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RESEARCH PAPER · Angewandte Chemie International Edition · 2019

A Niobium Oxyiodate Sulfate with a Strong Second‐Harmonic‐Generation Response Built by Rational Multi‐Component Design

Hong‐Xin Tang, Yu‐Xiao Zhang, Chao Zhuo, Ruibiao Fu, Hua Lin, Zuju Ma, Xin‐Tao Wu

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A Niobium Oxyiodate Sulfate with a Strong Second‐Harmonic‐Generation Response Built by Rational Multi‐Component DesignOriginalCs 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 activity19LiMg(IO 3 ) 3 : an excellent SHG material designed by single-site aliovalent substitution68Tb(HSO 4 )(SO 4 ) – a green emitting hydrogensulfate sulfate with second harmonic generation response21REI5O14 (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 Anion62Two Indium Sulfate Tellurites: Centrosymmetric In 2 (SO 4 )(TeO 3 )(OH) 2 (H 2 O) and Non-centrosymmetric In 3 (SO 4 )(TeO 3 ) 2 F 3 (H 2 O)33In Honor of Professor Xintao Wu on the Occasion of His Eightieth Birthday0Nontoxic KBBF Family Member Zn2BO3(OH): Balance between Beneficial Layered Structure and Layer Tendency81LiMII(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 response7Second harmonic generation responses of KH 2 PO 4 : importance of K and breaking down of Kleinman symmetry49Insight into the Expanded Mislinked Porphyrins with High Second Order Nonlinear Optical Response34Key Factors Controlling the Large Second Harmonic Generation in Nonlinear Optical Materials37K2Na(IO3)2(I3O8) with Strong Second Harmonic Generation Response Activated by Two Types of Isolated Iodate Anions46Dimensionality–Band Gap–Third-Harmonic Generation Property Relationship in Novel Main-Group Metal Iodates37A review on phase transition and structure-performance relationship of second-order nonlinear optical polymorphs107High Coordinate Metal Iodate Chlorides with Diverse Structural Motifs and Tunable Birefringence10From Ag2Zr(IO3)6 to LaZr(IO3)5F2: A Case of Constructing Wide‐band‐gap Birefringent Materials through Chemical Cosubstitution11From S–O–S to B–O–S to B–O–B Bridges: Ba[B(S2O7)2]2 as a Model System for the Structural Diversity in Borosulfate Chemistry28Cs 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 Groups22Y 2 (Te 4 O 10 )(SO 4 ): a new sulfate tellurite with a unique Te 4 O 10 polyanion and large birefringence36Sb6O7(SO4)2: A Promising Ultraviolet Nonlinear Optical Material with an Enhanced Second‐Harmonic‐Generation Response Activated by SbIII Lone‐Pair Stereoactivity62First chiral fluorinated lead vanadate selenite Pb 2 (V 2 O 4 F)(VO 2 )(SeO 3 ) 3 with five asymmetric motifs and large optical properties24Na 7 (IO 3 )(SO 4 ) 3 : the first noncentrosymmetric alkaline-metal iodate-sulfate with isolated [IO 3 ] and [SO 4 ] units28Tuning the first hyperpolarizability of hexaphyrins with different connections of mislinked pyrrole units: a theoretical study17Two bismuth iodate sulfates with enhanced optical anisotropy17A Polar Material with Facility of Crystal Growth and a Large Second-Harmonic Generation Response3Introduction of Li into Ag-Based Noncentrosymmetric Sulfides for High-Performance Infrared Nonlinear Optical Materials40Titanium Iodates with a Second-Harmonic-Generation Response8A New Anhydrous Polar Rare-Earth Iodate Fluoride, Ce(IO3)2F2, Exhibiting a Large Second-Harmonic-Generation Effect and Improved Overall Performance35Tin Chloride Sulfates A3Sn2(SO4)3–xCl1+2x (A = K, Rb, Cs; x = 0, 1) as Multifunctional Optical Materials33Be2(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 Response8[ 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 Incorporation50KCs2[Pb2Br5(HCOO)2]: A Polar 3D Lead‐Bromide Framework Exhibiting Strong Second‐Harmonic Generation Response10Linear 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 Stereoactivity552D van der Waals Layered [C(NH2)3]2SO3S Exhibits Desirable UV Nonlinear-Optical Trade-Off47Chemical substitution – oriented design of a new polar PbFIO3 achieving a balance between large second-harmonic generation response and wide band gap16Structural, Electronic, Mechanical, Linear and Nonlinear Optical, and Piezoelectric Properties of CsIO\(_3\) Materials from Ab Initio Study0From CeF2(SO4)·H2O to Ce(IO3)2(SO4): Defluorinated Homovalent Substitution for Strong Second-Harmonic-Generation Effect and Sufficient Birefringence53NaSb3O2(SO4)3·H2O: A New Alkali-Metal Antimony(III) Sulfate with a Unique Sb6O20H4 Unit and Moderate Birefringence19KCs2Pb2(HCOO)2Cl5: A Lead Formate with Strong Second-Harmonic-Generation Response Obtained by an Anionic Substitution3(C 3 N 6 H 7 ) 2 SiF 6 ·H 2 O: an ultraviolet birefringent crystal exceeding the intrinsic energy gap of an organic reagent38Ba 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 gaps28Unprecedented boat-shaped [Mo 2 O 5 (IO 3 ) 4 ] 2− polyanions induced a strong second harmonic generation response31High‐Performance Sulfate Optical Materials Exhibiting Giant Second Harmonic Generation and Large Birefringence21High‐Performance Sulfate Optical Materials Exhibiting Giant Second Harmonic Generation and Large Birefringence199Crystal Structure and Theoretical Analysis of Cs2Ca3(SO4)47Explorations of New SHG Materials in Mercury Iodate Sulfate System**9Advances in second-order nonlinear optical sulfates38CsY(SO4)2·4H2O: A Deep-Ultraviolet Birefringent Crystal Induced by an Edge-Sharing Connection26(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 Activity11Enhancements of Second Harmonic Generation and Birefringence in Traditional RbTiOPO4‐Type Crystals by Aliovalent Substitution of Ti Site1[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 topology20Constructing ultraviolet nonlinear optical crystals with large second harmonic generation and short absorption edges by using polar tetrahedral S 2 O 3 groups14Dramatically improved optical anisotropy by realizing stereochemically active lone pairs in a sulfate system, K 2 SO 4 ·HIO 323Na 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 birefringence8Solvent-free synthesis of magnesium phosphite-oxalates that show second-harmonic generation responses5β-(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 groups35C(NH2)3(I3O8)(HI3O8)(H2I2O6)(HIO3)4·3H2O: An Unprecedented Asymmetric Guanidinium Polyiodate with a Strong Second-Harmonic-Generation Response and a Wide Band Gap16K2(H2O)WO3F2: A new nonlinear optical material with remarkable second-harmonic generation response and enhanced laser damage threshold9CsHfF4(IO3): A Hafnium Iodate Exhibiting a Strong Second-Harmonic-Generation Effect and a Wide Band Gap Achieved by Mixed-Ligand Acentric Coordination8Host–Guest Symmetry Matching in Two Crystalline Magnesium Sulfate Oxalates Obtained Via a Solvent-Free Route8Host–Guest Symmetry and Charge Matching in Glycine-Templated Metal Sulfate–Oxalates Obtained by a Solvent-Free Method9Hg3(SeO3)2(SO4): A UV Nonlinear Optical Mercury Selenite Sulfate Constructed by Neat [Hg6O8(SeO3)4]∞ Layers and SO4 Tetrahedra27Halogen Bonding Assembles Anion⋅⋅⋅Anion Architectures in Non‐centrosymmetric Iodate and Bromate Crystals24α- and β-(C4H5N2O)(IO3)·HIO3: Two SHG Materials Based on Organic–Inorganic Hybrid Iodates14A survey of stereoactive oxysalts for linear and nonlinear optical applications40Giant Mid‐Infrared Second‐Harmonic Generation Response in a Densely‐Stacked Van Der Waals Transition‐Metal Oxychloride39Giant Mid‐Infrared Second‐Harmonic Generation Response in a Densely‐Stacked Van Der Waals Transition‐Metal Oxychloride8Ultrashort 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 Reduction3A chiral sodium lanthanum sulfate for second-order nonlinear optics and proton conduction6Three in one: a cadmium bismuth vanadate NLO crystal exhibiting a large second-harmonic generation response and enhanced birefringence12C(NH2)3MoO3(IO3): A Molybdenyl Iodate with Giant Birefringence Designed via a Cation–Anion Synergetic Interaction Strategy36Dual-Anion Strategy Induces Dual Enhancement Toward Ultrashort Phase-Matching Wavelength in Deep-UV Transparent d0 Transition Metal Oxyfluorides21Hg4(Te2O5)(SO4): A Giant Birefringent Sulfate Crystal Triggered by a Highly Selective Cation153Two Short-Wave UV Beryllium Selenites Exhibiting Diverse Optical Properties Stemming from Functional Group Arrangements8Second Harmonic Generation in β-K2TeW3O12: An Acentric Crystal Designed from Centric Phase via Pressure Modulation4Recent advances and future perspectives on rare-earth-based nonlinear optical materials with π-conjugated [XO3] (X = B, C, N) units66π-Lone pair synergy in (C7H4NO4)(IO3): Optimal balance among SHG, birefringence, and bandgap performance29(C10N2H10)(HI2O6)(HIO3)(IO3): A Birefringent Material Featuring Large π-Conjugated Organic Cation and Two Types of Iodate Anions2(C 7 H 3 NO 4 ) 2 Sb 2 F 2 ·2H 2 O: a pyridine-based compound shows large optical anisotropy4Different p-block elements induce C 3 [111] octahedral distortion in titanium to generate an intense nonlinear effect14Multifactorial Directed Regulation Of the [Io 3 ] − Units in Praseodymium-Contained Iodates0Cationic Modification in Hybrid Iodates: A Pathway to Superior Performance12Optimizing Acidic Oxygen Evolution Reaction via Modulation Doping in Van der Waals Layered Iridium Oxide10Optimizing Acidic Oxygen Evolution Reaction via Modulation Doping in Van der Waals Layered Iridium Oxide31Lithium Borate-Squarate: An Organic–Inorganic Groups-Mixed Nonlinear Optical Crystal with Large Birefringence4From AgHgI(SO4) to AgHg3I3.2Cl1.8(SO4): Symmetry Breaking of the Belousovite‐Type Topology by Mixed Halides to Achieve Strong Nonlinear Optical Effect14Thermal Evolution and Crystal Structure Features of Cs2SO4 and Cs2Ca3(SO4)4 Sulfates2Halide Ion-Directed Symmetry Control in π-Conjugated Molecular Crystals6A balance in SHG response, band gap and birefringence in a series of rare-earth sulfate-iodate6Multifactorial directed regulation of anionic units in praseodymium-contained iodates1Ag(Te2O3)(PO4): The first Ag-containing phosphate-tellurite nonlinear optical crystal featuring novel zigzag layered structure0Sulfonated Module Aggregation for Ultrahigh Birefringence in Aqueous-Processable Crystals26Ce-centered polyhedral arrangement pattern and optical performance in Ce-based nonlinear optical materials3Recent achievements of d0 transition-metal-based oxyfluorides: Crystal chemistry and application in second-order NLO materials10A dobrovolskyite-type Na4Ca(SO4)3 sulfate: structural phase transition, thermal expansion and ionic conductivity0Double second-order Jahn–Teller strategy driven NLO response in sulfate crystal Nb 2 O 2 (TeO 3 ) 2 (SO 4 ) with a large birefringence1Tailoring linear and nonlinear optical properties of 2D Sc 2 C MXenes via surface termination modulation0RbLa(SO 4 ) 2 : A KBBF-like Deep-UV Transparent Rare Earth Sulfate with Strong SHG Response and High Thermal Stability Enabled by Multicomponent Structural Design2An UV Transparent Metal‐Free Sulfate With Giant Birefringence Enabled by Optimal Structural Anisotropy4A Polar Cerium Iodate Ce 2 (IO 3 ) 6 (H 2 O) with a Strong Second-Harmonic Generation Response in Trivalent Ce-Based Materials1Cation‐Dominated Second‐Order Nonlinear Optical Response Enabled by π‐Conjugated Guanidinium Derivatives5Cation-sulfur-driven dimensional reduction engineering for tailoring sulfonate birefringent crystals with enhanced anisotropy2Non-π-conjugated tetrahedra-based optical crystals: The improvement of the linear and nonlinear optical properties by the combination of trigonal pyramidal [XO3] (X = I, Se, Te) units1Two Rare Earth-Based Sulfates with Enhanced Birefringence and Broad Optical Transparency Window0

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  1. Cs 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 activity

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  2. LiMg(IO 3 ) 3 : an excellent SHG material designed by single-site aliovalent substitution

    Chemical Science · 2019-01-01

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  3. Tb(HSO 4 )(SO 4 ) – a green emitting hydrogensulfate sulfate with second harmonic generation response

    Dalton Transactions · 2019-01-01

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  4. REI5O14 (RE=Y and Gd): Promising SHG Materials Featuring the Semicircle‐Shaped I5O143− Polyiodate Anion

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  5. REI5O14 (RE=Y and Gd): Promising SHG Materials Featuring the Semicircle‐Shaped I5O143− Polyiodate Anion

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  6. Two Indium Sulfate Tellurites: Centrosymmetric In 2 (SO 4 )(TeO 3 )(OH) 2 (H 2 O) and Non-centrosymmetric In 3 (SO 4 )(TeO 3 ) 2 F 3 (H 2 O)

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  7. In Honor of Professor Xintao Wu on the Occasion of His Eightieth Birthday

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  8. Nontoxic KBBF Family Member Zn2BO3(OH): Balance between Beneficial Layered Structure and Layer Tendency

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

    Angewandte Chemie International Edition · 2019-09-20

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

    Angewandte Chemie · 2019-09-20

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  11. A x Ce 9 (IO 3 ) 36 (A = K, La): the effects of a change in the intermediate valence on the second-harmonic generation response

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  12. Second harmonic generation responses of KH 2 PO 4 : importance of K and breaking down of Kleinman symmetry

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  14. Key Factors Controlling the Large Second Harmonic Generation in Nonlinear Optical Materials

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  15. K2Na(IO3)2(I3O8) with Strong Second Harmonic Generation Response Activated by Two Types of Isolated Iodate Anions

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  16. Dimensionality–Band Gap–Third-Harmonic Generation Property Relationship in Novel Main-Group Metal Iodates

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  17. A review on phase transition and structure-performance relationship of second-order nonlinear optical polymorphs

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

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

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  20. From S–O–S to B–O–S to B–O–B Bridges: Ba[B(S2O7)2]2 as a Model System for the Structural Diversity in Borosulfate Chemistry

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  21. Cs 3 Pb 2 (CH 3 COO) 2 X 5 (X=I, Br): Halides with Strong Second‐Harmonic Generation Response Induced by Acetate Groups

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  22. Cs3Pb2(CH3COO)2X5 (X=I, Br): Halides with Strong Second‐Harmonic Generation Response Induced by Acetate Groups

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  24. Sb6O7(SO4)2: A Promising Ultraviolet Nonlinear Optical Material with an Enhanced Second‐Harmonic‐Generation Response Activated by SbIII Lone‐Pair Stereoactivity

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  26. 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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  28. Two bismuth iodate sulfates with enhanced optical anisotropy

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  31. Titanium Iodates with a Second-Harmonic-Generation Response

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

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  34. Be2(BO3)(IO3): The First Anion‐mixed Van der Waals Member in the KBe2BO3F2 Family with a Very Strong Second Harmonic Generation Response

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  35. Be2(BO3)(IO3): The First Anion‐mixed Van der Waals Member in the KBe2BO3F2 Family with a Very Strong Second Harmonic Generation Response

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  36. [ 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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  37. [o‐C5H4NHOH]2[I7O18(OH)]⋅3 H2O: An Organic–Inorganic Hybrid SHG Material Featuring an [I7O18(OH)] Branched Polyiodate Chain

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  38. A2MoO2F3(IO2F2) (A = Rb, Cs): Strong Nonlinear Optical Responses and Enlarged Band Gaps through Fluorine Incorporation

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

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  39. KCs2[Pb2Br5(HCOO)2]: A Polar 3D Lead‐Bromide Framework Exhibiting Strong Second‐Harmonic Generation Response

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  40. Linear 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 Stereoactivity

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    Qi Wei, Kui Wang, Chao He, Li Wei, Xiaofei Li, Shuo Zhang, Xing‐Tao An, Jinhua Li, Guo‐Ming Wang

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  41. 2D van der Waals Layered [C(NH2)3]2SO3S Exhibits Desirable UV Nonlinear-Optical Trade-Off

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  42. Chemical substitution – oriented design of a new polar PbFIO3 achieving a balance between large second-harmonic generation response and wide band gap

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  46. KCs2Pb2(HCOO)2Cl5: A Lead Formate with Strong Second-Harmonic-Generation Response Obtained by an Anionic Substitution

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