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RESEARCH PAPER · Advanced Science · 2024

Rare‐Earth Substitution Induced Symmetry Breaking for The First Sc‐Based Nonlinear Optical Chalcogenide with High‐Performance

Chen‐Yi Zhao, Chun‐Li Hu, Nian‐Tzu Suen, Xiaohui Li, Haiping Xu, Wenfeng Zhou, Sheng‐Ping Guo

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Rare‐Earth Substitution Induced Symmetry Breaking for The First Sc‐Based Nonlinear Optical Chalcogenide with High‐PerformanceOriginalFrom NaSc 3 Ga 2 Q 8 (Q = S, Se) to KGa 2 In 3 S 8 : substitution of Sc 3+ with In 3+ to achieve doubled birefringence17LiAgCe2F10(H2O)2: Focusing on the Cation Size Effect to Reasonably Design a Nonlinear Optical Hydrated Cerium(IV) Fluoride10(CH5N3S)2Pb5Br10 and (CH5N3S)Pb2Br4: Two Nonlinear Optical Lead Thiosemicarbazide Bromides with Diverse Pb-Centered Building Units10A balance in SHG response, band gap and birefringence in a series of rare-earth sulfate-iodate6A novel metal-free crystal demonstrating superior birefringence attributed to the synergistic interaction of dual π-conjugated units8Optimizing the Hydrogen-Bond Network Drives Cadmium Ce(IV) Fluoride Hydrate with Significantly Enhanced Optical Anisotropy8Alkali Metal Substitution-Induced Structural Transformation for RbREP2Se6 (RE = Gd, Tb, Dy) with Second-Harmonic Generation Responses6Doubling Polarizability Anisotropy of The Tetrahedral Motifs to Achieve Phase Matching for Melilite-Type Compound2Structure–property relationships in noncentrosymmetric solid‐state materials7SrZnGeSe4: An Infrared Nonlinear Optical Crystal Material with Wide Transmission Range and Large SHG Response6Reactive flux assisted metal oxide–boron–sulfur routine for syntheses of CsRESiS 4 (RE = Sm, Gd–Ho): featuring nonlinear optical activity and wide band gaps5A high-performance IR nonlinear optical material Sr 3 MnGe 2 S 8 achieved via partial cation substitution-induced structural transformation2ANb 2 (PS 4 )(S 2 ) 3 (A = K, Rb, Cs): the first Nb-based NLO thiophosphates with [NbS 2 (S 2 ) 3 ] and [Nb 2 PS 6 (S 2 ) 4 ] units exhibiting tri-state structural transformation and high performance6A Homoatomic Heteroleptic Coordination Strategy for Exceptional Infrared Linear and Nonlinear Optical Properties in ANb 2 PS 4 (S 2 ) 3 (A = K,Rb,Cs)3Diamond-like Ag x Cu 3− x PS 4 ( x = 1 and 2) synthesized by the metal oxide–boron–chalcogen (MOBQ) routine: local high-entropy engineering for balanced infrared nonlinear optical performance1The modulation of structural polarity facilitating the gradient enhancement of second harmonic generation effects in hybrid metal halides5Rare-Earth Selenophosphates Cs 2 YP 2 Se 7 and KYP 2 Se 6 Synthesized by the RFMOBQ Routine: Structural Evolution and Nonlinear Optical Activity2Selenium-Based Molecular Cage Crystal β-P 4 Se 3 Br 2 : A Promising Candidate for Infrared Nonlinear Optical Applications1KHg 4 Ga 5 S 12 : A Diamond-like Tetrahedral Chalcogenide Exhibiting Giant Phase-Matching Second Harmonic Generation6Polar Antiperovskite Oxides: Promising Mid-Infrared Nonlinear Optical Materials with Strong Second-Harmonic Generation2Synergistic Distortion Engineering: Activating Nonlinear Optical Response in Quaternary Chalcogenides via Lattice‐Induced [MnS 4 ] Asymmetry1Spin-Resolved Second-Harmonic Generation from Europium 4f/5d States in a Weakly Stabilized Metastable Polymorph of Eu 2 P 2 S 60Cd/V Ratio-Driven Centrosymmetric Transition of Crystal Structures in Cesium Cadmium Vanadate Oxychlorides Cs 3 CdV 4 O 12 Cl and CsCdV 2 O 6 Cl0From KBa 4 Ge 3 S 10 Cl to ABa 3 EuGe 3 S 11 (A = Na, K) Synthesized by Reactive Flux Assisted Metal Oxide-Boron-Chalcogen (MOBQ) Method: Effect of Cation/Anion Cosubstitution on Crystal Structure and Nonlinear Optical Properties0Nonlinear Optical-Active NaAlP 2 S 6 Synthesized by the MOBQ Method: Synthesis, Structure, and Optical Properties0Mineral‐Inspired and Computation‐Assisted Rational Design of Polar Gittinsite‐Type Thiophosphates With Exceptional Nonlinear Optical Performance3Birefringence and Photocurrent Response of A Series of Rare-Earth Selenophosphates Cs4RE2(PSe4)2(P2Se6) (RE = La–Nd, Sm, Gd, Tb) Synthesized by the Metal Oxide–Boron–Chalcogen (MOBQ) Method0AVP2S7 (A = K, Rb): Dual-Optimized Infrared Nonlinear Optical Thiophosphates via Heterovalent-Substitution-Driven Symmetry Breaking and Reinforced Interlayer Interactions0AgEuPS4: Unlocking the Centrosymmetric Shackle of Rare-Earth Thiophosphates via Microscopic Distortion Cascading for Enhanced Second-Harmonic Generation Response0EuMn6Ga6S16: A Wide Bandgap Europium-Based Nonlinear Optical Sulfide0

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  1. From NaSc 3 Ga 2 Q 8 (Q = S, Se) to KGa 2 In 3 S 8 : substitution of Sc 3+ with In 3+ to achieve doubled birefringence

    Chemical Science · 2025-01-01

    Yun Xie, Wen‐Dong Yao, Qiu-Yang Du, Wenfeng Zhou, Nian‐Tzu Suen, Wenlong Liu, Sheng‐Ping Guo

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  2. LiAgCe2F10(H2O)2: Focusing on the Cation Size Effect to Reasonably Design a Nonlinear Optical Hydrated Cerium(IV) Fluoride

    Inorganic Chemistry · 2025-03-24

    Wen-Ye Gao, Yi‐Lei Lv, Siyu Ma, Cheng Chen, Wenlong Liu, Ru‐Ling Tang

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  3. (CH5N3S)2Pb5Br10 and (CH5N3S)Pb2Br4: Two Nonlinear Optical Lead Thiosemicarbazide Bromides with Diverse Pb-Centered Building Units

    Inorganic Chemistry · 2025-05-20

    Ru‐Ling Tang, Yue‐Qi Wei, Yi‐Lei Lv, Bing-Wei Miao, Cheng Chen, Wenlong Liu

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  4. A balance in SHG response, band gap and birefringence in a series of rare-earth sulfate-iodate

    Journal of Molecular Structure · 2025-07-01

    Chunxiang Wu, Y. X. Li, Zhengli Liang, Xiao Mei Jiang, Xiao Jiang, Hui Fang, Lixiang Qin, Xingyuan Bai, Lehui Liu, Lehui Liu, Xingxing Jiang, Xingxing Jiang, Hongming Liu, Hongming Liu

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  5. A novel metal-free crystal demonstrating superior birefringence attributed to the synergistic interaction of dual π-conjugated units

    Science China Materials · 2025-07-07

    Die-Xue Yang, Ru‐Ling Tang, Yi‐Lei Lv, Bing-Wei Miao, Wenlong Liu, Sheng‐Ping Guo

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  6. Optimizing the Hydrogen-Bond Network Drives Cadmium Ce(IV) Fluoride Hydrate with Significantly Enhanced Optical Anisotropy

    Inorganic Chemistry · 2025-07-25

    Wen-Ye Gao, Siyu Ma, Bing-Wei Miao, Wenfeng Zhou, Wenlong Liu, Ru‐Ling Tang

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  7. Alkali Metal Substitution-Induced Structural Transformation for RbREP2Se6 (RE = Gd, Tb, Dy) with Second-Harmonic Generation Responses

    Inorganic Chemistry · 2025-08-08

    Zongze Li, Zi-Nan Chen, Ning Wang, Mao‐Yin Ran, Wenlong Liu, Sheng‐Ping Guo

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  8. Doubling Polarizability Anisotropy of The Tetrahedral Motifs to Achieve Phase Matching for Melilite-Type Compound

    Inorganic Chemistry · 2025-08-18

    Zhi Bing Deng, Rui Xiao, Mao‐Yin Ran, Ao Guo, Xiang Chen, Wenlong Liu, Sheng‐Ping Guo

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  9. Structure–property relationships in noncentrosymmetric solid‐state materials

    Bulletin of the Korean Chemical Society · 2025-08-27

    Y.J Kim, Youngbin Chae, H. S. Lim, Kang Min Ok

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  10. SrZnGeSe4: An Infrared Nonlinear Optical Crystal Material with Wide Transmission Range and Large SHG Response

    Inorganic Chemistry · 2025-09-29

    Xia Wu, Mengjie Ma, Huilin Yin, Shuchang Wu, Hang Zhang, Kuixian Cai, Xiao‐Ming Jiang, Dajiang Mei

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  11. Reactive flux assisted metal oxide–boron–sulfur routine for syntheses of CsRESiS 4 (RE = Sm, Gd–Ho): featuring nonlinear optical activity and wide band gaps

    Inorganic Chemistry Frontiers · 2025-11-05

    Zhen-Cheng Wu, Fang-Xu Tian, Rui Xiao, Mao-Yin Ran, Wenlong Liu, Wen-Tong Chen, Sheng-Ping Guo

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  12. A high-performance IR nonlinear optical material Sr 3 MnGe 2 S 8 achieved via partial cation substitution-induced structural transformation

    Inorganic Chemistry Frontiers · 2025-11-14

    A-Lan Xu, Mao‐Yin Ran, Zuju Ma, Xin-Tao Wu, Hua Lin, Qi‐Long Zhu

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  13. ANb 2 (PS 4 )(S 2 ) 3 (A = K, Rb, Cs): the first Nb-based NLO thiophosphates with [NbS 2 (S 2 ) 3 ] and [Nb 2 PS 6 (S 2 ) 4 ] units exhibiting tri-state structural transformation and high performance

    Inorganic Chemistry Frontiers · 2025-12-09

    Zong-Ze Li, Yang Chi, Yu-Xuan Zhang, Ao Guo, Hui-Zhi Gao, Zheng-Ren Chen, Mao-Yin Ran, Wenlong Liu, Sheng-Ping Guo

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  14. 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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  15. Diamond-like Ag x Cu 3− x PS 4 ( x = 1 and 2) synthesized by the metal oxide–boron–chalcogen (MOBQ) routine: local high-entropy engineering for balanced infrared nonlinear optical performance

    Inorganic Chemistry Frontiers · 2026-01-01

    Ao Guo, Rong-Ling Zhu, Zi-Nan Chen, Zhi Deng, Zong-Ze Li, Shao-Peng Gui, Mao‐Yin Ran, Sheng‐Ping Guo

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

    Science China Chemistry · 2026-01-04

    Ru‐Ling Tang, Die-Xue Yang, Jian-Dong Guo, C. Z. Chen, Wenlong Liu, Sheng‐Ping Guo

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  17. Rare-Earth Selenophosphates Cs 2 YP 2 Se 7 and KYP 2 Se 6 Synthesized by the RFMOBQ Routine: Structural Evolution and Nonlinear Optical Activity

    Inorganic Chemistry · 2026-01-14

    Zong-Ze Li, Ming-Yang Li, N. Wang, Mao‐Yin Ran, Sheng‐Ping Guo

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  18. Selenium-Based Molecular Cage Crystal β-P 4 Se 3 Br 2 : A Promising Candidate for Infrared Nonlinear Optical Applications

    Inorganic Chemistry · 2026-01-14

    Xingwang Zhu, Chao Wang, Chensheng Lin, Cheng Hu, Shunda Yang, Tao Yan, Min Luo

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  19. KHg 4 Ga 5 S 12 : A Diamond-like Tetrahedral Chalcogenide Exhibiting Giant Phase-Matching Second Harmonic Generation

    Chemistry of Materials · 2026-02-03

    Weiping Guo, Chao Yang, Bingxuan Li, Hong‐Hua Cui, Lingyun Li, Yan Yu, Zhong‐Zhen Luo, Zhigang Zou

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  20. Polar Antiperovskite Oxides: Promising Mid-Infrared Nonlinear Optical Materials with Strong Second-Harmonic Generation

    Chemistry of Materials · 2026-03-26

    Yunseung Kuk, Kang Min Ok, P. Shiv Halasyamani

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  21. Synergistic Distortion Engineering: Activating Nonlinear Optical Response in Quaternary Chalcogenides via Lattice‐Induced [MnS 4 ] Asymmetry

    Advanced Optical Materials · 2026-04-21

    Guili Wang, Siyang Luo, Ming‐Hsien Lee, Jiyong Yao

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  22. Spin-Resolved Second-Harmonic Generation from Europium 4f/5d States in a Weakly Stabilized Metastable Polymorph of Eu 2 P 2 S 6

    Chemistry of Materials · 2026-05-08

    Minwei Xiang, Hanxiang Mi, X Y Wang, 蘇思豪, Xiyue Cheng, Shuiquan Deng

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  23. Cd/V Ratio-Driven Centrosymmetric Transition of Crystal Structures in Cesium Cadmium Vanadate Oxychlorides Cs 3 CdV 4 O 12 Cl and CsCdV 2 O 6 Cl

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    Xindan Xu, Lei Geng, Baozhu Zhu, Shoubao Zhang, Yuqi Song, Changyu Meng

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  24. From KBa 4 Ge 3 S 10 Cl to ABa 3 EuGe 3 S 11 (A = Na, K) Synthesized by Reactive Flux Assisted Metal Oxide-Boron-Chalcogen (MOBQ) Method: Effect of Cation/Anion Cosubstitution on Crystal Structure and Nonlinear Optical Properties

    Inorganic Chemistry · 2026-06-12

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  25. Nonlinear Optical-Active NaAlP 2 S 6 Synthesized by the MOBQ Method: Synthesis, Structure, and Optical Properties

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  26. Mineral‐Inspired and Computation‐Assisted Rational Design of Polar Gittinsite‐Type Thiophosphates With Exceptional Nonlinear Optical Performance

    Advanced Functional Materials · 2026-08-06

    Mao‐Yin Ran, Shao-Peng Gui, Jian Cheng, Yu‐Xuan Zhang, Wen‐Dong Yao, Wenlong Liu, Sheng‐Ping Guo

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  27. Birefringence and Photocurrent Response of A Series of Rare-Earth Selenophosphates Cs4RE2(PSe4)2(P2Se6) (RE = La–Nd, Sm, Gd, Tb) Synthesized by the Metal Oxide–Boron–Chalcogen (MOBQ) Method

    Inorganic Chemistry · 2026-08-10

    Si Yang, Zong-Ze Li, Ning Wang, Xin Lei Zhao, Sheng‐Ping Guo

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  28. AVP2S7 (A = K, Rb): Dual-Optimized Infrared Nonlinear Optical Thiophosphates via Heterovalent-Substitution-Driven Symmetry Breaking and Reinforced Interlayer Interactions

    Inorganic Chemistry · 2026-08-11

    Shao-Peng Gui, Zi-Nan Chen, Wei-Hua Yan, Yu‐Xuan Zhang, Mao‐Yin Ran, Sheng‐Ping Guo

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  29. AgEuPS4: Unlocking the Centrosymmetric Shackle of Rare-Earth Thiophosphates via Microscopic Distortion Cascading for Enhanced Second-Harmonic Generation Response

    Chemistry of Materials · 2026-08-13

    Ao Guo, Si Yang, Yang Chi, Yu‐Xuan Zhang, Tianwei He, Mao‐Yin Ran, Sheng‐Ping Guo

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  30. EuMn6Ga6S16: A Wide Bandgap Europium-Based Nonlinear Optical Sulfide

    Inorganic Chemistry · 2026-08-16

    Yu‐Xuan Zhang, Jiang-Hui Fan, Zhen‐Cheng Wu, Shao-Peng Gui, Mao‐Yin Ran, Sheng‐Ping Guo

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