anions and IO3– Groups on the Structures and Properties of Gallium Iodates13Noncentrosymmetric tellurite halides created by a depolymerization strategy: toward strong SHG intensity and wide bandgap16Novel cesium cerium( iv ) iodate Cs 2 Ce(IO 3 ) 6 : hydrothermal synthesis, crystal structures and thermal stability2High Proton Conduction for CPM-200 Achieved by Aliovalent-Predefinition of M3(μ3-O) Building Blocks and In Situ Encapsulation of Hydrated Metal Ions13Anhydrous Aluminum Iodate: Strong Second Harmonic Generation Effect Contributed by Unbonded and Antibonding Orbitals3Investigation of second-order NLO properties of novel 1,3,4-oxadiazole derivatives: a DFT study7Samarium Hydrogen Iodate, Sm(IO3)3·HIO3: Synthesis and Characterization0Lanthanide Contraction Eliminates Disorder while Holding Robust Second Harmonic Generation in a Series of Polyiodates13SbO(OH)2(IO3): The First Polar Sb5+‐Iodate with a Strong Second‐Harmonic Generation Response and a Wide Bandgap8Symmetry related proton conductivity tunability via aliovalent metal substitution in imidazolium templated stable metal-organic framework hybrid membranes6K 2 Na(I 3 O 8 ) 3 : a promising mid-infrared birefringent material with two different structures of octaoxotriiodate( v ) polyanions1From (C6H5N2)2CdCl4 to (C6H5N2)2ZnCl4, Chirality Transformation to Realize a Nonlinear Optical Organic–Inorganic Hybrid Halide with Balanced Comprehensive Performance19Two-Step Substitutions of Square Pyramidal VO5 with CdO4Br to Achieve Higher Laser-Induced Damage Threshold from Polar Oxybromides Rb4CdV5O15Br to Rb3CdV4O12Br10Potassium 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 Matching0Multifactorial directed regulation of anionic units in praseodymium-contained iodates1SrZnGeSe4: An Infrared Nonlinear Optical Crystal Material with Wide Transmission Range and Large SHG Response6Metal Chloride‐Iodate Nonlinear Optical Materials via Direct Chlorination of Centrosymmetric Metal Iodate Crystals0K2HGa(IO3)6: A new member of iodate families with [M(IO3)6] building blocks0Single-Anion Conductor Enabled by Quaterization and Ion Exchange in an Imidazole-Modified Metal–Organic Framework0High-temperature biphasic transition and dielectric switching in a tin-based organic-inorganic hybrid of (FTEA)2SnCl60KCd(IO 3 ) 2 Cl: A New UV NLO Crystal with Balanced Optical Properties Engineering via Target‐Driven Multi‐Ion Substitution Strategy7Solving the long-standing hygroscopicity and thermal stability issues of the nonlinear optical crystal α-LiIO 3 via homogeneous cation exchange0Stable lead succinate-iodides with strong second-harmonic generation response and large birefringence0Syntheses, 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 )0Chelate Anchoring at Open Sites of Zirconium‐Oxo Cluster by Bifunctional Carboxyl‐Sulfonyl Ligand Enhancing Stability and Proton Conductivity in MOF Fibrous Membrane8LiMn(IO 3 ) 3 : A Noncentrosymmetric Iodate Synthesized by Polyhedral Volume Ratio Modulation0First‐Principles Investigation of the Structural, Electronic, Optical, Elastic, and Thermal Properties of Defect Diamond‐Like Hg 3 P 2 S 80The Multi‐Scale Paradigm: An Integrated Design Logic for Nonlinear Optical Crystals1

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  5. M 4 LiBe 4 P 7 O 24 and M 4 Li(Li 3 P)P 7 O 24 (M = Cs, Rb): deep-ultraviolet nonlinear-optical phosphates with a tetrahedra-substituted paracelsian-like framework

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  10. Fluorine Substitution in Ethylamine Triggers Second Harmonic Generation in Noncentrosymmetric Crystalline [NH3CH2CH2F]3BiCl6

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  47. MIO 3 F (M = Co and Ni): Magnetic Iodate Fluorides with Zigzag Chains

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    Hang Liu, Yanhong Wang, Ya-Dong Zhou, Shuang Li, Yaling Dou, Tao Wang, Hongcheng Lu

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