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RESEARCH PAPER · Chemistry - A European Journal · 2016

Deep‐Ultraviolet Nonlinear Optics in a Borate Framework with 21‐Ring Channels

Qi Wei, Jiajia Wang, Chao He, Jian‐Wen Cheng, Guo‐Yu Yang

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Deep‐Ultraviolet Nonlinear Optics in a Borate Framework with 21‐Ring ChannelsOriginalTwo New Octaborates Constructed of Two Different Sub-clusters and Supported by Metal Complexes11Na7[Ga2B13O24(OH)4]: A Luminescent Sodium Gallium Borate Containing Two Different Types of Oxoboron Framework Building Blocks4Two 3D nonlinear optical and luminescent lanthanide-organic frameworks with multidirectional helical intersecting channels8Two deep-ultraviolet nonlinear optical alkaline-earth metal borates based on different types of oxoboron clusters56Two New Copper Borates with Mesoscale Cubic Supramolecular Cages Assembled from {Cu4@B20} Clusters27Na4Ca[B4O5(OH)4]3·14H2O: An Acentric Supramolecular Framework Borate Based on [B4O5(OH)4]2− Cluster Units8Extending Unique 1D Borate Chains to 3D Frameworks by Introducing Metallic Nodes44Na8MB21O36 (M = Rb and Cs): Noncentrosymmetric Borates with Unprecedented [B21O36]9– Fundamental Building Blocks36An Ultraviolet Nonlinear Optic Borate with 13-Ring Channels Constructed from Different Building Units56Novel borate supramolecular frameworks constructed from isolated B4/B5 clusters and 1-D B17-based chains8Na2(H2en)[B5O8(OH)]2[B3O4(OH)]2 and Na3(HCOO)[B5O8(OH)]: Two Borates Co‐Templated by Inorganic Cations and Organic Compounds20Synthesis and photoluminescence of amorphous AlBCO phosphors0A new mixed alkali metal borate: LiCs[B5O8(OH)]·H2O11Centrosymmetric (Hdima)2[Ge5B3O15(OH)] and Noncentrosymmetric Na4Ga3B4O12(OH): Solvothermal/Surfactant-Thermal Synthesis of Open-Framework Borogermanate and Galloborate34Li7(TeO3)3F: A Lithium Fluoride Tellurite with Large Second Harmonic Generation Responses and a Short Ultraviolet Cutoff Edge39K2[B3O3(OH)5]: A new deep-UV nonlinear optical crystal with isolated [B3O3(OH)5]2- anionic groups31Chemical Cosubstitution-Oriented Design of Rare-Earth Borates as Potential Ultraviolet Nonlinear Optical Materials267Ion-induced structural and optical performance evolution in LBO-like crystals: experimental and theoretical investigation13RbSe 3 B 2 O 9 (OH) and CsSe 3 B 2 O 9 (OH): one dimensional boroselenite-based anionic frameworks with second harmonic generation properties15The first lead fluorooxoborate PbB 5 O 8 F: achieving the coexistence of large birefringence and deep-ultraviolet cut-off edge75Linking 1D Transition-Metal Coordination Polymers and Different Inorganic Boron Oxides To Construct a Series of 3D Inorganic–Organic Hybrid Borates42SrB 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 Materials116Recent advances in ultraviolet and deep-ultraviolet second-order nonlinear optical crystals257Ba3Mg3(BO3)3F3 polymorphs with reversible phase transition and high performances as ultraviolet nonlinear optical materials470Second-order nonlinear optical crystals with mixed anions250The First Examples of Lithium‐Containing Mixed‐Alkali Strontium Borates with Different Dimensional Anionic Architectures and Short Cutoff Edges16An inorganic-organic hybrid solid with B5O7(OH)3 clusters bridged and decorated by zinc–amine complexes1The structure and classification of complex borates43Ba 3 Ca 4 (BO 3 ) 3 (SiO 4 )Cl: a new non-centrosymmetric complex alkaline-earth metal borosilicate chloride with a deep-ultraviolet cut-off edge19Hybridization-activated new deep ultraviolet transparent nonlinear optical material Ba 11 [Al(PO 4 ) 4 ](P 2 O 7 )(PO 4 ) 3 with balanced overall performance and parsimony-forbidden structure23K 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 frameworks8KBi(IO 3 ) 3 (OH) and NaBi(IO 3 ) 4 : from the centrosymmetric chain to a noncentrosymmetric double layer18Li 2 Na 2 [B 12 O 19 (OH) 2 ]: a new open framework borate with a pcu-type net constructed from large cyclic dodeca-oxoboron units8Li2CsB7O10(OH)4: A Deep-Ultraviolet Nonlinear-Optical Mixed-Alkaline Borate Constructed by Unusual Heptaborate Anions98Rational Design via Synergistic Combination Leads to an Outstanding Deep-Ultraviolet Birefringent Li2Na2B2O5 Material with an Unvalued B2O5 Functional Gene284Zeolitic Open-Framework Borates with Noncentrosymmetric Structures and Nonlinear Optical Properties24Targeting the Next Generation of Deep-Ultraviolet Nonlinear Optical Materials: Expanding from Borates to Borate Fluorides to Fluorooxoborates450LiK[B5O8(OH)]·1.5H2O: A novel lithium borate with nonlinear optical property11Module-Analysis-Assisted Design of Deep Ultraviolet Fluorooxoborates with Extremely Large Gap and High Structural Stability109Synthesis, characterization, and theoretical analysis of three new nonlinear optical materials K7MRE2B15O30 (M= Ca and Ba, RE= La and Bi)28Prediction of Fluorooxoborates with Colossal Second Harmonic Generation (SHG) Coefficients and Extremely Wide Band Gaps: Towards Modulating Properties by Tuning the BO 3 /BO 3 F Ratio in Layers99Prediction of Fluorooxoborates with Colossal Second Harmonic Generation (SHG) Coefficients and Extremely Wide Band Gaps: Towards Modulating Properties by Tuning the BO3/BO3F Ratio in Layers24Research and Development of Zincoborates: Crystal Growth, Structural Chemistry and Physicochemical Properties20Two novel 3D borates: porous-layer and layer-pillar frameworks19Effect of anion dimensionality on optical properties: the ∞ [B 7 O 10 (OH) 2 ] layer in CsB 7 O 10 (OH) 2 vs. the ∞ [B 7 O 12 ] framework in CsBaB 7 O 1219Two new Cu-based borate catalysts with cubic supramolecular cages for efficient catalytic hydrogen evolution30The UV-phosphor strontium fluorooxoborate Sr[B5O7F3]:Eu10Band-Gap Modulation of Nonlinear-Optical Fluorooxoborates by Controlling the F/B Ratios4A Promising Fluorooxoborate Framework with Flexibile Capability for Diverse Cations to Enhance the Second Harmonic Generation14Two Covalent Ultraviolet Nonlinear Optical Crystals3Ba 2 B 7 O 12 F with novel FBB [B 7 O 16 F] and deep-ultraviolet cut-off edge31Three Inorganic–Organic Hybrid Gallo-/Alumino-Borates with Porous-Layered Structures Containing [MB4O10(OH)] (M = Al/Ga) Cluster Units12Ba 3 [Al(PO 4 ) 3 ]: rational design of a promising deep-UV transparent SHG crystal with balanced overall performance originating from the condensation of quartz-type [Al(PO 4 ) 4 ] 9− units16Computationally assisted multistage design and prediction driving the discovery of deep-ultraviolet nonlinear optical materials41Five new rubidium borates with 0D clusters, 1D chains, 2D layers and 3D frameworks15Ultraviolet nonlinear optical crystals A 3 SrBi(P 2 O 7 ) 2 (A = K, Rb) with large second harmonic generation responses15Discovery of First Magnesium Fluorooxoborate with Stable Fluorine Terminated Framework for Deep‐UV Nonlinear Optical Application167Discovery of First Magnesium Fluorooxoborate with Stable Fluorine Terminated Framework for Deep‐UV Nonlinear Optical Application18Structural Chemistry of Metal‐Oxo Clusters1Structural Chemistry of Metal‐Oxo Clusters1Two Chiral Metal Complex Templated Aluminoborates Constructed from Three Types of Oxoboron Clusters17Cs4B4O3F10: First Fluorooxoborate with [BF4] Involving Heteroanionic Units and Extremely Low Melting Point18Two deep-ultraviolet nonlinear optical barium borates framework: Alkali metal enhances the second-harmonic generation response13A New Tubular Borate Built By [B14O24(OH)6]12− Cluster Units12K2Na3[{B6O10(OH)}{B3O4(OH)3}] ⋅ H2O: A Layered Borate Built by Mixed Oxoboron Clusters with Nonlinear‐Optical Property20An Overview on Recent Trends in Deep‐Ultraviolet (DUV) and Ultraviolet (UV) Nonlinear Optical Crystals25Four Inorganic–Organic Hybrid Borates: From 2D Layers to 3D Oxoboron Cluster Organic Frameworks8Ba 10 LuB 18 O 32 F 13 : the first example of borate in the Lu–B–O–F system with the unprecedented FBB [B 9 O 22 ]12Na 3 B 6 O 10 (HCOO): an ultraviolet nonlinear optical sodium borate-formate33Syntheses, structures and optical properties of two B 3 O 7 cluster-based borates9Two layered galloborates from centric to acentric structures: syntheses and NLO properties27Two porous-layered borates built by B 7 O 13 (OH) clusters and AlO 4 /GaO 4 tetrahedra7Na 3 Ti 3 O 3 (SeO 3 ) 4 F: A Phase-Matchable Nonlinear-Optical Crystal with Enlarged Second-Harmonic-Generation Intensity and Band Gap20Ba2B10O16(OH)2·(H3BO3)(H2O): A Possible Deep-Ultraviolet Nonlinear-Optical Barium Borate36Two New Borates Built by Different Types of {B9} Cluster Units14Two Mixed Alkali-Metal Borates Templated from Cations to Clusters10Two New Nonaborates with {B9} Cluster Open-Frameworks and Short Cutoff Edges4C(NH2)3Rb(I3O8)(IO3)(I2O6H2): An unprecedented organic–inorganic hybrid polyiodate with two different polyiodate groups13Crystal structure of Rb6[B12O18(OH)6]·2H2O0A Lewis acid–base paired InBO 3 catalyst: synthesis and high selectivity for isopropanol dehydrogenation10A series of novel phosphites/phosphates with deep-ultraviolet cut-off edges from 0D polar to 3D non-polar architectures13Two Acentric Aluminoborates Incorporated d10 Cations: Syntheses, Structures, and Nonlinear Optical Properties24Recent progress in ultraviolet and deep-ultraviolet nonlinear optical aluminoborates17FILLING OF CHANNELS OF THE ZEOLITE FRAMEWORK IN TRIGONAL POLAR NONABORATE Ва3Na0.9(OH)1.9[B9O16][B(OH)3]0Filling of Channels of the Zeolite Framework in Trigonal Polar Nonaborate Ва3Na0.9(OH)1.9[B9O16][B(OH)3]0KCs2[GaB5O10](OH): A Zeolitic Galloborate Framework with a Nonlinear Optical Property13The new non‐centrosymmetric zinc borate Zn2B10O17 with a unique crystal structure5Recent Progress in Crystalline Borates with Edge-Sharing BO4 Tetrahedra21Na1.5Cs0.5[Al{BO3}{B9O15(OH)3}1/3]: An Acentric Layered Aluminoborate with Nonlinear-Optical Properties9Galloborates as ultraviolet nonlinear optical crystals: advances and perspectives8Sr2[B5O8(OH)]2 ⋅ [B(OH)3] ⋅ H2O: A Strontium Borate That Shows Deep‐Ultraviolet‐Transparent Nonlinear Optical Properties17Two Hydroxyfluorooxoborates Achieving Deep‐Ultraviolet Cutoff Edges and Moderate Birefringence by Assembling Multi‐Anionic Groups6Structural Regulations of Layered Borates: From Centric Layers to Chiral Porous Layers3[H2dab][GaB5O10]: an Acentric Galloborate with a 4-Connected Uninodal Framework6Two Alkaline Metal Borates: from Layer to Layer-Pillared Framework8Two alkali metal borates built by {Li@B 14 } and {B 15 } cluster units1Inorganic Borate Functionalized {Ni6SiW9} Polyoxometalates: From Cluster to Cage Cluster4Second-Harmonic Generation in Organic–Inorganic Hybrid Cadmium Thiocyanates Containing Terminal Amino Acids22Non-equivalent terminating roles of hydroxyl and fluorine in hydroxy/fluorooxo-borate optical functional materials2Structures and Nonlinear Optical Properties of Two Acentric Borates with Cubic Cage-like Frameworks5Li6[{BO3}{B15O21(OH)6}]: An Acentric Layered Borate Constructed from Unprecedented Oxoboron Cluster Building Units6Borosilicates as deep-ultraviolet transparent nonlinear optical crystals: Structural motifs, performance limits and future directions9Construction of {BCo 9 }-Based Polyoxometalates with Banana- and Peanut-Shaped Structures: Catalytic Activity in Knoevenagel Condensation Reactions1Two {B 6 }-Based Borates: From 1D Chain to 3D Framework1Assembly of Functional Units for Constructing an Ultraviolet-Transparent Nonlinear Optical Mixed Alkaline Metal Borate-Formate1Two Acentric Borates with 2-/3-D Frameworks: Syntheses, Structures, and Nonlinear Optical Properties0Unlocking Hidden Potential via Reprogrammed Mineral Structures: How Anionic Transformation Achieves Ultraviolet Nonlinear Optical Performance0Two transition metal borates built from unprecedented {B11} clusters with nonlinear optical properties0

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  2. Na7[Ga2B13O24(OH)4]: A Luminescent Sodium Gallium Borate Containing Two Different Types of Oxoboron Framework Building Blocks

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  4. Two deep-ultraviolet nonlinear optical alkaline-earth metal borates based on different types of oxoboron clusters

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  5. Two New Copper Borates with Mesoscale Cubic Supramolecular Cages Assembled from {Cu4@B20} Clusters

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  6. Na4Ca[B4O5(OH)4]3·14H2O: An Acentric Supramolecular Framework Borate Based on [B4O5(OH)4]2− Cluster Units

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  7. Extending Unique 1D Borate Chains to 3D Frameworks by Introducing Metallic Nodes

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  8. Na8MB21O36 (M = Rb and Cs): Noncentrosymmetric Borates with Unprecedented [B21O36]9– Fundamental Building Blocks

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  11. Na2(H2en)[B5O8(OH)]2[B3O4(OH)]2 and Na3(HCOO)[B5O8(OH)]: Two Borates Co‐Templated by Inorganic Cations and Organic Compounds

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  34. Li 2 Na 2 [B 12 O 19 (OH) 2 ]: a new open framework borate with a pcu-type net constructed from large cyclic dodeca-oxoboron units

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  35. Li2CsB7O10(OH)4: A Deep-Ultraviolet Nonlinear-Optical Mixed-Alkaline Borate Constructed by Unusual Heptaborate Anions

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  36. Rational Design via Synergistic Combination Leads to an Outstanding Deep-Ultraviolet Birefringent Li2Na2B2O5 Material with an Unvalued B2O5 Functional Gene

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  38. Targeting the Next Generation of Deep-Ultraviolet Nonlinear Optical Materials: Expanding from Borates to Borate Fluorides to Fluorooxoborates

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  39. LiK[B5O8(OH)]·1.5H2O: A novel lithium borate with nonlinear optical property

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  41. Synthesis, characterization, and theoretical analysis of three new nonlinear optical materials K7MRE2B15O30 (M= Ca and Ba, RE= La and Bi)

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  42. Prediction of Fluorooxoborates with Colossal Second Harmonic Generation (SHG) Coefficients and Extremely Wide Band Gaps: Towards Modulating Properties by Tuning the BO 3 /BO 3 F Ratio in Layers

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  43. Prediction of Fluorooxoborates with Colossal Second Harmonic Generation (SHG) Coefficients and Extremely Wide Band Gaps: Towards Modulating Properties by Tuning the BO3/BO3F Ratio in Layers

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  45. Two novel 3D borates: porous-layer and layer-pillar frameworks

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  46. Effect of anion dimensionality on optical properties: the ∞ [B 7 O 10 (OH) 2 ] layer in CsB 7 O 10 (OH) 2 vs. the ∞ [B 7 O 12 ] framework in CsBaB 7 O 12

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  47. Two new Cu-based borate catalysts with cubic supramolecular cages for efficient catalytic hydrogen evolution

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  48. The UV-phosphor strontium fluorooxoborate Sr[B5O7F3]:Eu

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  49. Band-Gap Modulation of Nonlinear-Optical Fluorooxoborates by Controlling the F/B Ratios

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  50. A Promising Fluorooxoborate Framework with Flexibile Capability for Diverse Cations to Enhance the Second Harmonic Generation

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