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RESEARCH PAPER · Angewandte Chemie International Edition · 2023

Chain‐like [S x ] ( x =2–6) Units Realizing Giant Birefringence with Transparency in the Near‐Infrared for Optoelectronic Materials

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Chain‐like [S x ] ( x =2–6) Units Realizing Giant Birefringence with Transparency in the Near‐Infrared for Optoelectronic MaterialsOriginalBa 3 (BS 3 )(PS 4 ): the first alkaline-earth metal thioborate–thiophosphate with strong optical anisotropy originating from planar [BS 3 ] units8MB 3 P 2 S 10 (M = Rb, Cs): two new alkali metal thioboratephosphates with [B 6 P 4 S 20 ] T3-supertetrahedra2[Ba4(S2)][ZnGa4S10]: Design of an Unprecedented Infrared Nonlinear Salt‐Inclusion Chalcogenide with Disulfide‐Bonds36Improved Birefringence Activated by Tetrahedra Decorated with a Single Linear Unit38Improved Birefringence Activated by Tetrahedra Decorated with a Single Linear Unit1[RbSr 3 X][(BS 3 ) 2 ] (X = Cl, Br): two salt-inclusion thioborates with large birefringence and structure transformation from centrosymmetric to asymmetric8Vanadate Crystals with an Enhanced Birefringence and a Broadened Transparency Spectrum through Controlled [VO3]∞ Chain Arrangements and Alkali Metal Cation Introduction4Na 6 Mg 3 P 4 S 16 and RbMg 2 PS 4 Cl 2 : two Mg-based thiophosphates with ultrawide bandgaps resulting from [MgS 6 ] and [MgS x Cl 6− x ] octahedra4Greatly enhanced optical anisotropy in thiophosphates inspired by rational coupling of tetrahedra and ethane-like [P 2 S 6 ] 4− groups7Partial substitution with a significant effect: coexistence of a wide band gap and large birefringence in the oxychalcogenide AEGe 2 O 4 Se (AE = Sr and Ba)17Salt-inclusion sulfides [K 4 Cl][M II 11 In 9 S 26 ] (M II = Zn, Cd) displaying robust nonlinear optical activity4Polysulfide Anions [S x ] 2− ( x = 2, 3, 4, 5): Promising Functional Building Units for Infrared Nonlinear Optical Materials22Influence of Cation-Size Effects of Alkaline Earth (Ae) Metals on Dimensionality and Optical Anisotropy Regulation in K4AeP2S8 Thiophosphates5Homoatomic Polychalcogenide Nonlinear Optical Anionic Groups with Ultra-Large Optical Anisotropy31A solution-processable natural crystal with giant optical anisotropy for efficient manipulation of light polarization161Breaking Boundaries: Giant Ultraviolet Birefringence in Dimension‐Reduced Zn‐Based Crystals66Breaking Boundaries: Giant Ultraviolet Birefringence in Dimension‐Reduced Zn‐Based Crystals8CdInO(BO3): An oxyborate birefringent material explored from d10 metal compounds1Unprecedented Silver‐Based Hybrid Pyroelectric Enabling Wide Spectral Photo‐Pyroelectricity for Birefringence Photomodulation7Unprecedented Silver‐Based Hybrid Pyroelectric Enabling Wide Spectral Photo‐Pyroelectricity for Birefringence Photomodulation1Rare-Earth/d10 Dual-Metal Oxychalcogenides as Infrared Nonlinear-Optical Materials10Tin chalcohalide Sn 11 (PS 4 ) 4 I 10 obtained from structural-template-oriented synthesis: exhibiting balanced infrared nonlinear optical performance6BaSbBS 4 : a record-high-performance birefringent crystal identified by a target-driven closed-loop strategy28Cationic substitution engineering induces a new quaternary chalcogenide in the A–M IIIA –M IVA –Q system for optical crystal applications1Stereochemically active lone pair-induced large optical anisotropy in a novel infrared birefringent crystal Ba 2 La 2 Sb 4 S 10 (S 2 )5BaFS: Birefringence Enhanced by the Transformation from Optical Isotropy to Anisotropy via Interlayer Anion Substitution8Na2MP3O9 (M = K, Rb): Two Potential Zero-Order Waveplate Materials with DUV Cutoff Edges2Metal Cation Engineered UV Birefringent Crystals in π‐Conjugated Sulfonates with Record‐High Optical Anisotropy17Giant Birefringence Enabled by the Highly Anisotropic Linear IX 2 − (X = Cl, Br) Building Blocks6Giant Birefringence Enabled by the Highly Anisotropic Linear IX 2 − (X = Cl, Br) Building Blocks32NbGa 2 S 4 (S 2 ): A Rare Linear [S 2 ] 2− Coordination to Niobium Resulting in Simultaneously Large SHG Effect and Giant Birefringence20NbGa 2 S 4 (S 2 ): A Rare Linear [S 2 ] 2− Coordination to Niobium Resulting in Simultaneously Large SHG Effect and Giant Birefringence6[TeSeS 2 ] 2− : The First Heterotriple‐Chalcogenide Motifs Decode Giant Mid‐Far Infrared Birefringence18[TeSeS 2 ] 2− : The First Heterotriple‐Chalcogenide Motifs Decode Giant Mid‐Far Infrared Birefringence4CsICl 2 : A Record-Birefringent Inorganic Crystal with Ultrawide Infrared Transparency Enabled by Linear Interhalogen ICl 2 – Units36A Homoatomic Heteroleptic Coordination Strategy for Exceptional Infrared Linear and Nonlinear Optical Properties in ANb 2 PS 4 (S 2 ) 3 (A = K,Rb,Cs)3Achieving giant optical anisotropy in the mid-far infrared region via ideal alignment of dual functional motifs0Pyrazinamide–IBr: an organic–inorganic hybrid crystal exhibiting giant optical anisotropy0Protonation‐Triggered Structural Transformations in 4‐Hydroxypyridinium Halides for Solar‐Blind UV Functional Crystals3Protonation‐Triggered Structural Transformations in 4‐Hydroxypyridinium Halides for Solar‐Blind UV Functional Crystals8Anion-Centered Engineering for Simultaneously Enhancing Birefringence and Band Gap in Chalcogenides1Unveiling the Superior Birefringence Property of a Record‐Birefringent Crystal with Unique Building Block12Unveiling the Superior Birefringence Property of a Record‐Birefringent Crystal with Unique Building Block4Ba 4 CdGa 2 S 6 F 4 : A Chalcohalide Birefringent Crystal with Large Band Gap Designed by the Cation and Anion Cosubstitution Strategy2Density-Compensated Polarizability Anisotropy for Record Birefringence in Short-Wavelength Ultraviolet Inorganic Crystals11Overcoming the Bandgap‐Birefringence Trade‐Off: Proton‐Transfer Engineering of High‐Performance Ultraviolet‐Transparent Organic Crystal5CdY 2 Si 2 S 8 : A Wide Bandgap IR NLO Material with d 10 Metal-Induced Structure Transformation from CS to NCS1From Coplanarity to Coaxiality: A Linearity-Oriented Design Paradigm for Ultrahigh Ultraviolet Birefringent Inorganic Crystals4Achieving High‐Birefringence Thiophosphates From Low Polarizability Anisotropy Units by an Axial Linear Matching Strategy1Record‐High Birefringence with Ultralow Dichroic Loss Realized by Cation‐Templated Engineering Ordered Assembly of Linear Birefringent‐Active Unit6Lock‐and‐Key Assembly Enables Record Birefringence in Monocyclic π‐Conjugated Crystals via Spatial Confinement of Linear Polyhalide5Unlocking 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. Ba 3 (BS 3 )(PS 4 ): the first alkaline-earth metal thioborate–thiophosphate with strong optical anisotropy originating from planar [BS 3 ] units

    Dalton Transactions · 2023-01-01

    Jiazheng Zhou, Linan Wang, Hongshan Wang, Ling Luo, Junjie Li, Feng Yu

    Read original paper ↗ ·
  2. MB 3 P 2 S 10 (M = Rb, Cs): two new alkali metal thioboratephosphates with [B 6 P 4 S 20 ] T3-supertetrahedra

    Dalton Transactions · 2023-01-01

    Jiazheng Zhou, Xin Su, Ling Luo, Junjie Li, Feng Yu

    Read original paper ↗ ·
  3. [Ba4(S2)][ZnGa4S10]: Design of an Unprecedented Infrared Nonlinear Salt‐Inclusion Chalcogenide with Disulfide‐Bonds

    Small · 2023-06-04

    Kaixuan Ding, Hongping Wu, Zhanggui Hu, Jiyang Wang, Yicheng Wu, Hongwei Yu

    Read original paper ↗ ·
  4. Improved Birefringence Activated by Tetrahedra Decorated with a Single Linear Unit

    Angewandte Chemie International Edition · 2023-06-29

    Wenlong Xie, Fuming Li, Jianbang Chen, Zhihuang Yang, Guangmao Li, Shilie Pan

    Read original paper ↗ ·
  5. Improved Birefringence Activated by Tetrahedra Decorated with a Single Linear Unit

    Angewandte Chemie · 2023-06-29

    Wenlong Xie, Fuming Li, Jianbang Chen, Zhihuang Yang, Guangmao Li, Shilie Pan

    Read original paper ↗ ·
  6. [RbSr 3 X][(BS 3 ) 2 ] (X = Cl, Br): two salt-inclusion thioborates with large birefringence and structure transformation from centrosymmetric to asymmetric

    Chemical Communications · 2023-11-17

    Yihan Yun, Xueling Hou, Zhihua Yang, Guangmao Li, Shilie Pan

    Read original paper ↗ ·
  7. Vanadate Crystals with an Enhanced Birefringence and a Broadened Transparency Spectrum through Controlled [VO3]∞ Chain Arrangements and Alkali Metal Cation Introduction

    Inorganic Chemistry · 2023-11-24

    Jinlei Cheng, Die Xu, Juanjuan Lu, Feng Zhang, Xueling Hou

    Read original paper ↗ ·
  8. Na 6 Mg 3 P 4 S 16 and RbMg 2 PS 4 Cl 2 : two Mg-based thiophosphates with ultrawide bandgaps resulting from [MgS 6 ] and [MgS x Cl 6− x ] octahedra

    Dalton Transactions · 2023-12-05

    Yi Chu Huang, Dongdong Chu, Xueling Hou, Guangmao Li, Yong an Zhang

    Read original paper ↗ ·
  9. Greatly enhanced optical anisotropy in thiophosphates inspired by rational coupling of tetrahedra and ethane-like [P 2 S 6 ] 4− groups

    Inorganic Chemistry Frontiers · 2024-01-01

    Ning Zhao, Dazhi Lu, Jingjing Xu, Kui Wu, Haohai Yu, Huaijin Zhang

    Read original paper ↗ ·
  10. Partial substitution with a significant effect: coexistence of a wide band gap and large birefringence in the oxychalcogenide AEGe 2 O 4 Se (AE = Sr and Ba)

    Inorganic Chemistry Frontiers · 2024-01-01

    Mao‐Yin Ran, Shenghua Zhou, Wenbo Wei, A-Yang Wang, Xin‐Tao Wu, Hua Lin, Qi‐Long Zhu

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  11. Salt-inclusion sulfides [K 4 Cl][M II 11 In 9 S 26 ] (M II = Zn, Cd) displaying robust nonlinear optical activity

    Materials Chemistry Frontiers · 2024-01-01

    Yangping Zhang, Shao‐Min Pei, Xiao‐Ming Jiang, Bin‐Wen Liu, Guo‐Cong Guo

    Read original paper ↗ ·
  12. Polysulfide Anions [S x ] 2− ( x = 2, 3, 4, 5): Promising Functional Building Units for Infrared Nonlinear Optical Materials

    Small · 2024-01-23

    Miao Song, Yan Xiao, Daqing Yang, Ying Wang, Bingbing Zhang

    Read original paper ↗ ·
  13. Influence of Cation-Size Effects of Alkaline Earth (Ae) Metals on Dimensionality and Optical Anisotropy Regulation in K4AeP2S8 Thiophosphates

    Inorganic Chemistry · 2024-04-23

    Xinyu Tian, Ning Zhao, Kui Wu, Jingjing Xu, Dazhi Lu, Haohai Yu, Huaijin Zhang

    Read original paper ↗ ·
  14. Homoatomic Polychalcogenide Nonlinear Optical Anionic Groups with Ultra-Large Optical Anisotropy

    Journal of the American Chemical Society · 2024-05-31

    Aoge Yao, Fan Liu, Bohui Xu, Hao Huo, Zheshuai Lin, Lei Kang

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  15. A solution-processable natural crystal with giant optical anisotropy for efficient manipulation of light polarization

    Nature Photonics · 2024-06-14

    Zhou Yang, Zhengfeng Guo, Honggang Gu, Yanqiang Li, Yipeng Song, Shiyuan Liu, Maochun Hong, Sangen Zhao, Junhua Luo

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  16. Breaking Boundaries: Giant Ultraviolet Birefringence in Dimension‐Reduced Zn‐Based Crystals

    Angewandte Chemie International Edition · 2024-06-26

    Yang Li, Kang Min Ok

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  17. Breaking Boundaries: Giant Ultraviolet Birefringence in Dimension‐Reduced Zn‐Based Crystals

    Angewandte Chemie · 2024-06-26

    Yang Li, Kang Min Ok

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  18. CdInO(BO3): An oxyborate birefringent material explored from d10 metal compounds

    Journal of Molecular Structure · 2024-08-03

    Runqing Liu, Rongwei Shi, Jiming Huang, Fen Ye, Senlin Leng

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  19. Unprecedented Silver‐Based Hybrid Pyroelectric Enabling Wide Spectral Photo‐Pyroelectricity for Birefringence Photomodulation

    Angewandte Chemie International Edition · 2024-09-09

    Xi Rui Zeng, Li Ming Fu, Yi Liu, Yu Ma, Yaoyao Chen, Yang Zhou, Pengfei Zhu, Hongbin Zhang, Junhua Luo, Zhihua Sun

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  20. Unprecedented Silver‐Based Hybrid Pyroelectric Enabling Wide Spectral Photo‐Pyroelectricity for Birefringence Photomodulation

    Angewandte Chemie · 2024-09-09

    Xi Rui Zeng, Li Ming Fu, Yi Liu, Yu Ma, Yaoyao Chen, Yang Zhou, Pengfei Zhu, Hongbin Zhang, Junhua Luo, Zhihua Sun

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  21. Rare-Earth/d10 Dual-Metal Oxychalcogenides as Infrared Nonlinear-Optical Materials

    Inorganic Chemistry · 2024-11-06

    Fang-Xu Tian, Nan Zhang, Wen‐Dong Yao, Mingyang Li, Haiping Xu, Wenlong Liu, Jing Zhu, Sheng‐Ping Guo

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  22. Tin chalcohalide Sn 11 (PS 4 ) 4 I 10 obtained from structural-template-oriented synthesis: exhibiting balanced infrared nonlinear optical performance

    Inorganic Chemistry Frontiers · 2024-12-19

    Cuier Deng, Xi Qing Xu, Yuhan Hu, Jingyu Guo, Li‐Ming Wu, Ling Chen

    Read original paper ↗ ·
  23. BaSbBS 4 : a record-high-performance birefringent crystal identified by a target-driven closed-loop strategy

    Chemical Science · 2025-01-01

    Ming‐Zhi Zhang, Yue Zhao, Chun‐Li Hu, Jiang‐Gao Mao

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  24. Cationic substitution engineering induces a new quaternary chalcogenide in the A–M IIIA –M IVA –Q system for optical crystal applications

    CrystEngComm · 2025-01-01

    Yue Wang, Xuezhong Li, Zihao Lou, Yong‐Fang Shi

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  25. Stereochemically active lone pair-induced large optical anisotropy in a novel infrared birefringent crystal Ba 2 La 2 Sb 4 S 10 (S 2 )

    Inorganic Chemistry Frontiers · 2025-01-01

    Jingdong Yan, Xiangran Kong, Shichao Cheng, Tao Liu, Hongwei Leng, Yunfei Shang, Zuotao Lei, Chunhui Yang

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

    Small · 2025-01-14

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

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  27. Na2MP3O9 (M = K, Rb): Two Potential Zero-Order Waveplate Materials with DUV Cutoff Edges

    Inorganic Chemistry · 2025-03-04

    Huanhuan Zhao, Chenxu Li, Yi Huang, Qun Jing, Xuebin Yu, Zhaohui Chen

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

    Small · 2025-04-07

    Zichang Wang, Qing‐Yu Liu, Zhihua Yang, Xueling Hou, Minqiang Gai

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  29. Giant Birefringence Enabled by the Highly Anisotropic Linear IX 2 − (X = Cl, Br) Building Blocks

    Angewandte Chemie · 2025-04-16

    Chong‐An Chen, Yang Li, Hongbo Huang, Congcong Jin, Bingbing Zhang, Kang Min Ok

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  30. Giant Birefringence Enabled by the Highly Anisotropic Linear IX 2 − (X = Cl, Br) Building Blocks

    Angewandte Chemie International Edition · 2025-04-16

    Chong‐An Chen, Yang Li, Hongbo Huang, Congcong Jin, Bingbing Zhang, Kang Min Ok

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  31. NbGa 2 S 4 (S 2 ): A Rare Linear [S 2 ] 2− Coordination to Niobium Resulting in Simultaneously Large SHG Effect and Giant Birefringence

    Angewandte Chemie International Edition · 2025-05-29

    Wenli Zhao, Rui‐Xi Wang, Shuang Zhao, Li‐Ming Wu, Ling Chen

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  32. NbGa 2 S 4 (S 2 ): A Rare Linear [S 2 ] 2− Coordination to Niobium Resulting in Simultaneously Large SHG Effect and Giant Birefringence

    Angewandte Chemie · 2025-05-29

    Wenli Zhao, Rui‐Xi Wang, Shuang Zhao, Li‐Ming Wu, Ling Chen

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  33. [TeSeS 2 ] 2− : The First Heterotriple‐Chalcogenide Motifs Decode Giant Mid‐Far Infrared Birefringence

    Angewandte Chemie International Edition · 2025-06-17

    Bo Zhang, Wei‐Qi Huang, Jiaxiang Zhang, Xintao Wu, Hua Lin, Qi‐Long Zhu

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  34. [TeSeS 2 ] 2− : The First Heterotriple‐Chalcogenide Motifs Decode Giant Mid‐Far Infrared Birefringence

    Angewandte Chemie · 2025-06-17

    Bo Zhang, Wei‐Qi Huang, Jiaxiang Zhang, Xintao Wu, Hua Lin, Qi‐Long Zhu

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  35. CsICl 2 : A Record-Birefringent Inorganic Crystal with Ultrawide Infrared Transparency Enabled by Linear Interhalogen ICl 2 – Units

    Journal of the American Chemical Society · 2025-07-21

    Chong‐An Chen, Yang Li, Congcong Jin, Kang Min Ok

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  36. A Homoatomic Heteroleptic Coordination Strategy for Exceptional Infrared Linear and Nonlinear Optical Properties in ANb 2 PS 4 (S 2 ) 3 (A = K,Rb,Cs)

    Inorganic Chemistry · 2025-12-31

    Yumiao Niu, Yan Chun Xiao, Yidan Chen, Chu Chu, Daqing Yang, Ying Wang, Bingbing Zhang

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  37. Achieving giant optical anisotropy in the mid-far infrared region via ideal alignment of dual functional motifs

    Inorganic Chemistry Frontiers · 2026-01-01

    Yi-Wen Shan, Ming‐Zhi Zhang, C Hu, Jiang‐Gao Mao

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  38. Pyrazinamide–IBr: an organic–inorganic hybrid crystal exhibiting giant optical anisotropy

    Dalton Transactions · 2026-01-01

    Meng-Fan Duan, Jiang‐Gao Mao, Bing‐Ping Yang

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  39. Protonation‐Triggered Structural Transformations in 4‐Hydroxypyridinium Halides for Solar‐Blind UV Functional Crystals

    Angewandte Chemie · 2026-01-04

    Jing Lu, Xin Liu, Shuangxiong Zhao, Xuebing Deng, Qundong Fu, Jingyu Guo, Zheng Liu, Li‐Ming Wu, Ling Chen

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  40. Protonation‐Triggered Structural Transformations in 4‐Hydroxypyridinium Halides for Solar‐Blind UV Functional Crystals

    Angewandte Chemie International Edition · 2026-01-04

    Jing Lu, Xin Liu, Shuangxiong Zhao, Xuebing Deng, Qundong Fu, Jingyu Guo, Zheng Liu, Li‐Ming Wu, Ling Chen

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  41. Anion-Centered Engineering for Simultaneously Enhancing Birefringence and Band Gap in Chalcogenides

    Chemistry of Materials · 2026-01-19

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

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  42. Unveiling the Superior Birefringence Property of a Record‐Birefringent Crystal with Unique Building Block

    Angewandte Chemie International Edition · 2026-01-27

    Kaijie Xie, Zhiyong Bai, Weiqi Huang, Ji Qi, Tingjuan Lin, Muhammad Zeeshan, Yanqiang Li, Yang Zhou, Junhua Luo, Sangen Zhao

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  43. Unveiling the Superior Birefringence Property of a Record‐Birefringent Crystal with Unique Building Block

    Angewandte Chemie · 2026-01-27

    Kaijie Xie, Zhiyong Bai, Weiqi Huang, Ji Qi, Tingjuan Lin, Muhammad Zeeshan, Yanqiang Li, Yang Zhou, Junhua Luo, Sangen Zhao

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  44. Ba 4 CdGa 2 S 6 F 4 : A Chalcohalide Birefringent Crystal with Large Band Gap Designed by the Cation and Anion Cosubstitution Strategy

    Inorganic Chemistry · 2026-03-02

    Jingdong Yan, Xiangran Kong, Zichang Wang, Hongwei Leng, Tao Liu, Yunfei Shang, Nikolay Yudin, Z. L. Lei, Chunhui Yang

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  45. Density-Compensated Polarizability Anisotropy for Record Birefringence in Short-Wavelength Ultraviolet Inorganic Crystals

    Journal of the American Chemical Society · 2026-03-05

    Chong‐An Chen, Yang Li, Congcong Jin, S. D. Lee, Zhihua Yang, Kang Min Ok

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  46. Overcoming the Bandgap‐Birefringence Trade‐Off: Proton‐Transfer Engineering of High‐Performance Ultraviolet‐Transparent Organic Crystal

    Angewandte Chemie · 2026-03-05

    Lin Qiu, Xing‐Yu Li, Bing-Wei Miao, Hongjian Yu, Wenlong Liu, Yifan Sun, Ru‐Ling Tang

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  47. CdY 2 Si 2 S 8 : A Wide Bandgap IR NLO Material with d 10 Metal-Induced Structure Transformation from CS to NCS

    Inorganic Chemistry · 2026-03-26

    Hongbo Zhang, Haixia Wang, Aoya He, Jiaze Sun, Jindou Hu, G. L. Li

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  48. From Coplanarity to Coaxiality: A Linearity-Oriented Design Paradigm for Ultrahigh Ultraviolet Birefringent Inorganic Crystals

    Journal of the American Chemical Society · 2026-05-04

    Congcong Jin, Yang Li, Chong‐An Chen, Wei Zeng, S. D. Lee, Kang Min Ok

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  49. Achieving High‐Birefringence Thiophosphates From Low Polarizability Anisotropy Units by an Axial Linear Matching Strategy

    Advanced Optical Materials · 2026-05-18

    Ming‐Zhi Zhang, C Hu, Yi‐Wen Shan, Jiang‐Gao Mao

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  50. Record‐High Birefringence with Ultralow Dichroic Loss Realized by Cation‐Templated Engineering Ordered Assembly of Linear Birefringent‐Active Unit

    Advanced Functional Materials · 2026-05-22

    Jing‐Jing Zhao, Q Zhang, Shu‐Fang Li, Honggang Gu, Shiyuan Liu, Hongbo Huang, Bingbing Zhang, Dong Yan

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