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RESEARCH PAPER · Inorganic Chemistry · 2022

PbBi(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 Properties

Ying‐Jie Jia, Xingyu Zhang, Xingyu Zhang, Yi-Gang Chen, Xingxing Jiang, Jia-Neng Song, Zheshuai Lin, Xian‐Ming Zhang, Xian‐Ming Zhang

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PbBi(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 PropertiesOriginalAn effective pathway to design and synthesize UV birefringent crystals via rational assembly of π-conjugated [CO 3 ] 2− and [NO 3 ] − triangles32From AgTeO 2 F and Ag 2 (TeO 2 F 2 ) to Ag 3 F 3 (TeF 6 )(TeO 2 ) 12 : the first silver tellurite oxyfluorides with linear and nonlinear optical properties26From CdPb 8 (SeO 3 ) 4 Br 10 to Pb 3 (TeO 3 )Br 4 : the first tellurite bromide exhibiting an SHG response and mid-IR transparency21Mg 2 Pb 2 Si 2 O 7 F 2 : a new lead-containing alkali earth metal silicate fluoride with a short cutoff edge2Solvent-free synthesis of magnesium phosphite-oxalates that show second-harmonic generation responses5Structure and optical property evolution in PbM(PO 4 )X (M = Zn, Sn; X = halogen): SHG effect and birefringence21Growth and Optical Properties of Large-Sized NaVO2(IO3)2(H2O) Crystals for Second-Harmonic Generation Applications12Polar Bismuth Selenite Iodate Oxide BiSeIO6 with Three Types of Lone Pair Cations in One Structure6The First UV Nonlinear Optical Selenite Material: Fluorination Control in CaYF(SeO 3 ) 2 and Y 3 F(SeO 3 ) 485The First UV Nonlinear Optical Selenite Material: Fluorination Control in CaYF(SeO3)2 and Y3F(SeO3)47A survey of stereoactive oxysalts for linear and nonlinear optical applications40Four UV Transparent Linear and Nonlinear Optical Materials Explored from Pure Selenite Compounds22KBi(SeO4)(IO3)Cl: A mixed-anion oxychloride with three types of building units in one structure2Synthesis and structure-dependent optical properties of two new organic–inorganic hybrid antimony( iii ) chlorides19A UV non-hydrogen pure selenite nonlinear optical material for achieving balanced properties through framework-optimized structural transformation41Computer-aided screening of bismuth molybdates nonlinear optical crystals γ -Bi 2 MoO 63Discovery of excellent ultraviolet nonlinear optical materials in chlorates and bromates with highly stereochemically active lone pairs12Hydrogen bonding bolstered head-to-tail ligation of functional chromophores in a 0D SbF 3 ·glycine adduct for a short-wave ultraviolet nonlinear optical material32Hydrothermally synthesized first acentric apatite (Bi 5 Na 5 )[PO 4 ] 6 Cl 2 with wide Bi–Na isomorphism and doubled c -axis3Pb 2 (SeO 3 )(SiF 6 ): the first selenite fluorosilicate with a wide bandgap and large birefringence achieved through perfluorinated group modification45Exceptional Optical Anisotropy Enhancement Achieved Through Dual‐Ions Cosubstitution Strategy in Novel Hybrid Bismuth Halides23AX·(H2SeO3)n (A = K, Cs; X = Cl, Br; n = 1, 2): A Series of Ionic Cocrystals as Promising UV Birefringent Materials with Large Birefringence and Wide Band Gap20Hg3Se(SeO3)(SO4): A Mixed-Valent Selenium Compound with Mid-Infrared Transmittance Obtained by In Situ Reaction26UV-Transparent SHG Material Explored in an Alkali Metal Sulfate Selenite System16A congruent-melting rubidium zinc vanadium oxychloride exhibiting strong mid-infrared second-harmonic generation and high laser-induced damage threshold6Two Short-Wave UV Beryllium Selenites Exhibiting Diverse Optical Properties Stemming from Functional Group Arrangements8Old tree blossoms anew: Research progress on the structures and optical properties of ultraviolet selenites56Recent advances and future perspectives on rare-earth-based nonlinear optical materials with π-conjugated [XO3] (X = B, C, N) units66Analogous Chain Selenite Chlorides Ba 2 M(SeO 3 ) 2 Cl 2 (M = Cu 2+ , Ni 2+ , Co 2+ , Mn 2+ ) and Pb 2 Cu(SeO 3 ) 2 Cl 2 with Tunable Spin S : Syntheses and Characterizations7Polar Layered Magnet Ba 2 Cu 3 (SeO 3 ) 4 F 2 Composed of Bitriangular Chains: Observation of 1/3-Magnetization Plateau5RE(HSeO3)(SeO3)(H2O)·(H2O) (RE = Y, Gd): Two Rare-Earth Selenite Nonlinear Optical Crystals with Wide Band Gaps6Chiral-driven formation of hybrid cyanurates with large birefringence2Birefringence Disparity Induced by Synergistic Effects of Stereochemically Active Lone Pairs193Pb 8 O 7 I 2 ·2CsI: the salt-inclusion strategy enriches the structural chemistry in lead oxyhalides1Design and Synthesis of Vanadium-Based Infrared Nlo Crystal K4cdv5o15br Through Aliovalent Substitution with Strongly Polarized Active Units0Hg 2 (SeO 3 )(TeO 3 ): a novel tellurite–selenite birefringent crystal achieved by assembling multiple functional groups11A Wide Band Gap Germanate with the Largest Second Harmonic Generation Response Created by Hypoxic Strategy22A Wide Band Gap Germanate with the Largest Second Harmonic Generation Response Created by Hypoxic Strategy5LiAgCe2F10(H2O)2: Focusing on the Cation Size Effect to Reasonably Design a Nonlinear Optical Hydrated Cerium(IV) Fluoride10Cs2CdV2O6Br2: A Mid-Infrared Nonlinear Optical Vanadate Containing Both d0/d10 Transition Metal Cations and Bromine Anions5A3ZnNO3X4 (A = Rb, NH4, X = Cl, I): Regulating Cations and Halides Yields Birefringent Crystals with Significantly Enhanced Optical Anisotropy5Recent Progress in the Design and Synthesis of Nonlinear Optical Crystals with Stereochemically Active Lone Pairs8Tuning birefringence in alkaline-earth metal oxyhalides through diverse mixed-cation coordination architectures1ZnGa(SeO 3 ) 2 F: a UV transparent birefringent crystal explored in M( ii )–IIIA–selenite–F systems2LiV 3 Se 2 O 12 : A Promising Giant‐Birefringent Crystal Enabled by Significant Structural Distortion3A universal synthetic strategy for noncentrosymmetric lead oxyhalide frameworks with strong second-harmonic generation0Te–Se replacement induced structural transition and enhanced band gaps in Cd 5 Se 4 O 12 Cl 2 and Cd 5 Se 4 O 12 Br 21InO6X (X = Cl, Br): distinct functional motif family for nonlinear optical materials5Strategic Integration Between Trigonal Architecture Construction and Molecular Polarization Enhancement for Record SHG Effect in Selenates4Strategic Integration Between Trigonal Architecture Construction and Molecular Polarization Enhancement for Record SHG Effect in Selenates0V-Shaped Pseudo-Chains Coupled with Lone-Pair-Distorted [GeX 3 ] − Units Enable Large Birefringence in Ge(II) Hybrid Halides2Magnetic Copper Selenite-Sulfate Cu 3 O 2 (HSeO 3 )(HSO 4 )(H 2 O) with T26-Type Non-Archimedean Lattice Featuring a Robust 1/3-Magnetization Plateau2Breaking Inversion Symmetry via Vanadium Coordination Engineering in Bismuth Vanadium Selenites0The novel Zn-based ultraviolet birefringent crystals combined both large birefringence and wide bandgap2Structures of hexakis(antipyrine)lead(II) complexes: the first example of the stereochemically active and inactive 6 s 2 lone pair for one lead(II) complex0Advances in metal selenite nonlinear optical materials: halogens directed structure modulation and property optimization0

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  2. From AgTeO 2 F and Ag 2 (TeO 2 F 2 ) to Ag 3 F 3 (TeF 6 )(TeO 2 ) 12 : the first silver tellurite oxyfluorides with linear and nonlinear optical properties

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  3. From CdPb 8 (SeO 3 ) 4 Br 10 to Pb 3 (TeO 3 )Br 4 : the first tellurite bromide exhibiting an SHG response and mid-IR transparency

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  4. Mg 2 Pb 2 Si 2 O 7 F 2 : a new lead-containing alkali earth metal silicate fluoride with a short cutoff edge

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  5. Solvent-free synthesis of magnesium phosphite-oxalates that show second-harmonic generation responses

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  6. Structure and optical property evolution in PbM(PO 4 )X (M = Zn, Sn; X = halogen): SHG effect and birefringence

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  7. Growth and Optical Properties of Large-Sized NaVO2(IO3)2(H2O) Crystals for Second-Harmonic Generation Applications

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    Xiang Xu, Bingxuan Li, Lingxiong Huang, Bing‐Ping Yang, Ge Zhang, Jiang‐Gao Mao

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  8. Polar Bismuth Selenite Iodate Oxide BiSeIO6 with Three Types of Lone Pair Cations in One Structure

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  9. The First UV Nonlinear Optical Selenite Material: Fluorination Control in CaYF(SeO 3 ) 2 and Y 3 F(SeO 3 ) 4

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  10. The First UV Nonlinear Optical Selenite Material: Fluorination Control in CaYF(SeO3)2 and Y3F(SeO3)4

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  11. A survey of stereoactive oxysalts for linear and nonlinear optical applications

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  12. Four UV Transparent Linear and Nonlinear Optical Materials Explored from Pure Selenite Compounds

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  13. KBi(SeO4)(IO3)Cl: A mixed-anion oxychloride with three types of building units in one structure

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  14. Synthesis and structure-dependent optical properties of two new organic–inorganic hybrid antimony( iii ) chlorides

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  15. A UV non-hydrogen pure selenite nonlinear optical material for achieving balanced properties through framework-optimized structural transformation

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  16. Computer-aided screening of bismuth molybdates nonlinear optical crystals γ -Bi 2 MoO 6

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  17. Discovery of excellent ultraviolet nonlinear optical materials in chlorates and bromates with highly stereochemically active lone pairs

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  18. Hydrogen bonding bolstered head-to-tail ligation of functional chromophores in a 0D SbF 3 ·glycine adduct for a short-wave ultraviolet nonlinear optical material

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  19. Hydrothermally synthesized first acentric apatite (Bi 5 Na 5 )[PO 4 ] 6 Cl 2 with wide Bi–Na isomorphism and doubled c -axis

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  20. Pb 2 (SeO 3 )(SiF 6 ): the first selenite fluorosilicate with a wide bandgap and large birefringence achieved through perfluorinated group modification

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  21. Exceptional Optical Anisotropy Enhancement Achieved Through Dual‐Ions Cosubstitution Strategy in Novel Hybrid Bismuth Halides

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  22. AX·(H2SeO3)n (A = K, Cs; X = Cl, Br; n = 1, 2): A Series of Ionic Cocrystals as Promising UV Birefringent Materials with Large Birefringence and Wide Band Gap

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  23. Hg3Se(SeO3)(SO4): A Mixed-Valent Selenium Compound with Mid-Infrared Transmittance Obtained by In Situ Reaction

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  24. UV-Transparent SHG Material Explored in an Alkali Metal Sulfate Selenite System

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  25. A congruent-melting rubidium zinc vanadium oxychloride exhibiting strong mid-infrared second-harmonic generation and high laser-induced damage threshold

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  29. Analogous Chain Selenite Chlorides Ba 2 M(SeO 3 ) 2 Cl 2 (M = Cu 2+ , Ni 2+ , Co 2+ , Mn 2+ ) and Pb 2 Cu(SeO 3 ) 2 Cl 2 with Tunable Spin S : Syntheses and Characterizations

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  30. Polar Layered Magnet Ba 2 Cu 3 (SeO 3 ) 4 F 2 Composed of Bitriangular Chains: Observation of 1/3-Magnetization Plateau

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  31. RE(HSeO3)(SeO3)(H2O)·(H2O) (RE = Y, Gd): Two Rare-Earth Selenite Nonlinear Optical Crystals with Wide Band Gaps

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  33. Birefringence Disparity Induced by Synergistic Effects of Stereochemically Active Lone Pairs

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  34. 3Pb 8 O 7 I 2 ·2CsI: the salt-inclusion strategy enriches the structural chemistry in lead oxyhalides

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  45. LiV 3 Se 2 O 12 : A Promising Giant‐Birefringent Crystal Enabled by Significant Structural Distortion

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  46. A universal synthetic strategy for noncentrosymmetric lead oxyhalide frameworks with strong second-harmonic generation

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  47. Te–Se replacement induced structural transition and enhanced band gaps in Cd 5 Se 4 O 12 Cl 2 and Cd 5 Se 4 O 12 Br 2

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  49. Strategic Integration Between Trigonal Architecture Construction and Molecular Polarization Enhancement for Record SHG Effect in Selenates

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