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RESEARCH PAPER · Coordination Chemistry Reviews · 2025

Research progress and future prospect of chalcogenides with large optical anisotropy

Zhen-Cheng Wu, Sheng‐Ping Guo

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Research progress and future prospect of chalcogenides with large optical anisotropyOriginalSignificant enhancement in the birefringence of metal phosphite halides via the introduction of π-conjugated cations17AlGaSe3: Tuning Stability via Partial Cation Substitution and Achieving a Nonlinear Optical Property Leap6Synergistic Enhancement of Band Gap and Optical Anisotropy via Functional-Site Cosubstitution in Antiperovskite-Type Chalcohalides [Ba2K][X][MS4] (M = Ge, Si; X = Cl, Br)2Structure-property relationships in IR nonlinear optical chalcogenides with stereochemically active lone pairs29[HgX 2 ] Linear Group Enabled Ultraviolet Birefringent Crystal RbHg 5 Br 11 with Strong Optical Anisotropy and Wide Bandgap12CsGaGe₃Se₈: Enhanced optical anisotropy and bandgap via cation-substitution-driven dimensionality reduction0Exceptional Enhancement of Optical Anisotropy Achieved via the Strategy of Combining Rigid Groups with High Symmetry and π‐Conjugated Organic Groups in Hybrid Fluorides33π-Conjugated unit bridge for giant second-harmonic generation and birefringence in hybrid materials with dual heteroleptic polyhedra5Coordination‐Induced Amplification of Birefringence and Nonlinear Optical Response in a Chiral Metal–Organic Framework6Coordination‐Induced Amplification of Birefringence and Nonlinear Optical Response in a Chiral Metal–Organic Framework11Organic π-conjugated units as versatile building blocks for high-performance birefringent crystals6Hybrid Zinc‒Based Halides with Giant Optical Anisotropy via Protonation‒Engineered π ‒Conjugated Organic Group24Rational design of novel mixed metal sulfates with diverse dimensional structures and short UV cutoff edges1Dual-anion synergy drives remarkable birefringence in sulfate–nitrate crystals1Ba 3 (MoO 2 F 3 )PO 4 F 2 : Rational Design and Synthesis of an Alkaline-Earth Phosphate Fluoride as a Birefringent Crystal1[C(NH 2 ) 3 ] 2 PO 3 (OH): A Deep-Ultraviolet Birefringent Crystal Enabled by Synergy of π-Conjugated Cations and Heteroleptic Tetrahedra2Sb 2 (SeO 3 ) 2 SeO 4 : A Selenite–Selenate Crystal with Balanced Band Gap and Birefringence3Achieving giant optical anisotropy in the mid-far infrared region via ideal alignment of dual functional motifs0KGdSiSe 4 and KGdGeSe 4 : two rare earth-based selenides with wide bandgaps and large nonlinear optical responses0KTeOPO 4 and NH 4 SnClSO 4 : two new KTiOPO 4 derivatives as birefringent crystals featuring enhanced optical anisotropy0Synergistic dual-modification strategy of π-conjugated cations and tetrahedra: rational design of ultraviolet high-birefringence monofluorophosphates0Realizing Phase‐Matching of Nonlinear Optical [ABa 3 Br 2 ][Ga 5 Se 10 ] (A = Cs, Rb, K, Na) Through Large Anisotropic Lattice Distortion6Realizing Phase‐Matching of Nonlinear Optical [ABa 3 Br 2 ][Ga 5 Se 10 ] (A = Cs, Rb, K, Na) Through Large Anisotropic Lattice Distortion11Anion-Centered Engineering for Simultaneously Enhancing Birefringence and Band Gap in Chalcogenides1Programmable Anisotropic in Diazapyrene Cocrystals With Birefringence Exceeding 1.27Programmable Anisotropic in Diazapyrene Cocrystals With Birefringence Exceeding 1.21Ba 4 CdGa 2 S 6 F 4 : A Chalcohalide Birefringent Crystal with Large Band Gap Designed by the Cation and Anion Cosubstitution Strategy2[Ba2K][Br][SiS4]: An antiperovskite-type chalcohalide with simultaneously enhanced birefringence and band gap via cation-anion co-substitution0{[Ge 2 S 7 ] 6– } ∞ Chains-Mediated Framework Reorganization Triggers Dimensional Upgrade and Infrared Nonlinear Optical Response3Extremely low thermal conductivity of Ba2SiSe4−xTex: Structural aspects and bandgap tuning by mixing Se and Te0K 3 Mg 2 [K 6 MgCl 3 ][Ga 20 S 36 ]: A Diamond-like Framework Based on Mixed-Type Supertetrahedra for Excellent Nonlinear Optical Property1From Coplanarity to Coaxiality: A Linearity-Oriented Design Paradigm for Ultrahigh Ultraviolet Birefringent Inorganic Crystals4Heterovalent Coexistence‐Driven Symmetry Breaking and Dimensional Evolution: Designing Polar Heart‐Shaped Channels for Exceptional MFIR Nonlinear Optics5Achieving High‐Birefringence Thiophosphates From Low Polarizability Anisotropy Units by an Axial Linear Matching Strategy1Bridging 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 Frameworks0A 3 Zr 2 (PS 4 )(P 2 S 7 ) 2 (A = K, Rb, Cs) Synthesized by the Metal Oxide-Boron-Chalcogen Routine: A Series of Zirconium-Based Thiophosphate Nonlinear Optical Crystals Featuring PS 4 Tetrahedron and P 2 S 7 Dimer0Hierarchical Ordering Decouples the SHG–Birefringence–LIDT Trade‐Off in a Single‐Phase Mid‐Infrared Nonlinear Optical Crystal0Hierarchical Ordering Decouples the SHG–Birefringence–LIDT Trade‐Off in a Single‐Phase Mid‐Infrared Nonlinear Optical Crystal0Exceptional Solar‐Blind Birefringence Engineered by Complementary Hydrogen‐Bond Ordering of π‐Conjugated Units0Heavy‐Halide Coordination and Lattice‐Confined Molecular Alignment Enable Giant Birefringence in Hybrid Metal Halides0Engineering multi-metallic chalcogenides for advanced supercapacitors: Recent progress, challenges, and perspectives0From AgGaSe2 to MIIGa2Se4 (MII = Zn, Cd): Heterovalent Substitution Creates Ordered Vacancies for Balanced IR-NLO Performance0Bulk growth, optical and thermal properties of CsCdCl3 birefringent crystal0Domino‐Effect Amplification via Covalent‐Chain Engineering for Giant Birefringence in NaAsQ 2 (Q = S, Se) Crystals0[La3Br][GeS4]2: Cationic-Moiety-Guided Strategy Enables Record Birefringence and Broad Optical Window0

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  1. Significant enhancement in the birefringence of metal phosphite halides via the introduction of π-conjugated cations

    Chemical Science · 2025-01-01

    Ru‐Ling Tang, Yue Wang, Yi‐Lei Lv, Bing-Wei Miao, Wenlong Liu, Sheng‐Ping Guo

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  2. AlGaSe3: Tuning Stability via Partial Cation Substitution and Achieving a Nonlinear Optical Property Leap

    Inorganic Chemistry · 2025-08-22

    Jian Ping Cheng, Wen-Rui Zhou, Wen‐Dong Yao, Hai-Ping Xu, Wenlong Liu, Sheng‐Ping Guo

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  3. 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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  4. 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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  5. [HgX 2 ] Linear Group Enabled Ultraviolet Birefringent Crystal RbHg 5 Br 11 with Strong Optical Anisotropy and Wide Bandgap

    Advanced Science · 2025-09-09

    Yingtai Du, Wangfei Che, Yunfei Shi, Juanjuan Lu, Xiaodong Zhou, Ting Liu, Shilie Pan, Junjie Li

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  6. CsGaGe₃Se₈: Enhanced optical anisotropy and bandgap via cation-substitution-driven dimensionality reduction

    Inorganic Chemistry Communications · 2025-10-01

    Yue Wang, Rongfang Jiang, Zihao Lou, Yong‐Fang Shi

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  7. Exceptional Enhancement of Optical Anisotropy Achieved via the Strategy of Combining Rigid Groups with High Symmetry and π‐Conjugated Organic Groups in Hybrid Fluorides

    Advanced Science · 2025-10-06

    Ru‐Ling Tang, Bing-Wei Miao, Guo-Ren Zhu, Wenlong Liu, Sheng‐Ping Guo

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  8. π-Conjugated unit bridge for giant second-harmonic generation and birefringence in hybrid materials with dual heteroleptic polyhedra

    Chinese Chemical Letters · 2025-11-01

    Yumei Zhang, Wen‐Dong Yao, Yifan Fu, Zhen-Cheng Wu, Zhen-Cheng Wu, Wenlong Liu, Wenlong Liu, Jiajing Wu, Sheng‐Ping Guo

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  9. Coordination‐Induced Amplification of Birefringence and Nonlinear Optical Response in a Chiral Metal–Organic Framework

    Angewandte Chemie · 2025-11-02

    Xinchao Wang, Hongyuan Sha, Zhaoxing Wang, Fei Wang, Shangda Li, Jian Zhang

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  10. Coordination‐Induced Amplification of Birefringence and Nonlinear Optical Response in a Chiral Metal–Organic Framework

    Angewandte Chemie International Edition · 2025-11-03

    Xinchao Wang, Hongyuan Sha, Zhaoxing Wang, Fei Wang, Shangda Li, Jian Zhang

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  11. Organic π-conjugated units as versatile building blocks for high-performance birefringent crystals

    Chinese Journal of Structural Chemistry · 2025-11-19

    Zhenchao Bai, Sangen Zhao, Kang Min Ok, Junhua Luo

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  12. 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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  13. Rational design of novel mixed metal sulfates with diverse dimensional structures and short UV cutoff edges

    Journal of Molecular Structure · 2025-11-22

    Bingchen Xiao, Yanyan Ding, Jindan Tian, Lei Hou, Ming Xi, Ruoyan Qv, Yaoqing Chu, Lili Liu

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  14. Dual-anion synergy drives remarkable birefringence in sulfate–nitrate crystals

    Inorganic Chemistry Frontiers · 2025-11-24

    LeHui Liu, FeiFei Yuan, YiSheng Huang, LiZhen Zhang, ZhouBin Lin

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  15. 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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  16. [C(NH 2 ) 3 ] 2 PO 3 (OH): A Deep-Ultraviolet Birefringent Crystal Enabled by Synergy of π-Conjugated Cations and Heteroleptic Tetrahedra

    ACS Applied Optical Materials · 2025-12-16

    Huan Zhou, Meng Cheng, Zhihua Yang, Shilie Pan

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  17. Sb 2 (SeO 3 ) 2 SeO 4 : A Selenite–Selenate Crystal with Balanced Band Gap and Birefringence

    Crystal Growth & Design · 2025-12-25

    Han Bing Luo, Siyu Chen, Bailiang Li, Liling Cao, Xuehua Dong, Ling Huang, Guohong Zou

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  18. 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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  19. KGdSiSe 4 and KGdGeSe 4 : two rare earth-based selenides with wide bandgaps and large nonlinear optical responses

    Dalton Transactions · 2026-01-01

    Zhenglong Li, Guansong Zheng, Chen Bai, Leyan Nian, Shilie Pan, Junjie Li

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  20. KTeOPO 4 and NH 4 SnClSO 4 : two new KTiOPO 4 derivatives as birefringent crystals featuring enhanced optical anisotropy

    Journal of Materials Chemistry C · 2026-01-01

    Ruo-Nan Zhang, Xuping Shi, Abudukadi Tudi, Wenbin Zhang, Zhihua Yang, Fangfang Zhang, Shilie Pan, Shujuan Han

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  21. Synergistic dual-modification strategy of π-conjugated cations and tetrahedra: rational design of ultraviolet high-birefringence monofluorophosphates

    Journal of Materials Chemistry C · 2026-01-01

    Huan Zhou, Meng Cheng, Yuqi Qin, Congwei Xie, Junjie Li, Xueling Hou, Zhihua Yang

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  22. Realizing Phase‐Matching of Nonlinear Optical [ABa 3 Br 2 ][Ga 5 Se 10 ] (A = Cs, Rb, K, Na) Through Large Anisotropic Lattice Distortion

    Angewandte Chemie · 2026-01-05

    Meng‐Na Jing, Si‐Fan Lu, Xiao‐Ming Jiang, Bin‐Wen Liu, Guo‐Cong Guo

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  23. Realizing Phase‐Matching of Nonlinear Optical [ABa 3 Br 2 ][Ga 5 Se 10 ] (A = Cs, Rb, K, Na) Through Large Anisotropic Lattice Distortion

    Angewandte Chemie International Edition · 2026-01-05

    Meng‐Na Jing, Si‐Fan Lu, Xiao‐Ming Jiang, Bin‐Wen Liu, Guo‐Cong Guo

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  24. 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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  25. 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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  26. 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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  27. 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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  28. [Ba2K][Br][SiS4]: An antiperovskite-type chalcohalide with simultaneously enhanced birefringence and band gap via cation-anion co-substitution

    Inorganic Chemistry Communications · 2026-03-10

    Yue Wang, Hua Wang, Rongfang Jiang, Yongfang Shi

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  29. {[Ge 2 S 7 ] 6– } ∞ Chains-Mediated Framework Reorganization Triggers Dimensional Upgrade and Infrared Nonlinear Optical Response

    Chemistry of Materials · 2026-03-19

    Wen-Rui Zhou, Zhen-Cheng Wu, Yong-han WU Xue-jiao LIU, Mao‐Yin Ran, Sheng‐Ping Guo

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  30. Extremely low thermal conductivity of Ba2SiSe4−xTex: Structural aspects and bandgap tuning by mixing Se and Te

    Inorganic Chemistry Communications · 2026-04-22

    Sweta Yadav, Komal Srivastava, Swati, Sayani Barman, Sambit S.S. Rout, Jai Prakash

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  31. K 3 Mg 2 [K 6 MgCl 3 ][Ga 20 S 36 ]: A Diamond-like Framework Based on Mixed-Type Supertetrahedra for Excellent Nonlinear Optical Property

    Chemistry of Materials · 2026-04-22

    Jun-Long Chen, Shao‐Min Pei, Xiao‐Ming Jiang, Bin‐Wen Liu, Guo-Cong Guo

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  32. 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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  33. 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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  34. 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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  35. Bridging Motifs Induced Ordered Arrangement Contributing Large Birefringence for Hg 4 BiQ 2 Cl 5 (Q═S, Se)

    Small · 2026-06-02

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

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  36. 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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  37. A 3 Zr 2 (PS 4 )(P 2 S 7 ) 2 (A = K, Rb, Cs) Synthesized by the Metal Oxide-Boron-Chalcogen Routine: A Series of Zirconium-Based Thiophosphate Nonlinear Optical Crystals Featuring PS 4 Tetrahedron and P 2 S 7 Dimer

    Inorganic Chemistry · 2026-07-01

    Zi-Nan Chen, Zong-Ze Li, Ning Wang, Jian Cheng, Zhen‐Cheng Wu, Feng Qiu, Mao‐Yin Ran, Sheng‐Ping Guo

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  38. Hierarchical Ordering Decouples the SHG–Birefringence–LIDT Trade‐Off in a Single‐Phase Mid‐Infrared Nonlinear Optical Crystal

    Angewandte Chemie International Edition · 2026-07-24

    Yan Guo, Ming‐Xin Li, Ying Guo, Bin‐Wen Liu, Xiao‐Ming Jiang, Guo‐Cong Guo

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  39. Hierarchical Ordering Decouples the SHG–Birefringence–LIDT Trade‐Off in a Single‐Phase Mid‐Infrared Nonlinear Optical Crystal

    Angewandte Chemie · 2026-07-24

    Yan Guo, Ming‐Xin Li, Yi Guo, Bin‐Wen Liu, Xiao‐Ming Jiang, Guo‐Cong Guo

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  40. Exceptional Solar‐Blind Birefringence Engineered by Complementary Hydrogen‐Bond Ordering of π‐Conjugated Units

    Small · 2026-08-05

    Qianxi Hu, Junwei Feng, Long Chen, Minqiang Gai

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  41. Heavy‐Halide Coordination and Lattice‐Confined Molecular Alignment Enable Giant Birefringence in Hybrid Metal Halides

    Advanced Functional Materials · 2026-08-07

    Mingshu Zhang, Shuya Zhao, Zhen‐Cheng Wu, Zheyu Zhang, Sheng‐Ping Guo, Yan Zhou

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  42. Engineering multi-metallic chalcogenides for advanced supercapacitors: Recent progress, challenges, and perspectives

    Journal of Alloys and Compounds · 2026-09-01

    Sumanta Sahoo, Rajesh Kumar, Myung Jong Kim

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  43. 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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  44. Bulk growth, optical and thermal properties of CsCdCl3 birefringent crystal

    Journal of Crystal Growth · 2026-09-24

    Qian Wu, Wei Huang, Zhen Jia, Tianyu Wang, Haochen Li, Hongrui Liu, Bing Li, Haotian Tian, Ying Zhao, Mingjun Xia

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  45. Domino‐Effect Amplification via Covalent‐Chain Engineering for Giant Birefringence in NaAsQ 2 (Q = S, Se) Crystals

    Laser & Photonics Review · 2026-09-24

    Bo Zhang, Weiqi Huang, Yang Chi, Xin‐Tao Wu, Hua Lin, Qi‐Long Zhu

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  46. [La3Br][GeS4]2: Cationic-Moiety-Guided Strategy Enables Record Birefringence and Broad Optical Window

    Crystal Growth & Design · 2026-10-10

    Cuier Deng, Yuhan Hu, Ruixi Wang, Jingyu Guo

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