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RESEARCH PAPER · Coordination Chemistry Reviews · 2025

Recent progress in structural design strategies of high-birefringence optical crystals

A-Lan Xu, Mao‐Yin Ran, Xintao Wu, Hua Lin, Qi‐Long Zhu

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Recent progress in structural design strategies of high-birefringence optical crystalsOriginalExploring ultra-high optical anisotropy in polyiodides7Stereochemically active lone pair-induced large optical anisotropy in a novel infrared birefringent crystal Ba 2 La 2 Sb 4 S 10 (S 2 )5[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 – Units36Achieving the birefringence-bandgap trade-off: Hydrogen-bond engineered biuret-cyanurate14Modulation of Crystal Structure and Birefringence: Cation Size Effect in Alkali Metal Fluoroaluminoborates4A3ZnNO3X4 (A = Rb, NH4, X = Cl, I): Regulating Cations and Halides Yields Birefringent Crystals with Significantly Enhanced Optical Anisotropy5CaYIIIS 4 (III = Ga, In): Two Olivine-Type Compounds Exhibiting Exceptional Birefringence Properties1Synergistic Enhancement of Band Gap and Optical Anisotropy via Functional-Site Cosubstitution in Antiperovskite-Type Chalcohalides [Ba2K][X][MS4] (M = Ge, Si; X = Cl, Br)2Enhanced Birefringence in Hybrid Antimony Halides via π-Conjugated Organic Cation Design10Structure-property relationships in IR nonlinear optical chalcogenides with stereochemically active lone pairs29SrZnSiS4: Shattering the 4.0 eV Threshold toward Dual-Optimized Bandgap and Second-Harmonic Generation5[C(NH2)3]Pb(C2O4)Cl·H2O: A halogen- and lone-pair-tuned UV crystal with large birefringence originated from cooperative π-conjugation6Anionic Group Trimming Strategy: Oriented Fabrication of Sulfonate UV Birefringent Crystals with High Optical Anisotropy5K 2 GdB 3 O 6 F 2 : A Promising Short-Wave UV Birefringent Crystal via Optimized Assembly of π-Conjugated [B 3 O 6 ] Groups8Maximizing the second-harmonic generation response via coordination-induced localization of nonbonding electrons12Hybrid Zinc‒Based Halides with Giant Optical Anisotropy via Protonation‒Engineered π ‒Conjugated Organic Group24Ba 3 (MoO 2 F 3 )PO 4 F 2 : Rational Design and Synthesis of an Alkaline-Earth Phosphate Fluoride as a Birefringent Crystal1Hydrogen‐Bond‐Driven Metal‐Free Crystal (C 6 H 7 N 2 O)(NH 2 SO 3 ) with Giant Birefringence and Solar‐Blind Ultraviolet Transmission0Asymmetry-driven organic–inorganic hybrid strategy for constructing structures with exceptional organofunctionalized B–O units2Synthesis, Crystal Growth, Linear, and Nonlinear Optical Properties of Water-Grown Giant Optical Anisotropic Thiocyanates ABi(SCN) 4 (A = Rb, Cs)3Halide anion-mediated crystal structure engineering in guanidinoacetic acid halides for tunable birefringence0Na 2 SnSO 4 F 2 : an ultraviolet-transparent sulfate crystal with large birefringence driven by stereochemically active tin( ii )1Polarization optical metrology for linear birefringence in transparent anisotropic medium0Pyrazinamide–IBr: an organic–inorganic hybrid crystal exhibiting giant optical anisotropy0SnCl 2 [SC(NH 2 ) 2 ]: lone-pair and hydrogen-bonding triggered chromophore assembling for dual optical optimization0The 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 birefringence0Programmable Anisotropic in Diazapyrene Cocrystals With Birefringence Exceeding 1.27Programmable Anisotropic in Diazapyrene Cocrystals With Birefringence Exceeding 1.21Sn 4+ /Sn 2+ Aliovalent Substitution: A Strategy for Local Structure Engineering to Enhance Birefringence and Trigger Structural Symmetry Transition0[C 3 N 2 H 5 ]B 7 O 10 F 2 : Demonstrating a New Hydrogen‐Bond‐Induced Intralayer Charge‐Balanced Structure Model with Large Birefringence3(C 5 H 7 N 2 ) (C 8 H 4 O 4 ) PbBr: Jahn–Teller Distortion‐Induced Tilting of π‐Conjugated Planes Resolving the Second‐Order Polarizability–Structural Anisotropy Conflicts13(C 5 H 7 N 2 ) (C 8 H 4 O 4 ) PbBr: Jahn–Teller Distortion‐Induced Tilting of π‐Conjugated Planes Resolving the Second‐Order Polarizability–Structural Anisotropy Conflicts1Synergistic Enhancement of Optical Anisotropy in Nitrate Sulfamate for UV Applications: Role of Functional Group Alignment and Hydrogen Bond Network1Heterovalent Coexistence‐Driven Symmetry Breaking and Dimensional Evolution: Designing Polar Heart‐Shaped Channels for Exceptional MFIR Nonlinear Optics5K 2 ZrSi 2 O 7 with a Wide Transmission Range and Enhanced Birefringence Induced by the d 0 -TM Zr-Based Units2Redox‐Driven Strategy Enabling Leapfrog Enhancement of Birefringence in Layered Tin‐Based Optical Crystals1Bridging Motifs Induced Ordered Arrangement Contributing Large Birefringence for Hg 4 BiQ 2 Cl 5 (Q═S, Se)1Interlayer Electronic Decoupling Unlocks Giant Birefringence in π‐Conjugated Metal‐Organic Frameworks0Peroxide‐Assisted Solvate Engineering Enables Record‐High Birefringence in a Solar‐Blind Transparent Crystal0Peroxide‐Assisted Solvate Engineering Enables Record‐High Birefringence in a Solar‐Blind Transparent Crystal0Halogen-Mediated Dimensionality Reduction in Bismuth Oxychlorides: Trade-off between Birefringence and Band Gap0Local Aromatic Overlap Microregulation Enables Birefringence Enhancement in Isocompositional Hybrid Antimony Halides1Decoupling Contributions of Distinct Strategies for Enhancing Polarizability Anisotropy in Crystals Containing π-Conjugated Groups0From AgGaSe2 to MIIGa2Se4 (MII = Zn, Cd): Heterovalent Substitution Creates Ordered Vacancies for Balanced IR-NLO Performance0Reversible Symmetry Switching, Giant Birefringence, and UV Second‐Harmonic Generation in Hybrid Niobium Oxyfluorides0Reversible Symmetry Switching, Giant Birefringence, and UV Second‐Harmonic Generation in Hybrid Niobium Oxyfluorides0Photocatalytic Degradation of Methylene Blue and Rhodamine B by Mononuclear Copper (II) Complex with Phenanthroline-Based Ligand0Bulk growth, optical and thermal properties of CsCdCl3 birefringent crystal0Domino‐Effect Amplification via Covalent‐Chain Engineering for Giant Birefringence in NaAsQ 2 (Q = S, Se) Crystals0MAlB3O6F2 (M = Ca and Pb): Two New Fluoroaluminoborates Featuring π-Conjugated [BO3] and [AlO4F2] Units with Large Birefringence0Cation‐Regulated [CH 3 BO 2 F]‐Derived Borates: Synergistic Fluorination and Organic Functionalization for High‐Birefringence UV NLO Materials0

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  1. Exploring ultra-high optical anisotropy in polyiodides

    Inorganic Chemistry Frontiers · 2025-01-01

    Mingye Han, Hongbo Huang, Siyu Li, Xiao Yan, Bingbing Zhang, Ying Wang

    Read original paper ↗ ·

  2. 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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  3. [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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  4. [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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  5. 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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  6. Achieving the birefringence-bandgap trade-off: Hydrogen-bond engineered biuret-cyanurate

    Chinese Journal of Structural Chemistry · 2025-07-29

    Ziqi Chen, Miriding Mutailipu

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  7. Modulation of Crystal Structure and Birefringence: Cation Size Effect in Alkali Metal Fluoroaluminoborates

    Inorganic Chemistry · 2025-08-02

    Chao Wei, Danyang Dou, Bingbing Zhang, Ying Wang

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  8. A3ZnNO3X4 (A = Rb, NH4, X = Cl, I): Regulating Cations and Halides Yields Birefringent Crystals with Significantly Enhanced Optical Anisotropy

    Inorganic Chemistry · 2025-08-15

    Zhiyuan Zhang, Yabo Wu, Luyong Zhang, Xu Liu, Qiuyuan Feng, Lihan Deng, Jin Li, Shujuan Han

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  9. CaYIIIS 4 (III = Ga, In): Two Olivine-Type Compounds Exhibiting Exceptional Birefringence Properties

    Inorganic Chemistry · 2025-08-21

    Chengbo Li, Haipeng Zhou, Y. Q. Chen, Jinfeng Liu, Xiu Zhu, Guisheng Xu, Jiankang Wang

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  10. Synergistic Enhancement of Band Gap and Optical Anisotropy via Functional-Site Cosubstitution in Antiperovskite-Type Chalcohalides [Ba2K][X][MS4] (M = Ge, Si; X = Cl, Br)

    Inorganic Chemistry · 2025-08-26

    Yong‐Fang Shi, Shenghua Zhou, Xintao Wu, Hua Lin, Qi‐Long Zhu

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  11. Enhanced Birefringence in Hybrid Antimony Halides via π-Conjugated Organic Cation Design

    Crystal Growth & Design · 2025-09-02

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

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  12. Structure-property relationships in IR nonlinear optical chalcogenides with stereochemically active lone pairs

    Coordination Chemistry Reviews · 2025-09-03

    Hong Chen, Xin‐Tao Wu, Hua Lin

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  13. SrZnSiS4: Shattering the 4.0 eV Threshold toward Dual-Optimized Bandgap and Second-Harmonic Generation

    Inorganic Chemistry · 2025-09-04

    Huilin Yin, Xia Wu, Shuchang Wu, Changsheng Sun, Chengxiao Wang, Jiaman Sun, Yang Liu, Xiao‐Ming Jiang, Ximeng Lv, Dajiang Mei

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  14. [C(NH2)3]Pb(C2O4)Cl·H2O: A halogen- and lone-pair-tuned UV crystal with large birefringence originated from cooperative π-conjugation

    Journal of Molecular Structure · 2025-09-08

    Chao Ma, Yu-Ming Pan, Pei Feng Han, Meihong Duan

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  15. Anionic Group Trimming Strategy: Oriented Fabrication of Sulfonate UV Birefringent Crystals with High Optical Anisotropy

    ACS Applied Materials & Interfaces · 2025-09-16

    Hangwei Jia, Yaqi Jin, Shuai An, Xu Liu, Zhihua Yang, Xueling Hou, Shilie Pan

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  16. 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

    Inorganic Chemistry · 2025-10-14

    Mengru Liu, Huijian Zhao, Xianghao Kong, Ning Ye, Zhanggui Hu, Conggang Li

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  17. Maximizing the second-harmonic generation response via coordination-induced localization of nonbonding electrons

    Chemical Science · 2025-11-17

    Jia-Xiang Zhang, A-Lan Xu, Yang Chi, Xin-Tao Wu, Hua Lin, Qi‐Long Zhu

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

    Advanced Functional Materials · 2025-11-20

    Ruo‐Nan Li, Zhen‐Cheng Wu, Wen‐Dong Yao, Yi‐Fan Fu, Yu‐Mei Zhang, Wenlong Liu, Jiajing Wu, Sheng‐Ping Guo

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  19. Ba 3 (MoO 2 F 3 )PO 4 F 2 : Rational Design and Synthesis of an Alkaline-Earth Phosphate Fluoride as a Birefringent Crystal

    Crystal Growth & Design · 2025-11-26

    Feng Xu, Mengya Qin, Bin Su, Chao He, Shaohua Yu, Yu Li, Rong Guo, Chan Zheng

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  20. Hydrogen‐Bond‐Driven Metal‐Free Crystal (C 6 H 7 N 2 O)(NH 2 SO 3 ) with Giant Birefringence and Solar‐Blind Ultraviolet Transmission

    Advanced Optical Materials · 2025-12-10

    Zhenkai Cen, Z.-Y. Li, Guang Peng, Junbo Gong, Junbo Gong

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  21. Asymmetry-driven organic–inorganic hybrid strategy for constructing structures with exceptional organofunctionalized B–O units

    Inorganic Chemistry Frontiers · 2025-12-20

    Haoran Wang, chenxu li, Xue Bai, Qingyu Liu, Xueling Hou, Min Zhang

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  22. Synthesis, Crystal Growth, Linear, and Nonlinear Optical Properties of Water-Grown Giant Optical Anisotropic Thiocyanates ABi(SCN) 4 (A = Rb, Cs)

    Crystal Growth & Design · 2025-12-30

    Vivian Nguyen, Chu Chu, Monique Sutherlin, Bingbing Zhang, Jian Wang

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  23. Halide anion-mediated crystal structure engineering in guanidinoacetic acid halides for tunable birefringence

    Inorganic Chemistry Frontiers · 2026-01-01

    Wenjing Zhang, Yaozu Li, Chenyang Li, Wenjing Tan, Mingye Han, Bingbing Zhang, Ying Wang

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

    Dalton Transactions · 2026-01-01

    Jia Wang, Wenbin Zhang, X. Ma, Fangfang Zhang, Hong Du, Shujuan Han

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  25. Polarization optical metrology for linear birefringence in transparent anisotropic medium

    Light Advanced Manufacturing · 2026-01-01

    Shiwei Deng, Xunda Chang, Kerong Jiao, Kewu Li, Xin Xu, Yifan Wang, Jiayu Wang, Hua Shen, Yidong Tan

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  26. 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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  27. SnCl 2 [SC(NH 2 ) 2 ]: lone-pair and hydrogen-bonding triggered chromophore assembling for dual optical optimization

    Dalton Transactions · 2026-01-01

    Xing-Yu Bi, Yuting Gao, Chenyuan Ma, Zhi Gang Fang, Meihong Duan

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  28. The condensation of π-conjugated units: a new paradigm for designing high-performance optical crystals

    Chemical Society Reviews · 2026-01-01

    Hangwei Jia, Bailin Chen, Fangfang Zhang, Xueling Hou, Shilie Pan

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  29. Truss bridge-like anhydrous stacking in hybrid crystals triggers ultra-high stability and robust birefringence

    Inorganic Chemistry Frontiers · 2026-01-01

    Ping Wang, Qiya Huang, Xiaoli Meng, Lehui Liu, Qi Wu, Hongming Liu

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  30. Programmable Anisotropic in Diazapyrene Cocrystals With Birefringence Exceeding 1.2

    Angewandte Chemie International Edition · 2026-01-28

    Lingyan Sun, Gangji Yi, Guohong Zou, Cheng Jiang Zhang

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  31. Programmable Anisotropic in Diazapyrene Cocrystals With Birefringence Exceeding 1.2

    Angewandte Chemie · 2026-01-28

    Lingyan Sun, Gangji Yi, Guohong Zou, Cheng Jiang Zhang

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  32. Sn 4+ /Sn 2+ Aliovalent Substitution: A Strategy for Local Structure Engineering to Enhance Birefringence and Trigger Structural Symmetry Transition

    Inorganic Chemistry · 2026-01-29

    Bao Jiang, Hongheng Chen, Lei Wu, Xueyin Fu, Maierhaba Abudoureheman, Qun Jing, Yu-hong Su, Zhaohui Chen

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  33. [C 3 N 2 H 5 ]B 7 O 10 F 2 : Demonstrating a New Hydrogen‐Bond‐Induced Intralayer Charge‐Balanced Structure Model with Large Birefringence

    Small · 2026-02-20

    Chunjie Shen, Huan Zhou, Zhihua Yang, Xueling Hou, Feng Zhang, Shilie Pan

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  34. (C 5 H 7 N 2 ) (C 8 H 4 O 4 ) PbBr: Jahn–Teller Distortion‐Induced Tilting of π‐Conjugated Planes Resolving the Second‐Order Polarizability–Structural Anisotropy Conflicts

    Angewandte Chemie International Edition · 2026-03-28

    Ming‐Yan Yu, Can Yang, Yun‐Jie Wang, Xin Yan Su, Jian Cui, Yao‐Long Zhu, Qing‐Wen Zhu, Qi Wu, Li‐Ming Wu, Ling Chen

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  35. (C 5 H 7 N 2 ) (C 8 H 4 O 4 ) PbBr: Jahn–Teller Distortion‐Induced Tilting of π‐Conjugated Planes Resolving the Second‐Order Polarizability–Structural Anisotropy Conflicts

    Angewandte Chemie · 2026-03-28

    Ming‐Yan Yu, Can Yang, Yun‐Jie Wang, Xin Yan Su, Jian Cui, Yao‐Long Zhu, Qing‐Wen Zhu, Qi Wu, Li‐Ming Wu, Ling Chen

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  36. Synergistic Enhancement of Optical Anisotropy in Nitrate Sulfamate for UV Applications: Role of Functional Group Alignment and Hydrogen Bond Network

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  37. Heterovalent Coexistence‐Driven Symmetry Breaking and Dimensional Evolution: Designing Polar Heart‐Shaped Channels for Exceptional MFIR Nonlinear Optics

    Laser & Photonics Review · 2026-05-14

    B R Zhang, Ping Feng, Sheng‐Hua Zhou, Xin-Tao Wu, Hua Lin, Qi‐Long Zhu

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  38. K 2 ZrSi 2 O 7 with a Wide Transmission Range and Enhanced Birefringence Induced by the d 0 -TM Zr-Based Units

    Inorganic Chemistry · 2026-05-28

    Xueqing Liu, Xinyue Shi, Yuan Fang, Yipeng Pang, Degao Zhong, Bing Teng, Y Huang, Zhoubin Lin, Shijia Sun

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  39. Redox‐Driven Strategy Enabling Leapfrog Enhancement of Birefringence in Layered Tin‐Based Optical Crystals

    Advanced Functional Materials · 2026-06-01

    Hangwei Jia, Yaqi Jin, Muhammad Arif, Bailin Chen, Zhihua Yang, Xueling Hou, Shilie Pan

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  40. Bridging Motifs Induced Ordered Arrangement Contributing Large Birefringence for Hg 4 BiQ 2 Cl 5 (Q═S, Se)

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    Zhen‐Cheng Wu, Chang‐Hong Li, Yu‐Xuan Zhang, Mao‐Yin Ran, Sheng‐Ping Guo

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  41. Interlayer Electronic Decoupling Unlocks Giant Birefringence in π‐Conjugated Metal‐Organic Frameworks

    Advanced Materials · 2026-06-18

    Jia-Xiang Zhang, Xinyan Wu, Weishan Li, Haolin Zhong, Jinkun Guo, Qingsheng Zeng, Mao‐Yin Ran, Ze‐Fan Yao, Yu‐Qing Zheng, Qingqing Ji, Jin‐Hu Dou

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  42. Peroxide‐Assisted Solvate Engineering Enables Record‐High Birefringence in a Solar‐Blind Transparent Crystal

    Angewandte Chemie International Edition · 2026-06-22

    Yang Li, Congcong Jin, Kang Min Ok

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  43. Peroxide‐Assisted Solvate Engineering Enables Record‐High Birefringence in a Solar‐Blind Transparent Crystal

    Angewandte Chemie · 2026-06-22

    Yang Li, Congcong Jin, Kang Min Ok

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  44. Halogen-Mediated Dimensionality Reduction in Bismuth Oxychlorides: Trade-off between Birefringence and Band Gap

    Journal of Molecular Structure · 2026-08-03

    Huaiqiang Xun, Shumei Cao, Qingyue Cui, Yi Feng, Rui Wu, Chunmei Huang, Leyan Nian

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  45. Local Aromatic Overlap Microregulation Enables Birefringence Enhancement in Isocompositional Hybrid Antimony Halides

    Crystal Growth & Design · 2026-08-21

    Jia-Wei Li, Zi-Feng Cao, Jun-Pu Wang, Wen-Pei Jia, Zi-Lin Yang, Yongyan Xu, Kai Zhang, Song-Xue Luo, Hui-Li Zheng, Jian-Qiang Zhao

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  46. Decoupling Contributions of Distinct Strategies for Enhancing Polarizability Anisotropy in Crystals Containing π-Conjugated Groups

    Inorganic Chemistry · 2026-08-23

    Haoran Liu, Chenhui Hu, Xueli Du, Qingyu Liu, Xiaona Li, Zhihua Yang, Min Zhang

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  47. From AgGaSe2 to MIIGa2Se4 (MII = Zn, Cd): Heterovalent Substitution Creates Ordered Vacancies for Balanced IR-NLO Performance

    Chinese Journal of Structural Chemistry · 2026-09-01

    Hong Chen, Zheng-Tao Hu, Mao‐Yin Ran, 马祖驹, Xin-Tao Wu, Hua Lin

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  48. Reversible Symmetry Switching, Giant Birefringence, and UV Second‐Harmonic Generation in Hybrid Niobium Oxyfluorides

    Angewandte Chemie International Edition · 2026-09-03

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

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  49. Reversible Symmetry Switching, Giant Birefringence, and UV Second‐Harmonic Generation in Hybrid Niobium Oxyfluorides

    Angewandte Chemie · 2026-09-03

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

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  50. Photocatalytic Degradation of Methylene Blue and Rhodamine B by Mononuclear Copper (II) Complex with Phenanthroline-Based Ligand

    Transition Metal Chemistry · 2026-09-17

    Nur Khaliesa Zulkarnaen, Suzaliza Mustafar, Azlan Kamari, Shahrul Kadri Ayop, Masliana Muslimin, Suhana Arshad, Muhamad Azwan Hamali, Norlinda Daud, Ma. Leah Borines, Etty Nurlia Kusumawati

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