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RESEARCH PAPER · Inorganic Chemistry · 2016

Na2B6O9F2: A Fluoroborate with Short Cutoff Edge and Deep-Ultraviolet Birefringent Property Prepared by an Open High-Temperature Solution Method

Guoqiang Q. Shi, Fangfang Zhang, Bingbing Zhang, Dianwei Hou, Xinglong Chen, Zhihua Yang, Shilie Pan

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Na2B6O9F2: A Fluoroborate with Short Cutoff Edge and Deep-Ultraviolet Birefringent Property Prepared by an Open High-Temperature Solution MethodOriginalExperimental and ab initio studies of two UV nonlinear optical materials15Fluorooxoborates: Beryllium‐Free Deep‐Ultraviolet Nonlinear Optical Materials without Layered Growth892Fluorooxoborates: Beryllium‐Free Deep‐Ultraviolet Nonlinear Optical Materials without Layered Growth99Design and Synthesis of a Series of Novel Mixed Borate and Carbonate Halides21CsB 4 O 6 F: A Congruent‐Melting Deep‐Ultraviolet Nonlinear Optical Material by Combining Superior Functional Units184CsB4O6F: A Congruent‐Melting Deep‐Ultraviolet Nonlinear Optical Material by Combining Superior Functional Units895The First Alkaline‐Earth Fluorooxoborate Ba[B4O6F2]—Characterisation and Doping with Eu2+95MBaYB 6 O 12 (M = Rb, Cs): two new rare-earth borates with large birefringence and short ultraviolet cutoff edges42BaBOF 3 : a new aurivillius-like borate containing two types of F atoms32Ion-induced structural and optical performance evolution in LBO-like crystals: experimental and theoretical investigation13K 11 RbB 28 O 48 : a new triple-layered borate with an unprecedented [B 28 O 57 ] fundamental building block19Na 3 Ca 4 (TeO 3 )(PO 4 ) 3 : a new noncentrosymmetric tellurite phosphate with fascinating multimember-ring architectures and intriguing nonlinear optical performance30NH 4 B 11 O 16 (OH) 2 : a new ammonium borate with wavy-shaped polycyclic 2∞[B 11 O 16 (OH) 2 ] layers27A Member of Fluorooxoborates: Li2Na0.9K0.1B5O8F2 with the Fundamental Building Block B5O10F2 and a Short Cutoff Edge27Cation‐Tuned Synthesis of Fluorooxoborates: Towards Optimal Deep‐Ultraviolet Nonlinear Optical Materials191Cation‐Tuned Synthesis of Fluorooxoborates: Towards Optimal Deep‐Ultraviolet Nonlinear Optical Materials714K3B6O9F3: A New Fluorooxoborate with Four Different Anionic Units42SrB 5 O 7 F 3 Functionalized with [B 5 O 9 F 3 ] 6− Chromophores: Accelerating the Rational Design of Deep‐Ultraviolet Nonlinear Optical Materials738SrB5O7F3 Functionalized with [B5O9F3]6− Chromophores: Accelerating the Rational Design of Deep‐Ultraviolet Nonlinear Optical Materials116M2B10O14F6 (M = Ca, Sr): Two Noncentrosymmetric Alkaline Earth Fluorooxoborates as Promising Next-Generation Deep-Ultraviolet Nonlinear Optical Materials356A new alkaline-earth metal borate SrB3O4(OH)3·H2O with UV cutoff edge below 190 nm7CaB5O7F3: A Beryllium-Free Alkaline-Earth Fluorooxoborate Exhibiting Excellent Nonlinear Optical Performances192Polar Fluorooxoborate, NaB4O6F: A Promising Material for Ionic Conduction and Nonlinear Optics494Polar Fluorooxoborate, NaB4O6F: A Promising Material for Ionic Conduction and Nonlinear Optics67From LiB3O5 to NaRbB6O9F2: Fluorine‐Directed Evolution of Structural Chemistry33Synthesis and electronic structure studies of a novel nonlinear optical crystal L-leucinium squarate monohydrate: A spectroscopic view13Designing Deep‐UV Birefringent Crystals by Cation Regulation57Sn[B2O3F2]—The First Tin Fluorooxoborate as Possible NLO Material102Second-order nonlinear optical crystals with mixed anions250Na 3 B 7 O 11 F 2 : a new sodium-rich fluorooxoborate with a unique [B 14 O 24 F 4 ] ring and a short ultraviolet absorption edge27BaB8O12F2: a promising deep-UV birefringent material60A 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 arrangement17K 2 [B 4 O 5 (OH) 4 ]·H 2 O and K 2 [B 4 O 5 (OH) 4 ]: two new hydrated potassium borates with isolated [B 4 O 5 (OH) 4 ] 2− units and different structural frameworks8Mg(H 2 O) 6 B 4 O 5 (OH) 4 (H 2 O) 3 : a new hydrated borate with a short DUV cutoff edge9Sn 2 B 7 O 12 F with a 2∞[B 14 O 24 ] 6− layer constructed from the unprecedented [B 7 O 16 ] 11− fundamental building block18Two new tin( iv )-containing phosphate fluorides with two types of Sn( iv )–P–O–F frameworks and short cutoff edges0Abrupt Structural Transformation in Asymmetric ABPO4F (A = K, Rb, Cs)21Designing Three Fluorooxoborates with a Wide Transmittance Window by Anionic Group Substitution15RbB 11 O 16 (OH) 2 : First Hydroxyl Rubidium Borate with the B‐O 2D Layer Featuring Large Birefringence in the Rb‐B‐O‐H System5BaB 2 O 3 F 2 : A Barium Fluorooxoborate with a Unique [B 2 O 3 F] − Layer and Short Cutoff Edge38Synthesis, crystal structure and optical properties of a new fluoroborate compound: Al7-xLi1+xB4O16+xF1-x (x = 1/3)2Cation Modulation on the Crystal Structure and Band Gap of Fluorooxoborates A3B3O3F6 (A = Alkali and Mixed Alkali Metal)17Pb 3 Ba 3 Zn 6 (BO 3 ) 8 and α-BaZn 2 (BO 3 ) 2 : new members of the zincoborates containing two different dimensional Zn–O units8Al8(BO3)4(B2O5)F8: A F-Containing Aluminum Borate Featuring Two Types of Isolated B–O Groups12From BaAl 2 (BO 3 ) 2 O to SnAl 2 (BO 3 ) 2 F 2 : structure transformation based on ion regulation3Nd3+ and Pr3+ doped anti-zeolite matrix-LiBa12(BO3)7F4: Crystal structures, luminescence properties11Prediction of ternary fluorooxoborates with coplanar triangular units [BO x F 3−x ] x− from first-principles13RbB 3 O 4 F 2 : a rubidium fluorooxoborate with an unprecedented [B 3 O 5 F 2 ] 3− functionalized unit and a large birefringence37Synthesis, characterization and crystal structure of a new mixed alkali and alkaline-earth metal borate Rb 9 Ba 24 (BO 3 ) 196Noncentrosymmetric Fluorooxoborates A10B13O15F19 (A = K and Rb) with Unexpected [B10O12F13]7– Units and Deep-Ultraviolet Cutoff Edges26Structural Diversity of Molybdate Iodate and Fluoromolybdate: Syntheses, Structures, and Calculations on Na3(MoO4)(IO3) and Na3Cs(MoO2F4)218Enhanced nonlinear optical functionality in birefringence and refractive index dispersion of the deep-ultraviolet fluorooxoborates123Crystal Chemical Design of Functional Fluoride Borates with “Antizeolite” Structure12Ba 2 B 7 O 12 F with novel FBB [B 7 O 16 F] and deep-ultraviolet cut-off edge31Borates: A Rich Source for Optical Materials1089Na 2 La 2 B 10 O 19 : a new lanthanum sodium borate with infinite 2D layer 2∞[B 10 O 19 ] 8− and moderate birefringence4NaKB 6 O 9 F 2 : a new complex alkali metal fluorooxoborate with puckered layers10Sn 14 O 11 Br 6 : a promising birefringent material with a [Sn 14 O 11 Br 6 ] layer26Synthesis, crystal structure and theoretical calculations of two rare-earth borates with DUV cut-off edges6Fluorine‐Driven Enhancement of Birefringence in the Fluorooxosulfate: A Deep Evaluation from a Joint Experimental and Computational Study139NaRbB3O4F3: A New Fluorooxoborate with a Short UV Cutoff Edge Enriching the Structural Chemistry of Borate7Ba 2 B 5 O 8 (OH) 2 (NO 3 )·3H 2 O: the design of an alkaline earth metal borate-nitrate optimized from a hydroxylic borate4A 2 B 6 O 9 F 2 (A = NH 4 , K): new members of A 2 B 6 O 9 F 2 family with deep-UV cutoff edges and moderate birefringence17CsB 3 O 4 (OH) 2 : a new deep-ultraviolet birefringent crystal with [B 3 O 4 (OH) 2 ] anionic group8Molecular identification guided process design for deep removal of fluoride from electroplating effluent4Pb 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 groups4MM′B3O4F3 (M = K; M′ = Na, K, Cs): Alkali-Metal Fluorooxoborates with ∞1[B3O4F3] Chains and Deep-Ultraviolet Cutoff Edges12LiB5O5F2(OH)4: A new deep-ultraviolet birefringent crystal with [B5O5F2(OH)4] anionic group28NaBa3[M2B7O16(OH)2]F2 (M = Ge, Si): Two Synthetic F Analogues of Garrelsite with [B7O16(OH)2]13– Polyanions and Deep-Ultraviolet Cutoff Edges8An excellent deep-ultraviolet birefringent material based on [BO2]∞ infinite chains185NaB3O4F(OH): A Hydroxyfluorooxoborate with One-Dimensional Chain Featuring Large Birefringence and Short Ultraviolet Cutoff Edge5Li2PbB2O5: A Pyroborate with Large Birefringence Induced by the Synergistic Effect of Stereochemical Active Lone Pair Cations and π-Conjugated [B2O5] Groups14LiNaB6O9F2: A Promising UV NLO Crystal Having Fluorine‐Directed Optimal Performances and Double Interpenetrating 3[B6O9F2]∞ Networks33An effective pathway to design and synthesize UV birefringent crystals via rational assembly of π-conjugated [CO 3 ] 2− and [NO 3 ] − triangles32Li2AB5O8F2 (A = Na and K): two new deep-ultraviolet transparent fluorooxoborates with moderate birefringence designed by targeted dimensional modulation7BaB2P2O8F2: A Fluoroborophosphate with [B2P2O8F2]∞ Layers and Deep-Ultraviolet Cutoff Edge4Fluorooxoborates: A precious treasure of deep-ultraviolet nonlinear optical materials24Li3B8O13X (X = Cl and Br): Two New Noncentrosymmetric Crystals with Large Birefringence Induced by BO3 Units18Ba2B9O13F4·BF4: first fluorooxoborate with unprecedented infinite [B18O26F8] tubes and deep-ultraviolet cutoff edge14Na2BaB12O18F4: A Mixed Alkali/Alkaline-Earth Metal Fluorooxoborate with Two Unprecedented Interpenetrating Three-Dimensional B–O/F Anionic Networks and a Short Ultraviolet Cutoff Edge9CaB2O2F4: A Novel [BOF2]∞-Based Structural Template with a Strong Second Harmonic Generation Response and Large Band Gap2Chain‐like [S x ] ( x =2–6) Units Realizing Giant Birefringence with Transparency in the Near‐Infrared for Optoelectronic Materials53Chain‐like [S x ] ( x =2–6) Units Realizing Giant Birefringence with Transparency in the Near‐Infrared for Optoelectronic Materials5Three Polyborates with High-Symmetry [B12O24] Units Featuring Different Dimensions of Anion Groups8Fluorooxoborate Promoting the Exploration of Short-Wavelength Linear and Nonlinear Optical Crystals with Expected Properties and Versatile Structures27Ba3.75MgB7O14F2.5: A Mixed Alkaline-Earth Metal Borate Fluoride with Short Ultraviolet Cutoff Edge and Large Birefringence9Optically Anisotropic Mixed-Metal Fluoroiodate Ba2[GaF5(IO3F)] with a Wide Optical Transparent Window and a Moderate Birefringence6PbTeB 4 O 9 : a lead tellurium borate with unprecedented fundamental building block [B 4 O 10 ] and large birefringence12A deep-ultraviolet nonlinear-optical material with a wide bandgap and large static dielectric polarizability coefficient: Na 6 Si 3 F 181Designing excellent UV birefringent materials through the synergistic interaction of two highly distorted functional groups23New antimony fluorooxoborates with strong birefringence and unprecedented structural characterisation19Screening Aluminum-Based Compounds as Low-κ Dielectrics for High-Frequency Applications17NaRbB10O14(OH)4 and Na3CsB10O16(OH)2: Two Cases of Hydroxyborates with [B5Om(OH)n] Units and Deep Ultraviolet Cutoff Edges6Two Mixed Alkali Metal Isocyanurates with Wide Band Gap and Giant Birefringence2Sb2O2SeO3 and Sb2O(SeO3)2: Two-Layered Antimony(III) Selenites with Enhanced Birefringence10Structural Evolution and Optical Properties of Hydroxyfluorooxoborates MM′2n-1[B3O3F4(OH)]n (M = K, Cs, and Rb; M′ = K, NH4, and Cs; n = 1, 2, and 3)12CsBO(OH) 2 : a new hydroxyborate with the rare [BO(OH) 2 ] group and a deep ultraviolet cutoff edge3Dual Lone Pair Strategy for High Birefringence in Antimony(III)-Based Tellurite Sulfates with Short-Wave UV Transparency10Prediction of New Functional Fluorooxoborates with Expected Anionic Framework: A Case of CaB3O5F4Three Cases of Borates with Different Dimensional Frameworks Induced by Metal Cations1Study of Cleavage Fracture Strength of Cation-Tuned Yttrium Calcium Oxyborate Crystals0Computational design of new DUV NLO fluorooxoborates with [BO 3 ] : [BO 3 F] = 2 : 1 via an anionic framework dimensionality-fixed strategy0Topological structural chemistry of fluorooxoborates: From fundamental building blocks to macroscopic optical performance regulation0Hydrothermal growth, structural and optical properties of large-sized Cs2SiF6 single crystals as promising DUV optical window materials0

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  1. Experimental and ab initio studies of two UV nonlinear optical materials

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  2. Fluorooxoborates: Beryllium‐Free Deep‐Ultraviolet Nonlinear Optical Materials without Layered Growth

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  3. Fluorooxoborates: Beryllium‐Free Deep‐Ultraviolet Nonlinear Optical Materials without Layered Growth

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  4. Design and Synthesis of a Series of Novel Mixed Borate and Carbonate Halides

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  5. CsB 4 O 6 F: A Congruent‐Melting Deep‐Ultraviolet Nonlinear Optical Material by Combining Superior Functional Units

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  6. CsB4O6F: A Congruent‐Melting Deep‐Ultraviolet Nonlinear Optical Material by Combining Superior Functional Units

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  7. The First Alkaline‐Earth Fluorooxoborate Ba[B4O6F2]—Characterisation and Doping with Eu2+

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  8. MBaYB 6 O 12 (M = Rb, Cs): two new rare-earth borates with large birefringence and short ultraviolet cutoff edges

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  9. BaBOF 3 : a new aurivillius-like borate containing two types of F atoms

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  10. Ion-induced structural and optical performance evolution in LBO-like crystals: experimental and theoretical investigation

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  11. K 11 RbB 28 O 48 : a new triple-layered borate with an unprecedented [B 28 O 57 ] fundamental building block

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  12. Na 3 Ca 4 (TeO 3 )(PO 4 ) 3 : a new noncentrosymmetric tellurite phosphate with fascinating multimember-ring architectures and intriguing nonlinear optical performance

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  13. NH 4 B 11 O 16 (OH) 2 : a new ammonium borate with wavy-shaped polycyclic 2∞[B 11 O 16 (OH) 2 ] layers

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  14. A Member of Fluorooxoborates: Li2Na0.9K0.1B5O8F2 with the Fundamental Building Block B5O10F2 and a Short Cutoff Edge

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  15. Cation‐Tuned Synthesis of Fluorooxoborates: Towards Optimal Deep‐Ultraviolet Nonlinear Optical Materials

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  16. Cation‐Tuned Synthesis of Fluorooxoborates: Towards Optimal Deep‐Ultraviolet Nonlinear Optical Materials

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  17. K3B6O9F3: A New Fluorooxoborate with Four Different Anionic Units

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  18. SrB 5 O 7 F 3 Functionalized with [B 5 O 9 F 3 ] 6− Chromophores: Accelerating the Rational Design of Deep‐Ultraviolet Nonlinear Optical Materials

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  19. SrB5O7F3 Functionalized with [B5O9F3]6− Chromophores: Accelerating the Rational Design of Deep‐Ultraviolet Nonlinear Optical Materials

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  20. M2B10O14F6 (M = Ca, Sr): Two Noncentrosymmetric Alkaline Earth Fluorooxoborates as Promising Next-Generation Deep-Ultraviolet Nonlinear Optical Materials

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  21. A new alkaline-earth metal borate SrB3O4(OH)3·H2O with UV cutoff edge below 190 nm

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  22. CaB5O7F3: A Beryllium-Free Alkaline-Earth Fluorooxoborate Exhibiting Excellent Nonlinear Optical Performances

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  23. Polar Fluorooxoborate, NaB4O6F: A Promising Material for Ionic Conduction and Nonlinear Optics

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  24. Polar Fluorooxoborate, NaB4O6F: A Promising Material for Ionic Conduction and Nonlinear Optics

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  25. From LiB3O5 to NaRbB6O9F2: Fluorine‐Directed Evolution of Structural Chemistry

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  26. Synthesis and electronic structure studies of a novel nonlinear optical crystal L-leucinium squarate monohydrate: A spectroscopic view

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  27. Designing Deep‐UV Birefringent Crystals by Cation Regulation

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  28. Sn[B2O3F2]—The First Tin Fluorooxoborate as Possible NLO Material

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  29. Second-order nonlinear optical crystals with mixed anions

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  30. Na 3 B 7 O 11 F 2 : a new sodium-rich fluorooxoborate with a unique [B 14 O 24 F 4 ] ring and a short ultraviolet absorption edge

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  31. BaB8O12F2: a promising deep-UV birefringent material

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  32. 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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  33. 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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  34. 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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  35. K 2 [B 4 O 5 (OH) 4 ]·H 2 O and K 2 [B 4 O 5 (OH) 4 ]: two new hydrated potassium borates with isolated [B 4 O 5 (OH) 4 ] 2− units and different structural frameworks

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  36. Mg(H 2 O) 6 B 4 O 5 (OH) 4 (H 2 O) 3 : a new hydrated borate with a short DUV cutoff edge

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  37. Sn 2 B 7 O 12 F with a 2∞[B 14 O 24 ] 6− layer constructed from the unprecedented [B 7 O 16 ] 11− fundamental building block

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  38. Two new tin( iv )-containing phosphate fluorides with two types of Sn( iv )–P–O–F frameworks and short cutoff edges

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  39. Abrupt Structural Transformation in Asymmetric ABPO4F (A = K, Rb, Cs)

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  40. Designing Three Fluorooxoborates with a Wide Transmittance Window by Anionic Group Substitution

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  41. RbB 11 O 16 (OH) 2 : First Hydroxyl Rubidium Borate with the B‐O 2D Layer Featuring Large Birefringence in the Rb‐B‐O‐H System

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  42. 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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  43. Synthesis, crystal structure and optical properties of a new fluoroborate compound: Al7-xLi1+xB4O16+xF1-x (x = 1/3)

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  44. Cation Modulation on the Crystal Structure and Band Gap of Fluorooxoborates A3B3O3F6 (A = Alkali and Mixed Alkali Metal)

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  45. Pb 3 Ba 3 Zn 6 (BO 3 ) 8 and α-BaZn 2 (BO 3 ) 2 : new members of the zincoborates containing two different dimensional Zn–O units

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  46. Al8(BO3)4(B2O5)F8: A F-Containing Aluminum Borate Featuring Two Types of Isolated B–O Groups

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  47. From BaAl 2 (BO 3 ) 2 O to SnAl 2 (BO 3 ) 2 F 2 : structure transformation based on ion regulation

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