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RESEARCH PAPER · Angewandte Chemie International Edition · 2022

Promising Deep‐Ultraviolet Birefringent Materials via Rational Design and Assembly of Planar π‐Conjugated [B(OH)3] and [B3O3(OH)3] Functional Species

Jiahao Jiao, Meng Cheng, Rong Yang, Yuchen Yan, Min Zhang, Fangfang Zhang, Zhihua Yang, Shilie Pan

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Promising Deep‐Ultraviolet Birefringent Materials via Rational Design and Assembly of Planar π‐Conjugated [B(OH)3] and [B3O3(OH)3] Functional SpeciesOriginalA 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 birefringence17Ba 2 Zn 2 B 6 O 13 : coplanar [B 2 O 5 ] in unnoted U-shaped [B 6 O 13 ] groups achieving large birefringence6KF·B(OH) 3 : a KBBF-type material with large birefringence and remarkable deep-ultraviolet transparency33Na 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 edge8Performance of optical materials with the derivative of planar π-conjugated groups: Recent advances and future prospects37Cs2B4O5(OH)4: A new hydrated borate with a short UV cutoff edge2Ba6Zn6(B3O6)6(B6O12): Barium Zinc Borate Contains π-Conjugated [B3O6]3– Anions and [B6O12]6– Anion with Edge-Sharing BO4 Tetrahedra36Li0.5Na0.5AlB2O4F2: Fluoroaluminoborate with Aligned 1∞[BO2] Chain Induced by Unprecedented [AlO3F3]6− Species Features Enhanced Birefringence30Aluminoborates as Nonlinear Optical Materials79Aluminoborates as Nonlinear Optical Materials14An effective pathway to design and synthesize UV birefringent crystals via rational assembly of π-conjugated [CO 3 ] 2− and [NO 3 ] − triangles32K 5 [B 3 O 3 F 4 (OH)] 2 (NO 3 ): the first hydroxyfluorooxoborate-nitrate with a short ultraviolet cutoff edge and large birefringence18Linear π-conjugated units of the D ∞h point group as superior ultraviolet birefringent units1Mg 2 Pb 2 Si 2 O 7 F 2 : a new lead-containing alkali earth metal silicate fluoride with a short cutoff edge2Recent progress in borate-based short-wavelength nonlinear optical crystals with boron–oxygen skeleton modification28Two UV optical crystals with strong optical anisotropy, large band gaps and an α-BBO type structure7Fluorooxoborates: A precious treasure of deep-ultraviolet nonlinear optical materials24Structural Motif Cosubstitution Strategy for Designing Fluoroaluminoborate with the Sr2Be2B2O7-Type Double-Layered Structure14Theoretical Prediction‐Assisted Synthesis and Characterization of Infrared Nonlinear Optical Material NaSrBS324Cs 2 Mg(H 2 C 3 N 3 S 3 ) 4 ·8H 2 O: An Excellent Birefringent Material with Giant Optical Anisotropy in π-Conjugated Trithiocyanurate19“Cation Activation”: An Effective Strategy for the Enhancement of Birefringence36Three Polyborates with High-Symmetry [B12O24] Units Featuring Different Dimensions of Anion Groups8Mixed Alkali Metal and Alkaline Earth Metal Scandium Borate Birefringence Material with Layered Structure and Short Ultraviolet Cutoff Edge17Improved Birefringence Activated by Tetrahedra Decorated with a Single Linear Unit38Improved Birefringence Activated by Tetrahedra Decorated with a Single Linear Unit1The Strategy to Improve the Phase Matching Ability in Tetrahedron‐Based Deep‐Ultraviolet Nonlinear Optical Crystals21Centrosymmetric Rb2Sb(C2O4)2.5(H2O)3 and Noncentrosymmetric RbSb2(C2O4)F5: Two Antimony (III) Oxalates as UV Optical Materials20Rb 3 MgB 5 O 10 and LiBaAl(BO 3 ) 2 : covalent tetrahedra MO 4 -containing borates with deep-ultraviolet cutoff edges9K 2 RbB 8 PO 16 : A Borophosphate with Moderate Birefringence and Deep-Ultraviolet Transmission10Achieving great optical anisotropy with the well-directed alignment of π-conjugated groups due to hydrogen bonds9Cd8(BO3)4SiO4: Metal Cation Inducing the Formation of Isolated [BO3] and [SiO4] Units in Borate Silicate15“One stone two birds” design of borates featuring edge-sharing [BO 4 ] and different B–O configurations in one structure utilizing covalent tetrahedra8C 8 H 6 IN 3 O 4 : a birefringent crystal induced by uniformly aligned hybrid groups10Ca 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] tetrahedra5Exploration of antimony( iii ) oxyhalides via single-site substitution in quest of large birefringence10Recent advances in rational structure design for nonlinear optical crystals: leveraging advantageous templates153Syntheses, structures and characterization of noncentrosymmetric MZnPO 4 (M = K, NH 4 )4Hierarchical van der Waals Assemblies to Boost Deep‐Ultraviolet Nonlinear‐Optical Capabilities in Boron Phosphate8AX·(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 Gap20Extending Unique 1D Double-Chains to 2D Layers with Birefringent Gain by Introducing a Hydroxyl Group5Two Hydroxyfluorooxoborates Achieving Deep‐Ultraviolet Cutoff Edges and Moderate Birefringence by Assembling Multi‐Anionic Groups6Na3K6(CO3)3(NO3)2X·6H2O (X = NO3, Cl, Br): Exploring High-Performance UV Birefringent Crystals Induced by Coplanar π-Conjugated CO3 and NO3 Groups15NaRbB10O14(OH)4 and Na3CsB10O16(OH)2: Two Cases of Hydroxyborates with [B5Om(OH)n] Units and Deep Ultraviolet Cutoff Edges6Zn(C6H4NO2)2·4H2O: A Solar-Blind Birefringent Crystal5Review on birefringence in borates based on birefringence-active functional groups and arrangements57NaK5La2(SO4)6: Enhanced Birefringence of Multiple-Alkali Metal Sulfate Systems via Rare Earth Metal-Centered Polyhedra5(C3N2H5)B3O3F2(OH)2: Realizing Large Birefringence via a Synergistic Effect between Anion F/OH‐Ratio Optimization and Cation Activation25LiNa2Ca8B12O24F6Cl and Li1.2Na2.8B6O11: A Case of Cation-Induced Birefringence Enhancement via Dimensional Changes of Highly Polymerized [B12O24] Motifs10From B 3 O 3 (OH) 3 to B 3 O 3 F 3 : Uncovering Series of New Functional Units Based on [BO 2 F] Beneficial for Deep‐Ultraviolet Birefringence1Rational Design and Controlled Synthesis of High-Performance Inorganic Short-Wave UV Nonlinear Optical Materials150CsBO(OH) 2 : a new hydroxyborate with the rare [BO(OH) 2 ] group and a deep ultraviolet cutoff edge3RbB 7 O 10 (OH) 2 and NaB 11 O 16 (OH) 2 : alkali metal hydroxyborates with two-dimensional layered structures and large birefringence1Structural chemistry of antimony( iii ) oxalates with lone pairs: polyhedral distortion [SbO 4 F 2 ], π-conjugation [C 2 O 4 ], and birefringence tuning1新型非线性光学晶体和双折射晶体的研究进展（特邀）4Can Low Structural Anisotropy Produce High Optical Anisotropy? Anomalous Giant Optical Birefringent Effect in PI4AlI4 in Focus11K3[HCO3]2F: a new deep-UV birefringent crystal exhibiting strong optical anisotropy17Non-equivalent terminating roles of hydroxyl and fluorine in hydroxy/fluorooxo-borate optical functional materials2[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 birefringence10Promising UV/DUV nonlinear optical materials with X-membered (X = multiples of 6) rings in anhydrous inorganic borates20Triple Integration of π‐Conjugated Building Blocks: Unprecedented Assembly for Large Optical Anisotropy11Effect of Multiple Hydrogen Bonding on the π-Conjugated Groups and Optical Properties in Molecular Crystals5Asymmetry-driven organic–inorganic hybrid strategy for constructing structures with exceptional organofunctionalized B–O units2A multi-scale birefringence modulation strategy in DUV/UV crystals induced by organic cations1Design of borate-squarate hybrid crystals with large birefringence by synergistic assembly of planar π-conjugated groups0The condensation of π-conjugated units: a new paradigm for designing high-performance optical crystals4Truss bridge-like anhydrous stacking in hybrid crystals triggers ultra-high stability and robust birefringence0Unit Symmetry‐Breaking and Layered Linear Ordering Enabling Superior Short‐Wave Ultraviolet Birefringent Crystal8Solid–Liquid Phase Equilibrium in the Quaternary System H 3 BO 3 + CsCl + RbCl + H 2 O at 298.15 K and Identification of a Solid Solution Phase 2H 3 BO 3 ·3(Cs,Rb)Cl1Significant Enhancement of Birefringence Resulting from the Introduction of [BO 2 (OH)] Groups into Borosulfates0Boosting Ultraviolet Phase‐Matching Performance of B 3 O 7 ‐Based Systems via Synergistic Fluorination and Organic Modification Strategy1Synergistic Enhancement of Optical Anisotropy in Nitrate Sulfamate for UV Applications: Role of Functional Group Alignment and Hydrogen Bond Network1Hydrogen‐Bond‐Directed Assembly of Urea Derivatives: Exceptional Birefringence Achieved by π ‐Conjugated Unit Alignment3F−/OH− terminal modification of [B3O6] clusters: Constructing deep-ultraviolet hydroxyfluorooxoborates with tunable optical performance0Steric hindrance and hydrogen-bond networks synergistically directing molecular alignment for high-performance ultraviolet birefringent1K 3 Yb 2 (BO 3 ) 3 and Rb 3 Yb 2 (BO 3 ) 3 : Two Rare-Earth Borate Ultraviolet Nonlinear Optical Crystals1Parallel arrangement of functional building blocks: toward performance synergy in oxalate borate ultraviolet nonlinear optical crystals0From High Symmetry to High Symmetry: A Self‐Assembly Strategy for Synthesizing Large Birefringent Borates0Solid–Liquid Phase Equilibrium in the Ternary Systems C6H5B(OH)2 + KCl/RbCl/CsCl + H2O at 298.15 and 348.15 K0Fluorination‐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. A 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 birefringence

    Chemical Communications · 2022-01-01

    Zilong Chen, Zi‐Jian Li, Dongdong Chu, Fangfang Zhang, Xiaojing Li, Zhihua Yang, Xifa Long, Shilie Pan

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  2. Ba 2 Zn 2 B 6 O 13 : coplanar [B 2 O 5 ] in unnoted U-shaped [B 6 O 13 ] groups achieving large birefringence

    Chemical Communications · 2022-01-01

    Rui Zhang, Xin Su, Jie Zhang, Dulin Wen, Yineng Huang

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  3. KF·B(OH) 3 : a KBBF-type material with large birefringence and remarkable deep-ultraviolet transparency

    Chemical Communications · 2022-01-01

    Yang Li, Xinglong Chen, Kang Min Ok

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  4. Na 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 edge

    Dalton Transactions · 2022-01-01

    Jianlong Huang, Chengfa Wu, Jianbang Chen, Zhiyong Guo, Wenjuan Ma, Feng Yu, Bin Dai

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  5. Performance of optical materials with the derivative of planar π-conjugated groups: Recent advances and future prospects

    Inorganic Chemistry Frontiers · 2022-01-01

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  6. Cs2B4O5(OH)4: A new hydrated borate with a short UV cutoff edge

    Inorganica Chimica Acta · 2022-10-19

    Aixin Zhu, Jianbang Chen, Yanhui Zhang, Zhi Guo Su

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  7. Ba6Zn6(B3O6)6(B6O12): Barium Zinc Borate Contains π-Conjugated [B3O6]3– Anions and [B6O12]6– Anion with Edge-Sharing BO4 Tetrahedra

    Inorganic Chemistry · 2022-10-28

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  8. Li0.5Na0.5AlB2O4F2: Fluoroaluminoborate with Aligned 1∞[BO2] Chain Induced by Unprecedented [AlO3F3]6− Species Features Enhanced Birefringence

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  9. Aluminoborates as Nonlinear Optical Materials

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  10. Aluminoborates as Nonlinear Optical Materials

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  11. An effective pathway to design and synthesize UV birefringent crystals via rational assembly of π-conjugated [CO 3 ] 2− and [NO 3 ] − triangles

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    Zhaowei Hu, Lili Liu, Ruixin Zhang, Qun Jing, Huan Wang, Jindan Tian, Jiayue Xu, P. Shiv Halasyamani

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  12. K 5 [B 3 O 3 F 4 (OH)] 2 (NO 3 ): the first hydroxyfluorooxoborate-nitrate with a short ultraviolet cutoff edge and large birefringence

    Dalton Transactions · 2023-01-01

    Luyong Zhang, Shi‐Bin Wang, Fangfang Zhang, Zhihua Yang, Xueling Hou

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  13. Linear π-conjugated units of the D ∞h point group as superior ultraviolet birefringent units

    Physical Chemistry Chemical Physics · 2023-01-01

    Rong Yang, Abudukadi Tudi, Yu Dang, Kewang Zhang, Hongsheng Shi

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

    New Journal of Chemistry · 2023-01-01

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  15. Recent progress in borate-based short-wavelength nonlinear optical crystals with boron–oxygen skeleton modification

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  16. Two UV optical crystals with strong optical anisotropy, large band gaps and an α-BBO type structure

    Dalton Transactions · 2023-01-01

    Lehui Liu, Feifei Yuan, Yisheng Huang, Zhoubin Lin, Lizhen Zhang

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

    Chinese Journal of Structural Chemistry · 2023-02-03

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

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  19. Theoretical Prediction‐Assisted Synthesis and Characterization of Infrared Nonlinear Optical Material NaSrBS3

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  20. Cs 2 Mg(H 2 C 3 N 3 S 3 ) 4 ·8H 2 O: An Excellent Birefringent Material with Giant Optical Anisotropy in π-Conjugated Trithiocyanurate

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    Xia Hao, Chensheng Lin, Min Luo, Yuqiao Zhou, Ning Ye, Enbo Shangguan

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  21. “Cation Activation”: An Effective Strategy for the Enhancement of Birefringence

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

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  23. Mixed Alkali Metal and Alkaline Earth Metal Scandium Borate Birefringence Material with Layered Structure and Short Ultraviolet Cutoff Edge

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  24. Improved Birefringence Activated by Tetrahedra Decorated with a Single Linear Unit

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  25. Improved Birefringence Activated by Tetrahedra Decorated with a Single Linear Unit

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  26. The Strategy to Improve the Phase Matching Ability in Tetrahedron‐Based Deep‐Ultraviolet Nonlinear Optical Crystals

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  27. Centrosymmetric Rb2Sb(C2O4)2.5(H2O)3 and Noncentrosymmetric RbSb2(C2O4)F5: Two Antimony (III) Oxalates as UV Optical Materials

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

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  30. Achieving great optical anisotropy with the well-directed alignment of π-conjugated groups due to hydrogen bonds

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  31. Cd8(BO3)4SiO4: Metal Cation Inducing the Formation of Isolated [BO3] and [SiO4] Units in Borate Silicate

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  32. “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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  33. C 8 H 6 IN 3 O 4 : a birefringent crystal induced by uniformly aligned hybrid groups

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  34. 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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  35. 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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  36. Exploration of antimony( iii ) oxyhalides via single-site substitution in quest of large birefringence

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  37. Recent advances in rational structure design for nonlinear optical crystals: leveraging advantageous templates

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  38. Syntheses, structures and characterization of noncentrosymmetric MZnPO 4 (M = K, NH 4 )

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  39. Hierarchical van der Waals Assemblies to Boost Deep‐Ultraviolet Nonlinear‐Optical Capabilities in Boron Phosphate

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  40. 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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  41. Extending Unique 1D Double-Chains to 2D Layers with Birefringent Gain by Introducing a Hydroxyl Group

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  42. Two Hydroxyfluorooxoborates Achieving Deep‐Ultraviolet Cutoff Edges and Moderate Birefringence by Assembling Multi‐Anionic Groups

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  43. Na3K6(CO3)3(NO3)2X·6H2O (X = NO3, Cl, Br): Exploring High-Performance UV Birefringent Crystals Induced by Coplanar π-Conjugated CO3 and NO3 Groups

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  44. 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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  45. Zn(C6H4NO2)2·4H2O: A Solar-Blind Birefringent Crystal

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

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  47. NaK5La2(SO4)6: Enhanced Birefringence of Multiple-Alkali Metal Sulfate Systems via Rare Earth Metal-Centered Polyhedra

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  48. (C3N2H5)B3O3F2(OH)2: Realizing Large Birefringence via a Synergistic Effect between Anion F/OH‐Ratio Optimization and Cation Activation

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  49. LiNa2Ca8B12O24F6Cl and Li1.2Na2.8B6O11: A Case of Cation-Induced Birefringence Enhancement via Dimensional Changes of Highly Polymerized [B12O24] Motifs

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    Ziting Yan, Jinbin Fan, Dongdong Chu, Zhihua Yang, Juanjuan Lu, Shilie Pan, Min Zhang

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  50. From B 3 O 3 (OH) 3 to B 3 O 3 F 3 : Uncovering Series of New Functional Units Based on [BO 2 F] Beneficial for Deep‐Ultraviolet Birefringence

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