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RESEARCH PAPER · Angewandte Chemie International Edition · 2018

A Facile Route to Nonlinear Optical Materials: Three‐Site Aliovalent Substitution Involving One Cation and Two Anions

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A Facile Route to Nonlinear Optical Materials: Three‐Site Aliovalent Substitution Involving One Cation and Two AnionsOriginal“Two in one”: an unprecedented mixed anion, Ba 2 (C 3 N 3 O 3 )(CNO), with the coexistence of isolated sp and sp 2 π-conjugated groups15(H 3 O)HCs 2 Nb(IO 3 ) 9 and SrNbO(IO 3 ) 5 : a facile synthetic method using hydrofluoric acid as a solubilizer19A rich structural chemistry in π-conjugated hydroisocyanurates: layered structures of A 2 B(H 2 C 3 N 3 O 3 ) 4 · n H 2 O (A = K, Rb, Cs; B = Mg, Ca; n = 4, 10) with high ultraviolet transparency and strong optical anisotropy47LiMg(IO 3 ) 3 : an excellent SHG material designed by single-site aliovalent substitution68RE(H 2 C 3 N 3 O 3 ) 2 ·(OH)· x H 2 O (RE = La, Y and Gd): potential UV birefringent materials with strong optical anisotropy originating from the (H 2 C 3 N 3 O 3 ) − group31HBa2.5(IO3)6(I2O5) and HBa(IO3)(I4O11): Explorations of Second-Order Nonlinear Optical Materials in the Alkali-Earth Polyiodate System49Cs3Na(H2C3N3O3)4·3H2O: A Mixed Alkali‐Metal Hydroisocyanurate Nonlinear Optical Material Containing π‐Conjugated Six‐Membered‐Ring Units68REI5O14 (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 Characterization11Ba2M(C3N3O3)2 (M = Sr, Pb): Band Engineering from p−π Interaction via Homovalent Substitution in Metal Cyanurates Containing Planar π-Conjugated Groups39Research and Development of Zincoborates: Crystal Growth, Structural Chemistry and Physicochemical Properties20Five New Silver Rare‐Earth Iodates, AgLn(IO3)4 (Ln=Pr, Sm, Dy, Er and Tm): Synthesis, Structures and Properties6Nontoxic KBBF Family Member Zn2BO3(OH): Balance between Beneficial Layered Structure and Layer Tendency81A x Ce 9 (IO 3 ) 36 (A = K, La): the effects of a change in the intermediate valence on the second-harmonic generation response7A new iodate-phosphate Pb 2 (IO 3 )(PO 4 ) achieving great improvement in birefringence activated by (IO 3 ) − groups53K5(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 Behavior11Emergent Deep‐Ultraviolet Nonlinear Optical Candidates324Neue Kandidaten für die nichtlineare Optik im Tief‐UV‐Bereich43“Old dog, new tricks”: the lone pair effect inducing divergent optical responses in lead cyanurates containing π-bonds18Alkali-earth metal lead( ii ) oxyhalide Ba 27 Pb 8 O 8 Cl 54 exhibiting interesting [Pb 4 Ba 4 O 4 ] 8+ species8Ba(B 2 OF 3 (OH) 2 ) 2 with well-ordered OH/F anions and a unique B 2 OF 3 (OH) 2 dimer30New polymorphism for BaTi(IO 3 ) 6 with two polymorphs crystallizing in the same space group11Novel ultraviolet (UV) nonlinear optical (NLO) materials discovered by chemical substitution-oriented design302Designing Sulfide Borate as a Novel Type of Second-Order Nonlinear-Optical Material912D organic‐inorganic hybrid perovskite materials for nonlinear optics131CsVO2F(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 Framework22MII2M3IIIF3(Te6F2O16) (MII = Pb, Ba; MIII = Al, Ga): New mixed anionic tellurites with isolated Te6 coplanar rings23ZnIO3F: Zinc Iodate Fluoride with Large Birefringence and Wide Band Gap57Dimensionality–Band Gap–Third-Harmonic Generation Property Relationship in Novel Main-Group Metal Iodates37Aliovalent-substituted synthesis for a non-centrosymmetric phosphate with enhanced nonlinear-optical response5A review on phase transition and structure-performance relationship of second-order nonlinear optical polymorphs107New Alkaline-Earth Metal Fluoroiodates Exhibiting Large Birefringence and Short Ultraviolet Cutoff Edge with Highly Polarizable (IO 3 F) 2– Units63LiGaF2(IO3)2: A mixed-metal gallium iodate-fluoride with large birefringence and wide band gap39Ba2[MoO3(OH)(IO3)2]IO3: A Promising SHG Material Featuring a Λ-Shaped Functional Motif Achieved by Universal Mono-Site Substitution50Finding Optimal Mid-Infrared Nonlinear Optical Materials in Germanates by First-Principles High-Throughput Screening and Experimental Verification79From 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 Generation34Recent 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 substitution42AgBi(SO 4 )(IO 3 ) 2 : aliovalent substitution induces structure dimensional upgrade and second harmonic generation enhancement37Ba 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 birefringence22In situ hydrothermal synthesis of polar second-order nonlinear optical selenate Na 5 (SeO 4 )(HSeO 4 ) 3 (H 2 O) 219NaGaI 3 O 9 F: a new alkali metal gallium iodate combined with IO 3 − and IO 3 F 2− units16Rb3In(SO4)3: a defluorinated mixed main-group metal sulfate for ultraviolet transparent nonlinear optical materials with a large optical band gap26A 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 Performance35CsZrF4(IO3): The First Polar Zirconium Iodate with cis-[ZrO2F6] Polyhedra Inducing Optimized Balance of Large Band Gap and Second Harmonic Generation47Unique Unilateral-Chelated Mode-Induced d–p−π Interaction Enhances Second-Harmonic Generation Response in New Ln3LiMS7 Family41High-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 Chain21From K[ZnBP2O8] to K[(Zn0.5Al0.5)2P2O8]: Substitution-Induced Microporous Zincoaluminophosphate with a Congruent-Melting Behavior5A2MoO2F3(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]10An 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 Substitution10AMoO3(IO3) (A = Na and K): Two promising optical materials via properly assembling the Λ-shaped basic building units19Noncentrosymmetric Ba6In2Q10 (Q = S, Se): Structural Chemistry and Nonlinear-Optical Activity11A new I 3 O 9 3− group constructed from IO 3 − and IO 5 5− anion units in Cs 3 [Ga 2 O(I 3 O 9 )(IO 3 ) 4 (HIO 3 )]4Complex 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+ cations33Anion-Tuned Synthesis of Ag Coordination Compounds: Approaches for Optimizing Second-Harmonic-Generation (SHG) Response5Pressure‐Driven Two‐Step Second‐Harmonic‐Generation Switching in BiOIO34Pressure‐Driven Two‐Step Second‐Harmonic‐Generation Switching in BiOIO344Ba 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 anions16Band gap modulation and nonlinear optical properties of quaternary tellurates Li 2 GeTeO 613Cd 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 gaps28Cd 4 REO(BO 3 ) 3 (RE = Sm, Eu, Tb): three new cadmium–rare earth oxyborates with both good NLO and luminescence properties6Cs 2 VOF 4 (IO 2 F 2 ): Rationally designing a noncentrosymmetric early-transition-metal fluoroiodate24Mg(H 2 O) 6 [(IO 2 (OH)) 2 (IO 3 )] 2 : a new iodate with a very large band gap and optical anisotropy13Wide 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 response19Explorations of New SHG Materials in Mercury Iodate Sulfate System**9Yin–Yang Complementarity Strategy Achieving Giant Optical Anisotropy in a Metal-free Birefringent Material C(NH2)3(HC4O4)14Enhancements of Second Harmonic Generation and Birefringence in Traditional RbTiOPO4‐Type Crystals by Aliovalent Substitution of Ti Site1MIO 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 Bandgaps22Ag-based chalcogenides and derivatives as promising infrared nonlinear optical materials90Cd(NH 2 SO 3 ) 2 · x H 2 O ( x = 0, 2): new sulfamates with a unique coordination environment and reversible phase transitions20[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 topology20AIO3·H6TeO6 (A = NH4+, Rb+): Two telluric acid and iodate Co-crystalline compounds with second harmonic generation response4Ce 3 F 4 (SO 4 ) 4 : cationic framework assembly for designing polar nonlinear optical material through fluorination degree modulation23From H 12 C 4 N 2 CdI 4 to H 11 C 4 N 2 CdI 3 : a highly polarizable CdNI 3 tetrahedron induced a sharp enhancement of second harmonic generation response and birefringence50Ga(IO 3 ) 3 : a mid-IR nonlinear optical iodate with balanced performance between band gap and second harmonic generation response4Low temperature molten salt synthesis of noncentrosymmetric (NH 4 ) 3 SbF 3 (NO 3 ) 3 and centrosymmetric (NH 4 ) 3 SbF 4 (NO 3 ) 234Recent advances in F-containing iodate nonlinear optical materials6Searching for silicate nonlinear optical materials by combining calculation and experiment17Ultralow thermal conductivity in the mixed-anion solid solution Sn 2 SbS 2− x Se x I 319Wide‐Bandgap Rare‐Earth Iodate Single Crystals for Superior X‐Ray Detection and Imaging21ε-La(IO3)3: A Polar Iodate with High Thermal Stability and a Large Second-Harmonic-Generation Response Obtained by a Supercritical Hydrothermal Method8Designing 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 selenites70A selenite containing unusual [Ga2F(Se2O5)4(HSeO3)2]5- clusters with the polarization ‘lighted’ by F− anions15Halide-Induced Band Gap Enhancement from Ba2SnSe4 to KBa2SnSe4Cl2Centrosymmetric Rb2Sb(C2O4)2.5(H2O)3 and Noncentrosymmetric RbSb2(C2O4)F5: Two Antimony (III) Oxalates as UV Optical Materials20α- and β-(C4H5N2O)(IO3)·HIO3: Two SHG Materials Based on Organic–Inorganic Hybrid Iodates14A survey of stereoactive oxysalts for linear and nonlinear optical applications40Cs2Pb4Br10: A layered perovskite shows large birefringence11LiGa(IO3)4: An Excellent NLO Material with Unprecedented 2D [Ga(IO3)4]∞− Layer Synthesized by Aliovalent Substitution20Sr(NO 3 )(NH 2 SO 3 )·H 2 O: First Nitrate Sulfamate Revealing Remarkable Second Harmonic Generation and Optimized Birefringence25Optically Anisotropic Mixed-Metal Fluoroiodate Ba2[GaF5(IO3F)] with a Wide Optical Transparent Window and a Moderate Birefringence6NaMoO 3 (IO 3 )(H 2 O): water molecule introduction induces strong second harmonic generation response, widened band gap and large anisotropy8Achieving strong second harmonic generation effects induced via dimensional increase of PbX 6 octahedra and halogen substitutes in (C 10 H 11 N 3 )PbX 4 (X = Cl or Br)26Ba 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 chain2From 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 Iodates13Halide-driven polarity tuning and optimized SHG-bandgap balance in (C 4 H 11 N 2 )ZnX 3 (X = Cl, Br, I)34Noncentrosymmetric 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 stability2From ZnF2 to ZnF2(H2O)4: Partial Substitution Achieves Structural Transformation and Nonlinear Optical Activity while Keeping Short Ultraviolet Cutoff Edge19Anhydrous Aluminum Iodate: Strong Second Harmonic Generation Effect Contributed by Unbonded and Antibonding Orbitals3KSb2F7·2KNO3: Unveiling the peak birefringence in inorganic antimony oxysalts10Diversity 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)60π-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 Anions2Rational Design of Novel Polar Nonlinear Optical Materials in Alkali Metal Rare Earth Iodates5SbO(OH)2(IO3): The First Polar Sb5+‐Iodate with a Strong Second‐Harmonic Generation Response and a Wide Bandgap8From Ba2Bi2Zn(PO4)4 to Ba2Bi2Cu(PO4)4: Rational design of an ultraviolet phosphate with enhanced birefringence2Achieving balanced UV SHG responses, optical band gaps and birefringence in rare earth compounds Ln(IO 3 )(SO 4 )·3H 2 O (Ln = Y, Gd, Er, Ho, Dy, Eu)4CdF(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”11K5NaZr4F22(H2O)2: A Hydrated Zirconium Fluoride with a Second-Harmonic Generation Effect and a Short Ultraviolet Cutoff Edge Induced by Cosubstitution with Heterovalent Cations6Hydrothermal preparation, structures and properties of SrVO(IO3)5: a new alkaline-earth metal oxidovanadium iodate0[Pb(ptz)(OH)(H2O)]: A Hybrid Nonlinear Optical Crystal with Large Birefringence0Ag(Te2O3)(PO4): The first Ag-containing phosphate-tellurite nonlinear optical crystal featuring novel zigzag layered structure0Enhancing birefringence and second-harmonic generation response via aliovalent metal substitution2Ba2CrIO3F6: a magnetic alkaline-earth chromium fluoroiodate with ferromagnetic exchange interactions1Halogen-ion-driven polymorphs for high-performance nonlinear optical crystalline materials3From [C(NH2)3]2[Sn2(C2O4)3]·2H2O to [C(NH2)3]4[Sn(C2O4)2]2·H2O: Uneven-substitution-activated polar stannous oxalate with balanced bandgap and birefringence0LiMn(IO 3 ) 3 : A Noncentrosymmetric Iodate Synthesized by Polyhedral Volume Ratio Modulation0Unlocking Nonlinear Optics and Photoluminescence with Simultaneous Enhancement of Bandgap and Birefringence in Hybrid Sb-Based Halides2

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  1. “Two in one”: an unprecedented mixed anion, Ba 2 (C 3 N 3 O 3 )(CNO), with the coexistence of isolated sp and sp 2 π-conjugated groups

    Dalton Transactions · 2019-01-01

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  2. (H 3 O)HCs 2 Nb(IO 3 ) 9 and SrNbO(IO 3 ) 5 : a facile synthetic method using hydrofluoric acid as a solubilizer

    Chemical Communications · 2019-01-01

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  3. A rich structural chemistry in π-conjugated hydroisocyanurates: layered structures of A 2 B(H 2 C 3 N 3 O 3 ) 4 · n H 2 O (A = K, Rb, Cs; B = Mg, Ca; n = 4, 10) with high ultraviolet transparency and strong optical anisotropy

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

    Chemical Science · 2019-01-01

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  5. RE(H 2 C 3 N 3 O 3 ) 2 ·(OH)· x H 2 O (RE = La, Y and Gd): potential UV birefringent materials with strong optical anisotropy originating from the (H 2 C 3 N 3 O 3 ) − group

    Dalton Transactions · 2019-01-01

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  6. HBa2.5(IO3)6(I2O5) and HBa(IO3)(I4O11): Explorations of Second-Order Nonlinear Optical Materials in the Alkali-Earth Polyiodate System

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  7. Cs3Na(H2C3N3O3)4·3H2O: A Mixed Alkali‐Metal Hydroisocyanurate Nonlinear Optical Material Containing π‐Conjugated Six‐Membered‐Ring Units

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

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

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  10. Mixed Transition Metal (Oxy)fluoride Paramagnet Chains: Synthesis, Structure, and Characterization

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  11. Ba2M(C3N3O3)2 (M = Sr, Pb): Band Engineering from p−π Interaction via Homovalent Substitution in Metal Cyanurates Containing Planar π-Conjugated Groups

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  13. Five New Silver Rare‐Earth Iodates, AgLn(IO3)4 (Ln=Pr, Sm, Dy, Er and Tm): Synthesis, Structures and Properties

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

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  15. 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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  16. A new iodate-phosphate Pb 2 (IO 3 )(PO 4 ) achieving great improvement in birefringence activated by (IO 3 ) − groups

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

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  18. (NH4)Bi2(IO3)2F5: An Unusual Ammonium‐Containing Metal Iodate Fluoride Showing Strong Second Harmonic Generation Response and Thermochromic Behavior

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  19. (NH4)Bi2(IO3)2F5: An Unusual Ammonium‐Containing Metal Iodate Fluoride Showing Strong Second Harmonic Generation Response and Thermochromic Behavior

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  20. Emergent Deep‐Ultraviolet Nonlinear Optical Candidates

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  21. Neue Kandidaten für die nichtlineare Optik im Tief‐UV‐Bereich

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  22. “Old dog, new tricks”: the lone pair effect inducing divergent optical responses in lead cyanurates containing π-bonds

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  23. Alkali-earth metal lead( ii ) oxyhalide Ba 27 Pb 8 O 8 Cl 54 exhibiting interesting [Pb 4 Ba 4 O 4 ] 8+ species

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  24. Ba(B 2 OF 3 (OH) 2 ) 2 with well-ordered OH/F anions and a unique B 2 OF 3 (OH) 2 dimer

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  26. Novel ultraviolet (UV) nonlinear optical (NLO) materials discovered by chemical substitution-oriented design

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  27. Designing Sulfide Borate as a Novel Type of Second-Order Nonlinear-Optical Material

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  28. 2D organic‐inorganic hybrid perovskite materials for nonlinear optics

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  29. CsVO2F(IO3): An Excellent SHG Material Featuring an Unprecedented 3D [VO2F(IO3)]− Anionic Framework

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  30. CsVO2F(IO3): An Excellent SHG Material Featuring an Unprecedented 3D [VO2F(IO3)]− Anionic Framework

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  31. MII2M3IIIF3(Te6F2O16) (MII = Pb, Ba; MIII = Al, Ga): New mixed anionic tellurites with isolated Te6 coplanar rings

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  32. ZnIO3F: Zinc Iodate Fluoride with Large Birefringence and Wide Band Gap

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

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  34. Aliovalent-substituted synthesis for a non-centrosymmetric phosphate with enhanced nonlinear-optical response

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    Yaoguo Shen, Zhiqun Liu, Hualiang Yu, Bi‐Cheng Zhou

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