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RESEARCH PAPER · Chemical Communications · 2018

The first lead fluorooxoborate PbB 5 O 8 F: achieving the coexistence of large birefringence and deep-ultraviolet cut-off edge

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The first lead fluorooxoborate PbB 5 O 8 F: achieving the coexistence of large birefringence and deep-ultraviolet cut-off edgeOriginalNaBaM III Q 3 (M III = Al, Ga; Q = S, Se): first quaternary chalcogenides with isolated edge-sharing (MIII2Q 6 ) 6− dimers8Fluorooxoborates: Ushering in a New Era of Deep Ultraviolet Nonlinear Optical Materials102Thermal properties of 2:1 bismuth borate: Temperature‐dependent characterizations of lone electron pairs4Li 4 Na 2 CsB 7 O 14 : a new edge-sharing [BO 4 ] 5− tetrahedra containing borate with high anisotropic thermal expansion52A new barium fluorooxoborate BaB 5 O 8 F· x H 2 O with large birefringence and a wide UV transparency window25ABaSbQ 3 (A = Li, Na; Q = S, Se): diverse arrangement modes of isolated SbQ 3 ligands regulating the magnitudes of birefringences50Ba 3 B 10 O 17 F 2 ·0.1KF: the first mixed alkali/alkaline-earth metal fluorooxoborate with unprecedented double-layered B–O/F anionic arrangement17Chloride carbodiimide K 12 Pb 51 (CN 2 ) 30 Cl 54 with an unprecedented 45 Å unit cell axis and a large birefringence7Exploration of the deep-ultraviolet nonlinear optical materials in the derivatives of KBe2BO3F27RE(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 ) − group31The first lithium difluorophosphate LiPO 2 F 2 with a neutral polytetrahedral microporous architecture35Exploration of New Birefringent Crystals in Bismuth d0 Transition Metal Selenites35A New Cadmium‐Based Pb2Cd3(PO4)2(P2O7) with Two Types of Isolated P–O Groups18Optical and Magnetic Properties of Cu-Containing Borates with “Antizeolite” Structure11BaB 2 O 3 F 2 : A Barium Fluorooxoborate with a Unique [B 2 O 3 F] − Layer and Short Cutoff Edge38[Ln6O8] Cluster‐Encapsulating Polyplumbites as New Polyoxometalate Members and Record Inorganic Anion‐Exchange Materials for ReO4− Sequestration21LiBa2MIIIQ4 (MIII = Al, Ga, In; Q = S, Se): A Series of Metal Chalcogenides with a Structural Transition12NaYTe2O7: A new compound with mixed valence of tellurium and large birefringence6Rb3Na(H2C3N3O3)4·3H2O with Large Birefringence28[Al(H 2 O) 6 ](IO 3 ) 2 (NO 3 ): a material with enhanced birefringence induced by synergism of two superior functional motifs29Ba(B 2 OF 3 (OH) 2 ) 2 with well-ordered OH/F anions and a unique B 2 OF 3 (OH) 2 dimer30Enhanced optical anisotropy via dimensional control in alkali-metal chalcogenides18Gd(NO 3 )(Se 2 O 5 )·3H 2 O: a nitrate–selenite nonlinear optical material with a short ultraviolet cutoff edge28PbSrSiO 4 : a new ultraviolet nonlinear optical material with a strong second harmonic generation response and moderate birefringence37RbB 3 O 4 F 2 : a rubidium fluorooxoborate with an unprecedented [B 3 O 5 F 2 ] 3− functionalized unit and a large birefringence37Refractive properties of the α-BaGeO 3 crystal and their origins: a density functional theory study2A Promising Fluorooxoborate Framework with Flexibile Capability for Diverse Cations to Enhance the Second Harmonic Generation14Noncentrosymmetric Fluorooxoborates A10B13O15F19 (A = K and Rb) with Unexpected [B10O12F13]7– Units and Deep-Ultraviolet Cutoff Edges26PbB5O7F3: A High-Performing Short-Wavelength Nonlinear Optical Material120An Unprecedented Antimony(III) Borate with Strong Linear and Nonlinear Optical Responses224An Unprecedented Antimony(III) Borate with Strong Linear and Nonlinear Optical Responses42Volume Modulation of Nonlinear Optical Properties by Cation Substitution8Crystal Chemical Design of Functional Fluoride Borates with “Antizeolite” Structure12A(H3C3N3O3)(NO3) (A = K, Rb): Alkali-Metal Nitrate Isocyanurates with Strong Optical Anisotropy47Borates: A Rich Source for Optical Materials1089Synergism of multiple functional chromophores significantly enhancing the birefringence in layered non-centrosymmetric chalcohalides20BaB 4 O 5 F 4 with reversible phase transition featuring unprecedented fundamental building blocks of [B 16 O 21 F 16 ] in the α -phase and [B 4 O 6 F 4 ] in the β -phase19Hg 3 (Te 3 O 8 )(SO 4 ): a new sulfate tellurite with a novel structure and large birefringence explored from d 10 metal compounds39Li 5 Cs(SO 4 ) 3 : a potential zero-order wave plate material with short deep-ultraviolet cutoff edge20NaKB 6 O 9 F 2 : a new complex alkali metal fluorooxoborate with puckered layers10Pb 2.28 Ba 1.72 B 10 O 19 featuring a three-dimensional B–O anionic network with edge-sharing [BO 4 ] obtained under ambient pressure6RbMo 2 P 3 O 14 with large birefringence mainly induced by highly distorted [MoO 6 ] in uncommon [Mo 2 P 3 O 14 ] ∞ layers9Bi2[B2(SeO3)6]: A Metal Boroselenite with a Unique Zero-Dimensional [B2(SeO3)6]6– Anionic Group and Large Birefringence31Cs4B4O3F10: First Fluorooxoborate with [BF4] Involving Heteroanionic Units and Extremely Low Melting Point18Cs2ZnSn3S8: A Sulfide Compound Realizes a Large Birefringence by Modulating the Dimensional Structure24Sr2Pb(BeB5O10)(BO3): An Excellent Ultraviolet Nonlinear-Optical Beryllium Borate by the Pb-Modified Construction of a Conjugated System and Lone-Pair Effect14The First Mixed Calcium Zinc Borate with a Flexible [B8O17] Fundamental Building Block and Short UV Cutoff Edge7Li 4 MgGe 2 S 7 : The First Alkali and Alkaline‐Earth Diamond‐Like Infrared Nonlinear Optical Material with Exceptional Large Band Gap213Li4MgGe2S7: The First Alkali and Alkaline‐Earth Diamond‐Like Infrared Nonlinear Optical Material with Exceptional Large Band Gap15NaRbB3O4F3: A New Fluorooxoborate with a Short UV Cutoff Edge Enriching the Structural Chemistry of Borate7Hierarchical Modulation of Optical Anisotropy Driven by Metal Cation Polyhedra in Fluorooxoborates MIIB4O6F2 (MII=Be, Mg, Pb, Zn, Cd)6(C 3 N 6 H 7 ) 2 SiF 6 ·H 2 O: an ultraviolet birefringent crystal exceeding the intrinsic energy gap of an organic reagent38Na 2 SrB 16 O 26 : a new borate with independent interpenetrating B–O networks and deep-ultraviolet cutoff edge4Na 3 YB 8 O 15 : a new rare-earth borate with an infinite one-dimensional [B 8 O 15 ] ∞ chain and a short ultraviolet cutoff edge8Pb 2 Al 2 B 3 O 8 F 3 : structure and properties of a new fluoroaluminoborate with non-traditional chain-like B 3 O 8 groups4PNO: a promising deep-UV nonlinear optical material with the largest second harmonic generation effect17Sc 2 F 2 (B 2 O 5 ): a deep ultraviolet scandium borate fluoride exhibiting large birefringence induced by the synergistic effect of B 2 O 5 and ScO n F 2 groups38Lead Tellurite Crystals BaPbTe2O6 and PbVTeO5F with Large Nonlinear-/Linear-Optical Responses due to Active Lone Pairs and Distorted Octahedra20MM′B3O4F3 (M = K; M′ = Na, K, Cs): Alkali-Metal Fluorooxoborates with ∞1[B3O4F3] Chains and Deep-Ultraviolet Cutoff Edges12Effect of bond valence sum on the structural modeling of lead borate glass2NaB3O4F(OH): A Hydroxyfluorooxoborate with One-Dimensional Chain Featuring Large Birefringence and Short Ultraviolet Cutoff Edge5(C3N6H7)2SbF5·H2O Exhibiting Strong Optical Anisotropy from the Optimal Arrangement of π-Conjugated (C3N6H7)+ Groups31LiNaB6O9F2: A Promising UV NLO Crystal Having Fluorine‐Directed Optimal Performances and Double Interpenetrating 3[B6O9F2]∞ Networks33Rb 3 B 5 O 8 F 2 and K 0.6 Rb 2.4 B 5 O 8 F 2 : two new deep-ultraviolet transparent nonlinear optical fluorooxoborates designed by cation regulation13C 10 H 10 ClNO 3 : exploration of birefringent crystals in an isoquinoline system20Hydroxyfluorooxoborate (NH 4 )[C(NH 2 ) 3 ][B 3 O 3 F 4 (OH)] for exploring the effects of cation substitution on structure and optical properties26Fluorooxoborates: A precious treasure of deep-ultraviolet nonlinear optical materials24Na2BaB12O18F4: A Mixed Alkali/Alkaline-Earth Metal Fluorooxoborate with Two Unprecedented Interpenetrating Three-Dimensional B–O/F Anionic Networks and a Short Ultraviolet Cutoff Edge9Chemical perspectives on heteroanionic compounds: a potential playground for multiferroics7NaRbB10O14(OH)4 and Na3CsB10O16(OH)2: Two Cases of Hydroxyborates with [B5Om(OH)n] Units and Deep Ultraviolet Cutoff Edges6PbBeB2O5: A High-Performance Ultraviolet Nonlinear-Optical Crystal with Functional [BeB2O8]8– Group3[C8H6BrN2O]Cl and [C8H6IN2O]Cl: Two birefringent crystals with π-conjugated quinazoline groups2Expanding silver fluorooxoborate crystal chemistry: Ag 2 B 5 O 8 F with 3D double interpenetrating frameworks and Ag 3 B 5 O 8 F 2 with 2D layers5Three Cases of Borates with Different Dimensional Frameworks Induced by Metal Cations1Topological structural chemistry of fluorooxoborates: From fundamental building blocks to macroscopic optical performance regulation0

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  2. Fluorooxoborates: Ushering in a New Era of Deep Ultraviolet Nonlinear Optical Materials

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  3. Thermal properties of 2:1 bismuth borate: Temperature‐dependent characterizations of lone electron pairs

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  4. Li 4 Na 2 CsB 7 O 14 : a new edge-sharing [BO 4 ] 5− tetrahedra containing borate with high anisotropic thermal expansion

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  5. A new barium fluorooxoborate BaB 5 O 8 F· x H 2 O with large birefringence and a wide UV transparency window

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  6. ABaSbQ 3 (A = Li, Na; Q = S, Se): diverse arrangement modes of isolated SbQ 3 ligands regulating the magnitudes of birefringences

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  7. Ba 3 B 10 O 17 F 2 ·0.1KF: the first mixed alkali/alkaline-earth metal fluorooxoborate with unprecedented double-layered B–O/F anionic arrangement

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  8. Chloride carbodiimide K 12 Pb 51 (CN 2 ) 30 Cl 54 with an unprecedented 45 Å unit cell axis and a large birefringence

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  10. 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

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  11. The first lithium difluorophosphate LiPO 2 F 2 with a neutral polytetrahedral microporous architecture

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  12. Exploration of New Birefringent Crystals in Bismuth d0 Transition Metal Selenites

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  13. A New Cadmium‐Based Pb2Cd3(PO4)2(P2O7) with Two Types of Isolated P–O Groups

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  14. Optical and Magnetic Properties of Cu-Containing Borates with “Antizeolite” Structure

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  15. BaB 2 O 3 F 2 : A Barium Fluorooxoborate with a Unique [B 2 O 3 F] − Layer and Short Cutoff Edge

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  16. [Ln6O8] Cluster‐Encapsulating Polyplumbites as New Polyoxometalate Members and Record Inorganic Anion‐Exchange Materials for ReO4− Sequestration

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  17. LiBa2MIIIQ4 (MIII = Al, Ga, In; Q = S, Se): A Series of Metal Chalcogenides with a Structural Transition

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  18. NaYTe2O7: A new compound with mixed valence of tellurium and large birefringence

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  19. Rb3Na(H2C3N3O3)4·3H2O with Large Birefringence

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  20. [Al(H 2 O) 6 ](IO 3 ) 2 (NO 3 ): a material with enhanced birefringence induced by synergism of two superior functional motifs

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  21. 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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  22. Enhanced optical anisotropy via dimensional control in alkali-metal chalcogenides

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  33. Crystal Chemical Design of Functional Fluoride Borates with “Antizeolite” Structure

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  36. Synergism of multiple functional chromophores significantly enhancing the birefringence in layered non-centrosymmetric chalcohalides

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  37. BaB 4 O 5 F 4 with reversible phase transition featuring unprecedented fundamental building blocks of [B 16 O 21 F 16 ] in the α -phase and [B 4 O 6 F 4 ] in the β -phase

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  40. NaKB 6 O 9 F 2 : a new complex alkali metal fluorooxoborate with puckered layers

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  41. Pb 2.28 Ba 1.72 B 10 O 19 featuring a three-dimensional B–O anionic network with edge-sharing [BO 4 ] obtained under ambient pressure

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  42. RbMo 2 P 3 O 14 with large birefringence mainly induced by highly distorted [MoO 6 ] in uncommon [Mo 2 P 3 O 14 ] ∞ layers

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  43. Bi2[B2(SeO3)6]: A Metal Boroselenite with a Unique Zero-Dimensional [B2(SeO3)6]6– Anionic Group and Large Birefringence

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  49. Li4MgGe2S7: The First Alkali and Alkaline‐Earth Diamond‐Like Infrared Nonlinear Optical Material with Exceptional Large Band Gap

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  50. NaRbB3O4F3: A New Fluorooxoborate with a Short UV Cutoff Edge Enriching the Structural Chemistry of Borate

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