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RESEARCH PAPER · Angewandte Chemie International Edition · 2023

Birefringence Regulation by Clarifying the Relationship Between Stereochemically Active Lone Pairs and Optical Anisotropy in Tin‐based Ternary Halides

Jingyu Guo, Junben Huang, Abudukadi Tudi, Xueling Hou, Shujuan Han, Zhihua Yang, Shilie Pan

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Birefringence Regulation by Clarifying the Relationship Between Stereochemically Active Lone Pairs and Optical Anisotropy in Tin‐based Ternary HalidesOriginal(C 5 H 6.16 N 2 Cl 0.84 )(IO 2 Cl 2 ): a birefringent crystal featuring unprecedented (IO 2 Cl 2 ) − anions and π-conjugated organic cations56Three Borates Belonging to the A(I)7Ae(II)Re(III)2B15O30 Family as Promising Nonlinear Optical Crystals12Hydroxyl-Driven Enhanced Birefringence in Borophosphates3PbTeB 4 O 9 : a lead tellurium borate with unprecedented fundamental building block [B 4 O 10 ] and large birefringence12(C(NH2)3)2(I2O5F)(IO3)(H2O) and C(NH2)3IO2F2: Two Guanidine Fluorooxoiodates with Wide Band Gap and Large Birefringence20[Sn 3 OF]PO 4 vs. [Sn 3 F 3 ]PO 4 : enhancing birefringence by breaking the R 3 symmetry and realigning lone pairs12A highly birefringent metal-free crystal assembled by cooperative non-covalent interactions30Amine-directed synthesis, valence state control, and optical properties of two new organic–inorganic tin chlorides7Equivalent cation-tuning to realize a new Ce( iv ) fluoride with excellent comprehensive nonlinear optical performances12Explorations of highly birefringent materials in the vanadium oxyfluoride–iodate system by fluoride ion modulation8From 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 groups13Novel antimony phosphates with enlarged birefringence induced by lone pair cations4Sb4O5I2: Enhancing Birefringence through Optimization of Sb/I Ratio for Alignment of Stereochemically Active Lone Pairs18Giant Optical Anisotropy in a Covalent Molybdenum Tellurite via Oxyanion Polymerization43C(NH2)3MoO3(IO3): A Molybdenyl Iodate with Giant Birefringence Designed via a Cation–Anion Synergetic Interaction Strategy36Enhanced UV Nonlinear Optical Properties in Layered Germanous Phosphites through Functional Group Sequential Construction11Enhanced UV Nonlinear Optical Properties in Layered Germanous Phosphites through Functional Group Sequential Construction116RE(HSeO3)(SeO3)(H2O)·(H2O) (RE = Y, Gd): Two Rare-Earth Selenite Nonlinear Optical Crystals with Wide Band Gaps6(C10N2H10)(HI2O6)(HIO3)(IO3): A Birefringent Material Featuring Large π-Conjugated Organic Cation and Two Types of Iodate Anions2Novel 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 Response10(C 6 H 5 N 2 )HgCl 3 : Discovery of a Polar Hg‐Based Hybrid Halide as Preeminent Nonlinear Optical and Birefringent Material Activated by π‐Conjugated Organic Cation Substitution38(C 5 N 2 H 7 )IO 2 F 2 and (C 3 N 6 H 8 )(IO 2 F 2 ) 2 : two new organic–inorganic hybrid fluoroiodate birefringent crystals7A π-conjugated organic molecule-modified strategy to achieve high-performance metal nitrate birefringent crystals9Bulk crystal growth and optical properties of a novel organic–inorganic hybrid nonlinear optical thiocyanate: [Mn(CH 3 CONH 2 ) 2 ] [Hg(SCN) 4 ]10Cation tuning in anionic framework hydroborates: tailored deep-ultraviolet optical crystals with large birefringence1Hg 2 (HTe 2 O 5 )(PO 4 ): a novel phosphate crystal with enhanced birefringence enabled by the synergistic modification of multiple functional groups12Hg[CS(NH 2 ) 2 ] 4 (SiF 6 ): a fluorosilicate crystal with large birefringence achieved via multi-functional group modification6M 3 MoO 4 (HCO 3 ) (M = Rb and Cs): cation-tuned synthesis of two noncentrosymmetric molybdate-carbonates with isolated [MoO 4 ] and [HCO 3 ] groups0Optimizing optical anisotropy in low-dimensional structures via intralayer hydrogen bonding modulation and anionic substitution17BaFS: Birefringence Enhanced by the Transformation from Optical Isotropy to Anisotropy via Interlayer Anion Substitution8Design and Synthesis of Two Sn-Centered Mixed Halide Crystals with Enhanced Birefringence8Underlying Dynamics of Double-Halide Perovskites: Unraveling Structural Complexity, Bandgap Modulation, Optical, and Carrier Dynamics for Next-Generation Optoelectronics24Metal Cation Engineered UV Birefringent Crystals in π‐Conjugated Sulfonates with Record‐High Optical Anisotropy17Improving the Performance of Birefringent Crystals by Molecular Assembly Strategy in the Solar‐Blind UV Region14[CON3H6BF4]: An Efficient Metal‐Free Borate with Optimized Birefringence Achieved by Structural Design Strategy15Dual‐Sided Multidentate Coordination Strategy Enables Record Birefringence in UV‐Transparent Antimony‐Based Hybrid Crystals37Dual‐Sided Multidentate Coordination Strategy Enables Record Birefringence in UV‐Transparent Antimony‐Based Hybrid Crystals11Reversal Enhancement of Birefringence by Stereochemically Active Lone Pairs in Sn(II)-Based Mixed Halides0Low‐Dimensional Organic–Inorganic Hybrid Metal Halide with Large Optical Anisotropy9[Pb(ptz)(OH)(H2O)]: A Hybrid Nonlinear Optical Crystal with Large Birefringence0K 2 GdB 3 O 6 F 2 : A Promising Short-Wave UV Birefringent Crystal via Optimized Assembly of π-Conjugated [B 3 O 6 ] Groups8Hybrid Zinc‒Based Halides with Giant Optical Anisotropy via Protonation‒Engineered π ‒Conjugated Organic Group24K 6 Mo 8 PO 29 OH·H 2 O and K 6 Mo 5 P 2 O 23 ·7H 2 O: strongly distorted [MoO 6 ] octahedral groups effectively enhance birefringence0Achieving Ultra‐High Optical Anisotropy via Structural Regulation and Coplanar Engineering of Extended π‐Conjugated [H 2–x C 3 N 3 S 3 ] (x = 1, 2) Groups3A 2 Sb 2 SO 4 F 6 (A = NH 4 + , Na + ): two sulfate fluoride crystals exhibiting enhanced birefringence driven by stereochemically active antimony( iii )1Layered perovskite-like nitrates A 2 Ca(NO 3 ) 2 Cl 2 (A = Rb, Cs) as ultraviolet birefringent optical materials3Na 2 SnSO 4 F 2 : an ultraviolet-transparent sulfate crystal with large birefringence driven by stereochemically active tin( ii )1The modulation of structural polarity facilitating the gradient enhancement of second harmonic generation effects in hybrid metal halides5Halogen Anion-Mediated Substitution of Nitrate: Toward Polar Materials with Intense Second-Harmonic Generation Effects3Electronegativity Adaption Approach for Solar‐Blind UV Birefringent Crystals With Ultrawide Bandgaps2Enhanced Birefringence in Organic–Inorganic Hybrid Antimony Halides via Partial Halogen Substitution1Rb 2 ZnGe 3 Se 8 : A Large-Birefringence Layered Chalcogenide Enabled by Anisotropic Electrons in Tetrahedral Units0Unlocking Structural Anisotropy by Guest-Symmetry Modulation Strategy to Achieve Giant Birefringence in Molecular Crystals0Cation-Modulated Activation of Linear Units in an Ordered Arrangement Achieves the Largest Optical Anisotropy in Wide-Bandgap Metal Chalcogenides0

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  1. (C 5 H 6.16 N 2 Cl 0.84 )(IO 2 Cl 2 ): a birefringent crystal featuring unprecedented (IO 2 Cl 2 ) − anions and π-conjugated organic cations

    Chemical Science · 2023-01-01

    Qianqian Chen, Chun‐Li Hu, Mingzhi Zhang, Jiang‐Gao Mao

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  2. Three Borates Belonging to the A(I)7Ae(II)Re(III)2B15O30 Family as Promising Nonlinear Optical Crystals

    Crystal Growth & Design · 2023-08-21

    Chengfa Wu, Yu Dang, Jianbang Chen, Xueling Hou, Hongsheng Shi

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  3. Hydroxyl-Driven Enhanced Birefringence in Borophosphates

    Inorganic Chemistry · 2023-11-22

    Yang Xia, Wen-Bin Zhang, Xueting Pan, Xueling Hou, Shujuan Han

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  4. PbTeB 4 O 9 : a lead tellurium borate with unprecedented fundamental building block [B 4 O 10 ] and large birefringence

    Chemical Communications · 2023-11-28

    Ruonan Zhang, Abudukadi Tudi, Xia Yang, Xuping Wang, Zhihua Yang, Shujuan Han, Shilie Pan

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  5. (C(NH2)3)2(I2O5F)(IO3)(H2O) and C(NH2)3IO2F2: Two Guanidine Fluorooxoiodates with Wide Band Gap and Large Birefringence

    Inorganic Chemistry · 2023-12-22

    Juhui Cui, Shi‐Bin Wang, Abudukadi Tudi, Minqiang Gai, Zhihua Yang, Shilie Pan

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  6. [Sn 3 OF]PO 4 vs. [Sn 3 F 3 ]PO 4 : enhancing birefringence by breaking the R 3 symmetry and realigning lone pairs

    Inorganic Chemistry Frontiers · 2024-01-01

    Yuhan Hu, Xi Xu, Ruixi Wang, Jingyun Han, Shunsong Zhang, Shuhui Zhan, Jingyu Guo, Li‐Ming Wu, Ling Chen

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  7. A highly birefringent metal-free crystal assembled by cooperative non-covalent interactions

    Materials Horizons · 2024-01-01

    Yanqiang Li, Zhou Yang, Belal Ahmed, Qian-Ting Xu, Weiqi Huang, Yipeng Song, Xianyu Song, Bin Chen, Junhua Luo, Sangen Zhao

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  8. Amine-directed synthesis, valence state control, and optical properties of two new organic–inorganic tin chlorides

    Dalton Transactions · 2024-01-01

    Xuemei Wen, Gangji Yi, Zhizhuan Zhang, Caihong Guo, Hongmei Zeng, Ling Huang, Guohong Zou, Zhien Lin

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  9. Equivalent cation-tuning to realize a new Ce( iv ) fluoride with excellent comprehensive nonlinear optical performances

    Inorganic Chemistry Frontiers · 2024-01-01

    Beibei Zhang, Wen‐Ye Gao, Wei Lin Xu, L. Ma, Wenlong Liu, Ru‐Ling Tang, Sheng‐Ping Guo

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  10. Explorations of highly birefringent materials in the vanadium oxyfluoride–iodate system by fluoride ion modulation

    Journal of Materials Chemistry C · 2024-01-01

    Yu Huang, Xueying Zhang, Sangen Zhao, Jiang‐Gao Mao, Bing‐Ping Yang

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  11. From 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 groups

    Inorganic Chemistry Frontiers · 2024-01-01

    Cheng Chen, Danyang Dou, Yunjie Bai, Bingbing Zhang, Ying Wang

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  12. Novel antimony phosphates with enlarged birefringence induced by lone pair cations

    Dalton Transactions · 2024-01-01

    Mei Hu, Jialong Wang, Nuerbiye Tuerhong, Zhiyuan Zhang, Qun Jing, Zhaohui Chen, Yonglei Yang, Ming‐Hsien Lee

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  13. Sb4O5I2: Enhancing Birefringence through Optimization of Sb/I Ratio for Alignment of Stereochemically Active Lone Pairs

    Inorganic Chemistry · 2024-01-11

    Jingyu Guo, Xiangtong Zhan, Jiating Lan, Xin Liu, Shuang Zhao, Xi Xu, Li‐Ming Wu, Ling Chen

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  14. Giant Optical Anisotropy in a Covalent Molybdenum Tellurite via Oxyanion Polymerization

    Advanced Science · 2024-01-30

    Tianhui Wu, Xingxing Jiang, Kaining Duanmu, Chao Wu, Zheshuai Lin, Zhipeng Huang, Mark Graeme Humphrey, Chi Zhang

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  15. C(NH2)3MoO3(IO3): A Molybdenyl Iodate with Giant Birefringence Designed via a Cation–Anion Synergetic Interaction Strategy

    Chemistry of Materials · 2024-02-08

    Wei Zeng, Yao Tian, Xuehua Dong, Ling Huang, Hongmei Zeng, Zhien Lin, Guohong Zou

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  16. Enhanced UV Nonlinear Optical Properties in Layered Germanous Phosphites through Functional Group Sequential Construction

    Angewandte Chemie · 2024-06-08

    Yao Tian, Wei Zeng, Xuehua Dong, Ling Huang, Yuqiao Zhou, Hongmei Zeng, Zhien Lin, Guohong Zou

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  17. Enhanced UV Nonlinear Optical Properties in Layered Germanous Phosphites through Functional Group Sequential Construction

    Angewandte Chemie International Edition · 2024-06-08

    Yao Tian, Wei Zeng, Xuehua Dong, Ling Huang, Yuqiao Zhou, Hongmei Zeng, Zhien Lin, Guohong Zou

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

    Inorganic Chemistry · 2024-10-08

    Junjiang Li, Huanke Zhao, Xinyuan Zhang, Pifu Gong, Zheshuai Lin, Yicheng Wu

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  19. (C10N2H10)(HI2O6)(HIO3)(IO3): A Birefringent Material Featuring Large π-Conjugated Organic Cation and Two Types of Iodate Anions

    Inorganic Chemistry · 2024-10-19

    Yuhang Wang, De-Xuan Jiang, De‐Xuan Liu, Fu-Ying Li, He Zhao, Jie Pan, Qi Wei, Li Wei, Guo‐Yu Yang

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  20. Novel antimony-based mixed halides exhibiting an excellent SHG response and a broad transmission range

    Inorganic Chemistry Frontiers · 2024-12-05

    Luli Wang, Han Luo, Siyu Chen, Ling Huang, Liling Cao, Xuehua Dong, Guohong Zou

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  21. K 15 La 7 (BO 3 ) 12 : A KBBF-Like Nonlinear-Optical Material with a Short Cutoff Edge and a Strong Second-Harmonic-Generation Response

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    Fanlu Bu, Xiaorong Liu, Hongwei Yu, Runqing Liu, Zhanggui Hu, Jiyang Wang, Yicheng Wu, Hongping Wu

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  22. (C 6 H 5 N 2 )HgCl 3 : Discovery of a Polar Hg‐Based Hybrid Halide as Preeminent Nonlinear Optical and Birefringent Material Activated by π‐Conjugated Organic Cation Substitution

    Advanced Optical Materials · 2024-12-30

    Ru‐Ling Tang, Die‐Xue Yang, Liang Ma, Yi‐Lei Lv, Wenlong Liu, Sheng‐Ping Guo

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  23. (C 5 N 2 H 7 )IO 2 F 2 and (C 3 N 6 H 8 )(IO 2 F 2 ) 2 : two new organic–inorganic hybrid fluoroiodate birefringent crystals

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  24. A π-conjugated organic molecule-modified strategy to achieve high-performance metal nitrate birefringent crystals

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  25. Bulk crystal growth and optical properties of a novel organic–inorganic hybrid nonlinear optical thiocyanate: [Mn(CH 3 CONH 2 ) 2 ] [Hg(SCN) 4 ]

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  26. Cation tuning in anionic framework hydroborates: tailored deep-ultraviolet optical crystals with large birefringence

    New Journal of Chemistry · 2025-01-01

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  27. Hg 2 (HTe 2 O 5 )(PO 4 ): a novel phosphate crystal with enhanced birefringence enabled by the synergistic modification of multiple functional groups

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  28. Hg[CS(NH 2 ) 2 ] 4 (SiF 6 ): a fluorosilicate crystal with large birefringence achieved via multi-functional group modification

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    Pengfei Li, Xinlei Liu, Si-Qi Zhou, Mingchang Wang, Jingjing Wu, Yu‐Wu Zhong, Jiannian Yao

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  29. M 3 MoO 4 (HCO 3 ) (M = Rb and Cs): cation-tuned synthesis of two noncentrosymmetric molybdate-carbonates with isolated [MoO 4 ] and [HCO 3 ] groups

    Journal of Materials Chemistry C · 2025-01-01

    Jianlong Huang, Wenhu Wang, JuanJuan Lu, Feng Yu

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  30. Optimizing optical anisotropy in low-dimensional structures via intralayer hydrogen bonding modulation and anionic substitution

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  31. BaFS: Birefringence Enhanced by the Transformation from Optical Isotropy to Anisotropy via Interlayer Anion Substitution

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    Chao‐Hong Xie, Xiao‐Ming Jiang, Bin‐Wen Liu, Guo‐Cong Guo

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  32. Design and Synthesis of Two Sn-Centered Mixed Halide Crystals with Enhanced Birefringence

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  33. Underlying Dynamics of Double-Halide Perovskites: Unraveling Structural Complexity, Bandgap Modulation, Optical, and Carrier Dynamics for Next-Generation Optoelectronics

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  34. Metal Cation Engineered UV Birefringent Crystals in π‐Conjugated Sulfonates with Record‐High Optical Anisotropy

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  35. Improving the Performance of Birefringent Crystals by Molecular Assembly Strategy in the Solar‐Blind UV Region

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  36. [CON3H6BF4]: An Efficient Metal‐Free Borate with Optimized Birefringence Achieved by Structural Design Strategy

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  37. Dual‐Sided Multidentate Coordination Strategy Enables Record Birefringence in UV‐Transparent Antimony‐Based Hybrid Crystals

    Angewandte Chemie International Edition · 2025-07-10

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  38. Dual‐Sided Multidentate Coordination Strategy Enables Record Birefringence in UV‐Transparent Antimony‐Based Hybrid Crystals

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  39. Reversal Enhancement of Birefringence by Stereochemically Active Lone Pairs in Sn(II)-Based Mixed Halides

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  40. Low‐Dimensional Organic–Inorganic Hybrid Metal Halide with Large Optical Anisotropy

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  41. [Pb(ptz)(OH)(H2O)]: A Hybrid Nonlinear Optical Crystal with Large Birefringence

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  42. K 2 GdB 3 O 6 F 2 : A Promising Short-Wave UV Birefringent Crystal via Optimized Assembly of π-Conjugated [B 3 O 6 ] Groups

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  43. Hybrid Zinc‒Based Halides with Giant Optical Anisotropy via Protonation‒Engineered π ‒Conjugated Organic Group

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  44. K 6 Mo 8 PO 29 OH·H 2 O and K 6 Mo 5 P 2 O 23 ·7H 2 O: strongly distorted [MoO 6 ] octahedral groups effectively enhance birefringence

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  45. Achieving Ultra‐High Optical Anisotropy via Structural Regulation and Coplanar Engineering of Extended π‐Conjugated [H 2–x C 3 N 3 S 3 ] (x = 1, 2) Groups

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  46. A 2 Sb 2 SO 4 F 6 (A = NH 4 + , Na + ): two sulfate fluoride crystals exhibiting enhanced birefringence driven by stereochemically active antimony( iii )

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  47. Layered perovskite-like nitrates A 2 Ca(NO 3 ) 2 Cl 2 (A = Rb, Cs) as ultraviolet birefringent optical materials

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  48. Na 2 SnSO 4 F 2 : an ultraviolet-transparent sulfate crystal with large birefringence driven by stereochemically active tin( ii )

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  49. The modulation of structural polarity facilitating the gradient enhancement of second harmonic generation effects in hybrid metal halides

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  50. Halogen Anion-Mediated Substitution of Nitrate: Toward Polar Materials with Intense Second-Harmonic Generation Effects

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