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RESEARCH PAPER · Angewandte Chemie International Edition · 2022

Aluminoborates as Nonlinear Optical Materials

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Aluminoborates as Nonlinear Optical MaterialsOriginalAnisotropic structure building unit involving diverse chemical bonds: a new opportunity for high-performance second-order NLO materials181Hg 3 O 2 (NO 3 )F: a mercury nitrate oxyfluoride with an unprecedented [(Hg 3 O 2 F) + ] ∞ cationic framework and excellent optical anisotropy21Fluorooxoborates: A precious treasure of deep-ultraviolet nonlinear optical materials24Recent progress in ultraviolet and deep-ultraviolet nonlinear optical aluminoborates17[K2PbX][Ga7S12] (X = Cl, Br, I): The First Lead‐Containing Cationic Moieties with Ultrahigh Second‐Harmonic Generation and Band Gaps Exceeding the Criterion of 2.33 eV46Structural Motif Cosubstitution Strategy for Designing Fluoroaluminoborate with the Sr2Be2B2O7-Type Double-Layered Structure14Y(HSeO3)(SeO3)(H2O)·(H2O) and Y2(SeO3)2(SeO4)(H2O)2·(H2O)0.75: Two yttrium selenites with a short UV cut-off edge explored from pure selenite compounds20Three Polyborates with High-Symmetry [B12O24] Units Featuring Different Dimensions of Anion Groups8Recent Progress in Crystalline Borates with Edge-Sharing BO4 Tetrahedra21Wide band gaps in nonlinear optical materials AMgAgGa6S11 (A = K, Rb) achieved by the incorporation of dual s-block elements in Ag-based sulfide11A survey of stereoactive oxysalts for linear and nonlinear optical applications40ASn(C10H12N2O8)Cl·H2O (A = K, Rb): Nonlinear optical crystals with new distorted Sn(IV)-centered nitrogen-oxygen-chloride polyhedron and wide band gaps6A potassium lead 2-methylmalonate-iodide nonlinear optical crystal with strong second-harmonic generation response and large birefringence2A prediction-driven database to enable rapid discovery of nonlinear optical materials46Tailored Synthesis of Two Metal Borates KSrM3B2O9 (M = Al and Ga) Exhibiting Wide Ultraviolet Transparency4Rb 3 MgB 5 O 10 and LiBaAl(BO 3 ) 2 : covalent tetrahedra MO 4 -containing borates with deep-ultraviolet cutoff edges9A Sharp Improvement of Sulfate's Birefringence Induced by the Synergistic Effect of Heteroleptic and Dimeric Strategies14K 2 RbB 8 PO 16 : A Borophosphate with Moderate Birefringence and Deep-Ultraviolet Transmission10Nonlinear Optical Phosphide CuInSi2P4: The Inaugural Member of Diamond-Like Family I–III–IV2–V4 Inspired by ZnGeP216“One stone two birds” design of borates featuring edge-sharing [BO 4 ] and different B–O configurations in one structure utilizing covalent tetrahedra8Ca 3 Al 2 B 8 O 18 : borate with a graphene-like layer featuring two types of topological six-membered rings induced by [AlO 4 ] units7CsAlB 3 O 6 Cl: the rational construction of a KBBF-type structure with aligned 2 ∞ [AlB 3 O 6 Cl] layers via introducing unprecedented [AlO 3 Cl] tetrahedra5From BaAlBO 3 F 2 to BaAlB 3 O 6 F 2 and BaAl 2 (B 3 O 6 ) 2 F 2 : the enhancement of birefringence and band gap by extending the π-conjugated system combined with [Al–O/F] functional groups13K, Rb-hydroxyborates series with deep-ultraviolet KRbB 5 O 8 (OH) possessing moderate second harmonic generation response0K3B6O10Br紫外非线性光学晶体研究进展(特邀)7Recent advances in rational structure design for nonlinear optical crystals: leveraging advantageous templates153Shooting short-wavelength nonlinear optical materials with targeted balance performances in hydroxyborates through first-principles high-throughput screening4Design of Deep-Ultraviolet Zero-Order Waveplate Materials by Rational Assembly of [AlO2F4] and [SO4] Groups9KREP 2 S 6 (RE = Sm, Gd, Tb, Dy): A Series of Polar Rare-Earth Thiophosphates with High Laser-Induced Damage Thresholds and Moderate Nonlinear-Optical Responses Synergistically Contributed by Isolated P 2 S 6 Units and {[RE 2 S 15 ] 24– } ∞ Layers8Dual-Anion Strategy Induces Dual Enhancement Toward Ultrashort Phase-Matching Wavelength in Deep-UV Transparent d0 Transition Metal Oxyfluorides21A2Pb3[H2N(CH2COO)2]3Cl5 (A = K, Rb): Porous Crystals Constructed on [Pb3Cl5O6] Clusters with Comprehensive Nonlinear Optical Performance3NaRbB10O14(OH)4 and Na3CsB10O16(OH)2: Two Cases of Hydroxyborates with [B5Om(OH)n] Units and Deep Ultraviolet Cutoff Edges6Structure‐Prediction‐Oriented Synthesis of Thiophosphates as Promising Infrared Nonlinear Optical Materials24Structure‐Prediction‐Oriented Synthesis of Thiophosphates as Promising Infrared Nonlinear Optical Materials1Synthesis, structure, and oxygen reduction reaction activity of 1-isopropylimidazole and 1-propylimidazole ligand-nickel borate crystals2Review on birefringence in borates based on birefringence-active functional groups and arrangements57A3Sc(SO4)3 (A = K, Rb, Cs): Three Deep‐Ultraviolet Transparent Alkali‐Scandium Sulfates with Strong Second‐Harmonic Generation Response and High Thermal Stability14RE(HSeO3)(SeO3)(H2O)·(H2O) (RE = Y, Gd): Two Rare-Earth Selenite Nonlinear Optical Crystals with Wide Band Gaps6Elucidating the Photo‐Induced Electronic Structure and Mechanisms of ZnAl‐Layered Double Hydroxide: A DFT Study0Novel antimony-based mixed halides exhibiting an excellent SHG response and a broad transmission range20K 15 La 7 (BO 3 ) 12 : A KBBF-Like Nonlinear-Optical Material with a Short Cutoff Edge and a Strong Second-Harmonic-Generation Response10An excellent ultraviolet nonlinear optical crystal derived from the polar methylphosphonate unit8Coordinated assembly of alkali and alkaline earth metals with the perfluorinated [AlF 6 ] group to design deep-ultraviolet zero-order waveplate materials2LiBa 3 Al 2 B 3 O 11 : a deep-ultraviolet transparent optical borate featuring a 2D [Al 2 B 3 O 11 ] ∞ layered structure0Na 2 PbB 6 O 10 SO 4 and Ca 2.58 Pb 0.42 B 6 O 11 SO 4 : first borate–sulfates featuring 3D porous borate anionic frameworks0层状结构深紫外非线性光学晶体研究进展(特邀)2Deep-UV laser source based on χ (2) optical frequency conversion and χ (3) stimulated Raman scattering4A Promising Deep Ultraviolet Nonlinear Optical Crystal Activated by the Ordered Structure Design40A Promising Deep Ultraviolet Nonlinear Optical Crystal Activated by the Ordered Structure Design3Templated borates derived copper-based oxygen reduction reaction catalysts for zinc-air batteries2[C( NH2 )3] 2SiF6 : Design of Deep Ultraviolet Crystals with Large Birefringence Based on a Fluorination‐Oriented Strategy13NH4B5O7(OH)2 and CsRbB10O14(OH)4·H2O: Two Hydroxyborates Feature Significant Optical Anisotropy and Contain 1∞[B5O7(OH)2] Chains1Cation-modulated aligned arrangement of [B3O7] units in an unprecedented 2∞[B3O5] layer with remarkable birefringence10Modulation of Crystal Structure and Birefringence: Cation Size Effect in Alkali Metal Fluoroaluminoborates4Alkali Metal Substitution-Induced Structural Transformation for RbREP2Se6 (RE = Gd, Tb, Dy) with Second-Harmonic Generation Responses6Design, synthesis and characterization of a novel chalcone derivative crystal with high second harmonic generation efficiency1Enhancement of Birefringence in Alkali Metal Sulfates Induced by Rare Earth Metal-Centered Polyhedra and Structure Regulation via Cations2Tuning birefringence in alkaline-earth metal oxyhalides through diverse mixed-cation coordination architectures1ANb 2 (PS 4 )(S 2 ) 3 (A = K, Rb, Cs): the first Nb-based NLO thiophosphates with [NbS 2 (S 2 ) 3 ] and [Nb 2 PS 6 (S 2 ) 4 ] units exhibiting tri-state structural transformation and high performance6Asymmetry-driven organic–inorganic hybrid strategy for constructing structures with exceptional organofunctionalized B–O units2[Al(H 2 O) 6 ](NO 3 )Cl 2 : achieving parallel arrangement of functional units and birefringence enhancement through free halogen-mediated structural regulation0Ba 4 Al 4 SnS 12 : balancing bandgap and nonlinear optical performance in thioaluminate via multifunctional group engineering0CsB(OH) 4 (H 2 O) 2 and Na(NH 4 ) 2 B 10 O 16 OH(H 2 O): a hydroxylation modification strategy regulates the borate structures and optical properties0Synergism of [C 2 N 4 H 7 S] cations and anionic modulators: tailoring second-order nonlinear optics and birefringence in organic–inorganic crystals6Tailoring linear and nonlinear optical properties of 2D Sc 2 C MXenes via surface termination modulation0Rare-Earth Selenophosphates Cs 2 YP 2 Se 7 and KYP 2 Se 6 Synthesized by the RFMOBQ Routine: Structural Evolution and Nonlinear Optical Activity2The Achievement of a Strong Second Harmonic Generation Response and a Large Birefringence in Sulfates4An Ultraviolet Transparent Nonlinear Optical Crystal Assembled from a Polarizable Tetrahedral Unit1Boosting Ultraviolet Phase‐Matching Performance of B 3 O 7 ‐Based Systems via Synergistic Fluorination and Organic Modification Strategy1Record‐High Birefringence with Ultralow Dichroic Loss Realized by Cation‐Templated Engineering Ordered Assembly of Linear Birefringent‐Active Unit6Deep-Ultraviolet Transparent Zr/Hf Fluorides with Second-Harmonic Generation Effects Induced by Alkali-Metal Modulation2Breakthrough in High Quality LaBGeO 5 Crystal for Deep Ultraviolet Quasi-Phase Matching Application0Nonlinear Optical-Active NaAlP 2 S 6 Synthesized by the MOBQ Method: Synthesis, Structure, and Optical Properties0[CN4H8]SiF6: Fluorination-guided design of deep-UV crystal with large birefringence0Potential Deep Ultraviolet Phosphate With Y‐Based: 1 [(PO 3 ) 4 ] ∞ Chains AYP 4 O 12 (A = K, NH 4 ) and the First [P 3 O 10 ] Anionic Framework KLiYP 3 O 100A Hydrogen-Bonded Molecular Crystal with Strong Optical Anisotropy and Large Second-Harmonic Generation Response0MAlB3O6F2 (M = Ca and Pb): Two New Fluoroaluminoborates Featuring π-Conjugated [BO3] and [AlO4F2] Units with Large Birefringence0Fluorination‐Driven Molecular Polarization Engineering in Hydroxyfluorooxoborates for Generating Strong Short‐Wavelength Nonlinear Optical Responses0Cation‐Regulated [CH 3 BO 2 F]‐Derived Borates: Synergistic Fluorination and Organic Functionalization for High‐Birefringence UV NLO Materials0

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  1. Anisotropic structure building unit involving diverse chemical bonds: a new opportunity for high-performance second-order NLO materials

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  2. Hg 3 O 2 (NO 3 )F: a mercury nitrate oxyfluoride with an unprecedented [(Hg 3 O 2 F) + ] ∞ cationic framework and excellent optical anisotropy

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  3. Fluorooxoborates: A precious treasure of deep-ultraviolet nonlinear optical materials

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  4. Recent progress in ultraviolet and deep-ultraviolet nonlinear optical aluminoborates

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  5. [K2PbX][Ga7S12] (X = Cl, Br, I): The First Lead‐Containing Cationic Moieties with Ultrahigh Second‐Harmonic Generation and Band Gaps Exceeding the Criterion of 2.33 eV

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  6. Structural Motif Cosubstitution Strategy for Designing Fluoroaluminoborate with the Sr2Be2B2O7-Type Double-Layered Structure

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  7. Y(HSeO3)(SeO3)(H2O)·(H2O) and Y2(SeO3)2(SeO4)(H2O)2·(H2O)0.75: Two yttrium selenites with a short UV cut-off edge explored from pure selenite compounds

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  8. Three Polyborates with High-Symmetry [B12O24] Units Featuring Different Dimensions of Anion Groups

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  9. Recent Progress in Crystalline Borates with Edge-Sharing BO4 Tetrahedra

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  10. Wide band gaps in nonlinear optical materials AMgAgGa6S11 (A = K, Rb) achieved by the incorporation of dual s-block elements in Ag-based sulfide

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

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  12. ASn(C10H12N2O8)Cl·H2O (A = K, Rb): Nonlinear optical crystals with new distorted Sn(IV)-centered nitrogen-oxygen-chloride polyhedron and wide band gaps

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  13. A potassium lead 2-methylmalonate-iodide nonlinear optical crystal with strong second-harmonic generation response and large birefringence

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  14. A prediction-driven database to enable rapid discovery of nonlinear optical materials

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  15. Tailored Synthesis of Two Metal Borates KSrM3B2O9 (M = Al and Ga) Exhibiting Wide Ultraviolet Transparency

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  16. Rb 3 MgB 5 O 10 and LiBaAl(BO 3 ) 2 : covalent tetrahedra MO 4 -containing borates with deep-ultraviolet cutoff edges

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  17. A Sharp Improvement of Sulfate's Birefringence Induced by the Synergistic Effect of Heteroleptic and Dimeric Strategies

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  18. K 2 RbB 8 PO 16 : A Borophosphate with Moderate Birefringence and Deep-Ultraviolet Transmission

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  19. Nonlinear Optical Phosphide CuInSi2P4: The Inaugural Member of Diamond-Like Family I–III–IV2–V4 Inspired by ZnGeP2

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  20. “One stone two birds” design of borates featuring edge-sharing [BO 4 ] and different B–O configurations in one structure utilizing covalent tetrahedra

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  21. Ca 3 Al 2 B 8 O 18 : borate with a graphene-like layer featuring two types of topological six-membered rings induced by [AlO 4 ] units

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  22. CsAlB 3 O 6 Cl: the rational construction of a KBBF-type structure with aligned 2 ∞ [AlB 3 O 6 Cl] layers via introducing unprecedented [AlO 3 Cl] tetrahedra

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  30. Dual-Anion Strategy Induces Dual Enhancement Toward Ultrashort Phase-Matching Wavelength in Deep-UV Transparent d0 Transition Metal Oxyfluorides

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  31. A2Pb3[H2N(CH2COO)2]3Cl5 (A = K, Rb): Porous Crystals Constructed on [Pb3Cl5O6] Clusters with Comprehensive Nonlinear Optical Performance

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  32. NaRbB10O14(OH)4 and Na3CsB10O16(OH)2: Two Cases of Hydroxyborates with [B5Om(OH)n] Units and Deep Ultraviolet Cutoff Edges

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  33. Structure‐Prediction‐Oriented Synthesis of Thiophosphates as Promising Infrared Nonlinear Optical Materials

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  34. Structure‐Prediction‐Oriented Synthesis of Thiophosphates as Promising Infrared Nonlinear Optical Materials

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  35. Synthesis, structure, and oxygen reduction reaction activity of 1-isopropylimidazole and 1-propylimidazole ligand-nickel borate crystals

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  36. Review on birefringence in borates based on birefringence-active functional groups and arrangements

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  37. A3Sc(SO4)3 (A = K, Rb, Cs): Three Deep‐Ultraviolet Transparent Alkali‐Scandium Sulfates with Strong Second‐Harmonic Generation Response and High Thermal Stability

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

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  39. Elucidating the Photo‐Induced Electronic Structure and Mechanisms of ZnAl‐Layered Double Hydroxide: A DFT Study

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  42. An excellent ultraviolet nonlinear optical crystal derived from the polar methylphosphonate unit

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  43. Coordinated assembly of alkali and alkaline earth metals with the perfluorinated [AlF 6 ] group to design deep-ultraviolet zero-order waveplate materials

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  48. A Promising Deep Ultraviolet Nonlinear Optical Crystal Activated by the Ordered Structure Design

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  49. A Promising Deep Ultraviolet Nonlinear Optical Crystal Activated by the Ordered Structure Design

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  50. Templated borates derived copper-based oxygen reduction reaction catalysts for zinc-air batteries

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