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RESEARCH PAPER · Angewandte Chemie International Edition · 2022

Perfectly Encoding π‐Conjugated Anions in the RE5(C3N3O3)(OH)12 (RE=Y, Yb, Lu) Family with Strong Second Harmonic Generation Response and Balanced Birefringence

Xianghe Meng, Xingyu Zhang, Qingxiong Liu, Zhengyang Zhou, Xingxing Jiang, Yonggang Wang, Zheshuai Lin, Mingjun Xia

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Perfectly Encoding π‐Conjugated Anions in the RE5(C3N3O3)(OH)12 (RE=Y, Yb, Lu) Family with Strong Second Harmonic Generation Response and Balanced BirefringenceOriginal(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 cations56A 0.5 H 2 C 6 N 7 O 3 ·4H 2 O (A = Ca 2+ , Sr 2+ ) iso-cyamelurates with ultra-large π-conjugated group and excellent nonlinear optical properties10A lithium–scandium sulfate with second-harmonic generation response and deep-ultraviolet transparency7A UV solar-blind nonlinear optical crystal with confined π-conjugated groups13Cs[B 3 O 3 F 2 (OH) 2 ]: discovery of a hydroxyfluorooxoborate guided by selective organic–inorganic transformation13From H 12 C 4 N 2 CdI 4 to H 11 C 4 N 2 CdI 3 : a highly polarizable CdNI 3 tetrahedron induced a sharp enhancement of second harmonic generation response and birefringence50Recent advances on the synthesis of Sb(III)-based inorganic ultraviolet nonlinear optical materials47Two UV optical crystals with strong optical anisotropy, large band gaps and an α-BBO type structure7The First UV Nonlinear Optical Selenite Material: Fluorination Control in CaYF(SeO 3 ) 2 and Y 3 F(SeO 3 ) 485The First UV Nonlinear Optical Selenite Material: Fluorination Control in CaYF(SeO3)2 and Y3F(SeO3)47Unveiling the Superior Optical Properties of Novel Melamine‐Based Nonlinear Optical Material with Strong Second‐Harmonic Generation and Giant Optical Anisotropy74A Hydrogen Bonded Supramolecular Framework Birefringent Crystal89A Hydrogen Bonded Supramolecular Framework Birefringent Crystal13Cs 2 Mg(H 2 C 3 N 3 S 3 ) 4 ·8H 2 O: An Excellent Birefringent Material with Giant Optical Anisotropy in π-Conjugated Trithiocyanurate19Y(HSeO3)(SeO3)(H2O)·(H2O) and Y2(SeO3)2(SeO4)(H2O)2·(H2O)0.75: Two yttrium selenites with a short UV cut-off edge explored from pure selenite compounds20Three‐in‐One Strategy Constructing the First High‐Performance Nonlinear Optical Sulfide Crystallizing with the P43 Space Group27From Centrosymmetry to Noncentrosymmetry: Precise Structural Regulation and Characterization on ZnHPO3·2H2O Polymorphs13(NH 4 ) 2 (I 5 O 12 )(IO 3 ) and K 1.03 (NH 4 ) 0.97 (I 5 O 12 )(IO 3 ): Mixed‐Valent Polyiodates with Unprecedented I 5 O 12 − Unit Exhibiting Strong Second‐Harmonic Generation Responses and Giant Birefringence22α- and β-(C4H5N2O)(IO3)·HIO3: Two SHG Materials Based on Organic–Inorganic Hybrid Iodates14Designing a Dimension Reduced Hybrid Perovskite with Robust Large Birefringence by Expanding Cationic π‐Delocation40Rational Design of Noncentrosymmetric Organic–Inorganic Hybrids with a π-Conjugated Pyridium-Type Cation for High Nonlinear-Optical Performance19Heterologous Isomorphic Substitution Induces Optical Property Enhancement for Deep-UV Crystals: a Case in Rb[B3O3F2(OH)2]10A Two‐Dimensional Hybrid Perovskite With Heat Switching Birefringence47A Two‐Dimensional Hybrid Perovskite With Heat Switching Birefringence7A potassium lead 2-methylmalonate-iodide nonlinear optical crystal with strong second-harmonic generation response and large birefringence2Ln 2 F 2 (OH 2 )(MoO 3 ) 2 (SeO 3 ) 2 : Promising Multifunctional Nonlinear Optical Materials Created by Partial Fluorination Strategy under Corrosion Resistant Supercritical Reactions25CsSn2(HPO3)2I: The first inorganic metal phosphite iodide as a promising birefringent material exhibits a large birefringence with ideally layered framework24C(NH2)3Cd(C2O4)Cl(H2O)·H2O and BaCd(C2O4)1.5Cl(H2O)2: Two Oxalate Chlorides Obtained by Chemical Scissors Strategy Exhibiting Low-Dimensional Structural Networks and Balanced Overall Optical Properties14[(C 5 H 6 N 2 ) 2 H](Sb 4 F 13 ): a polyfluoroantimonite with a strong second harmonic generation effect60A UV non-hydrogen pure selenite nonlinear optical material for achieving balanced properties through framework-optimized structural transformation41A-site cation manipulation of exemplary second harmonic generation response and optical anisotropy in rare-earth borates18Discovery of excellent ultraviolet nonlinear optical materials in chlorates and bromates with highly stereochemically active lone pairs12N 2 H 4 Zn(HC 3 N 3 O 3 ): exceptionally strong second harmonic generation and ultra-long phosphorescence16Research progress in optical materials with cationic organic planar π-conjugated groups containing CN bonds34Synthesis and Characterization of Metal Iso-cyamelurate K0.5In0.5(H2C6N7O3)2·9H2O with Large Birefringence8Tunable Optical Anisotropy in Rare‐Earth Borates with Flexible [BO3] Clusters7PbBeB2O5: A High-Performance Ultraviolet Nonlinear-Optical Crystal with Functional [BeB2O8]8– Group3A3Sc(SO4)3 (A = K, Rb, Cs): Three Deep‐Ultraviolet Transparent Alkali‐Scandium Sulfates with Strong Second‐Harmonic Generation Response and High Thermal Stability14NaK5La2(SO4)6: Enhanced Birefringence of Multiple-Alkali Metal Sulfate Systems via Rare Earth Metal-Centered Polyhedra5(C5H12N2S)Hg(NO3)2: A Mercury Nitrate Nonlinear Optical Crystal Motivated by Heteroatom Coordination Strategy9A Robust Phosphonate‐Based Hydrogen‐Bonded Organic Framework Birefringent Crystal39Achieving the Birefringence Optimization by Methyl Modulation in Organic Nonlinear Optical Crystals15(C10N2H10)(HI2O6)(HIO3)(IO3): A Birefringent Material Featuring Large π-Conjugated Organic Cation and Two Types of Iodate Anions2A Giant Optically Anisotropic Phosphate Driven by Mixed Valence Mercury Units22Two α‐SiO 2 ‐Related Deep‐Ultraviolet Phase‐Matchable Optical Nonlinear Beryllium Silicate Crystals Na 2 BeSiO 4 and Li 2 BeSiO 4 with Enhanced SHG Effect10Unveiling Charge Dependent Law to Enhance Birefringence in 2‐Aminopyrimidine Family21K6NaCaRe2(B5O10)3 (Re = Y, Lu): Two NLO Compounds Exhibiting a Short Absorption Edge in the A7–xA’xAeRe2(B5O10)3 (x = 0, 1) Family4(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“Three functions in one”: multifunctional rare-earth cyamelurates with magnetism, luminescence, and giant optical nonlinearity6A remarkable solar-blind ultraviolet nonlinear optical crystal with comprehensive performance and enhanced thermal stability4An excellent ultraviolet nonlinear optical crystal derived from the polar methylphosphonate unit8Greatly enhancing birefringence of fluorosilicates through the synergetic effect of functional units13Hydrogen bonding regulation-oriented design of pyridine sulfonate as a promising UV birefringent crystal characterized by enhanced structural anisotropy11Optimizing optical anisotropy in low-dimensional structures via intralayer hydrogen bonding modulation and anionic substitution17Sr2Zn(C3N3O3)2: An Alkaline Earth and d10 Transition Metal Based Ultraviolet Cyanurate with Large Birefringence6An alkali and rare earth metal mixed cyanurate KLa2(C3N3O3)2Cl with large birefringence: Synthesis and characterization2Na3Y2F3P2O8 and K4Y3F5P4O14: [YOF] Polyhedra Inducing Birefringence Enhancement in Non-π-Conjugated Phosphate Systems3Enhanced Shielding and Corrosion Resistance of the ZCEOSS@PANI Composite by Polymer Encapsulation3LiAgCe2F10(H2O)2: Focusing on the Cation Size Effect to Reasonably Design a Nonlinear Optical Hydrated Cerium(IV) Fluoride10Unearthing Hydrogen Bonded Metal‐Free Crystal with Remarkable Optical Anisotropy9From AgHgI(SO4) to AgHg3I3.2Cl1.8(SO4): Symmetry Breaking of the Belousovite‐Type Topology by Mixed Halides to Achieve Strong Nonlinear Optical Effect14Exploiting Rigid Inorganic π‐Conjugated Units and Deprotonatable Organic π‐Conjugated Dimers for Enhanced Linear and Nonlinear Optical Properties9Decoupling the SHG‐Birefringence Trade‐off in UV NLO Materials via Triple‐Control Coordination Engineering: Achieving Synergistic Performance Optimization88Decoupling the SHG‐Birefringence Trade‐off in UV NLO Materials via Triple‐Control Coordination Engineering: Achieving Synergistic Performance Optimization13[CON3H6BF4]: An Efficient Metal‐Free Borate with Optimized Birefringence Achieved by Structural Design Strategy15Controllable Synthesis of a Strong Ultraviolet Nonlinear Optical Crystal by Tailoring the Lead Oxychloride Polyhedron3Polar Lithium l -Aspartate Monohydrate: A Semiorganic Ultraviolet Transparent Nonlinear Optical Crystal1(C9H7BrN)BF4 and (C9H7BrN)2SiF6: Two Birefringent Crystals with Distinct Optical Anisotropy Regulated by Anions7Optimizing the Hydrogen-Bond Network Drives Cadmium Ce(IV) Fluoride Hydrate with Significantly Enhanced Optical Anisotropy8The birefringence optimization by hydroxyl in organic nonlinear optical crystals3Anionic Group Trimming Strategy: Oriented Fabrication of Sulfonate UV Birefringent Crystals with High Optical Anisotropy5Ag(Te2O3)(PO4): The first Ag-containing phosphate-tellurite nonlinear optical crystal featuring novel zigzag layered structure0Effect of Multiple Hydrogen Bonding on the π-Conjugated Groups and Optical Properties in Molecular Crystals5Chiral Lead-Oxyiodide Nonlinear Optical Crystals Constructed on l -Malate Groups5Achieving 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) Groups3From centrosymmetric (C 4 H 8 N 5 )(SbF 4 ) to polar (C 4 H 7 N 4 O)(SbF 4 ): a new UV nonlinear optical material achieved by functional group modulation8Halide anion-mediated crystal structure engineering in guanidinoacetic acid halides for tunable birefringence0Stable lead succinate-iodides with strong second-harmonic generation response and large birefringence0Synergism of [C 2 N 4 H 7 S] cations and anionic modulators: tailoring second-order nonlinear optics and birefringence in organic–inorganic crystals6The 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 birefringence0Confinement-assembled ultraviolet nonlinear optical crystal from pyridine-expanded π-systems with exhibiting strong SHG and birefringence18Hydrogen‐Bond‐Modulated Alignment of Iminodiacetic Acid Cations for Achieving Ultraviolet Second Harmonic Generation6Unit Symmetry‐Breaking and Layered Linear Ordering Enabling Superior Short‐Wave Ultraviolet Birefringent Crystal8Strategic Oxygen‐Substitution in Perfluorinated Ce(IV) Coordination Frameworks Triggers Dual‐Wavelength Nonlinear Optical Materials With Exceptional Performances32RbLa(SO 4 ) 2 : A KBBF-like Deep-UV Transparent Rare Earth Sulfate with Strong SHG Response and High Thermal Stability Enabled by Multicomponent Structural Design2Ternary Anion‐Engineered Rare Earth Crystals for Broadband UV Transparency and Enhanced Second‐Harmonic Generation1Redox‐Driven Strategy Enabling Leapfrog Enhancement of Birefringence in Layered Tin‐Based Optical Crystals1Two Rare Earth-Based Sulfates with Enhanced Birefringence and Broad Optical Transparency Window0Assembly of dual π-conjugated units toward enhanced birefringence in a 2D organic sulfonate crystal0

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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. A 0.5 H 2 C 6 N 7 O 3 ·4H 2 O (A = Ca 2+ , Sr 2+ ) iso-cyamelurates with ultra-large π-conjugated group and excellent nonlinear optical properties

    Inorganic Chemistry Frontiers · 2023-01-01

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  3. A lithium–scandium sulfate with second-harmonic generation response and deep-ultraviolet transparency

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  4. A UV solar-blind nonlinear optical crystal with confined π-conjugated groups

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  5. Cs[B 3 O 3 F 2 (OH) 2 ]: discovery of a hydroxyfluorooxoborate guided by selective organic–inorganic transformation

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  6. From H 12 C 4 N 2 CdI 4 to H 11 C 4 N 2 CdI 3 : a highly polarizable CdNI 3 tetrahedron induced a sharp enhancement of second harmonic generation response and birefringence

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    Huai‐Yu Wu, Chun‐Li Hu, Miao‐Bin Xu, Qianqian Chen, Nan Ma, Xiao‐Ying Huang, Ke‐Zhao Du, Jin Chen

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  7. Recent advances on the synthesis of Sb(III)-based inorganic ultraviolet nonlinear optical materials

    Chinese Journal of Structural Chemistry · 2023-01-01

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  8. Two UV optical crystals with strong optical anisotropy, large band gaps and an α-BBO type structure

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  9. The First UV Nonlinear Optical Selenite Material: Fluorination Control in CaYF(SeO 3 ) 2 and Y 3 F(SeO 3 ) 4

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  10. The First UV Nonlinear Optical Selenite Material: Fluorination Control in CaYF(SeO3)2 and Y3F(SeO3)4

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  11. Unveiling the Superior Optical Properties of Novel Melamine‐Based Nonlinear Optical Material with Strong Second‐Harmonic Generation and Giant Optical Anisotropy

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  12. A Hydrogen Bonded Supramolecular Framework Birefringent Crystal

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  13. A Hydrogen Bonded Supramolecular Framework Birefringent Crystal

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  14. Cs 2 Mg(H 2 C 3 N 3 S 3 ) 4 ·8H 2 O: An Excellent Birefringent Material with Giant Optical Anisotropy in π-Conjugated Trithiocyanurate

    Inorganic Chemistry · 2023-05-11

    Xia Hao, Chensheng Lin, Min Luo, Yuqiao Zhou, Ning Ye, Enbo Shangguan

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  15. Y(HSeO3)(SeO3)(H2O)·(H2O) and Y2(SeO3)2(SeO4)(H2O)2·(H2O)0.75: Two yttrium selenites with a short UV cut-off edge explored from pure selenite compounds

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  16. Three‐in‐One Strategy Constructing the First High‐Performance Nonlinear Optical Sulfide Crystallizing with the P43 Space Group

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  17. From Centrosymmetry to Noncentrosymmetry: Precise Structural Regulation and Characterization on ZnHPO3·2H2O Polymorphs

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  18. (NH 4 ) 2 (I 5 O 12 )(IO 3 ) and K 1.03 (NH 4 ) 0.97 (I 5 O 12 )(IO 3 ): Mixed‐Valent Polyiodates with Unprecedented I 5 O 12 − Unit Exhibiting Strong Second‐Harmonic Generation Responses and Giant Birefringence

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  19. α- and β-(C4H5N2O)(IO3)·HIO3: Two SHG Materials Based on Organic–Inorganic Hybrid Iodates

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  20. Designing a Dimension Reduced Hybrid Perovskite with Robust Large Birefringence by Expanding Cationic π‐Delocation

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  21. Rational Design of Noncentrosymmetric Organic–Inorganic Hybrids with a π-Conjugated Pyridium-Type Cation for High Nonlinear-Optical Performance

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  22. Heterologous Isomorphic Substitution Induces Optical Property Enhancement for Deep-UV Crystals: a Case in Rb[B3O3F2(OH)2]

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  23. A Two‐Dimensional Hybrid Perovskite With Heat Switching Birefringence

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  25. A potassium lead 2-methylmalonate-iodide nonlinear optical crystal with strong second-harmonic generation response and large birefringence

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  26. Ln 2 F 2 (OH 2 )(MoO 3 ) 2 (SeO 3 ) 2 : Promising Multifunctional Nonlinear Optical Materials Created by Partial Fluorination Strategy under Corrosion Resistant Supercritical Reactions

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  28. C(NH2)3Cd(C2O4)Cl(H2O)·H2O and BaCd(C2O4)1.5Cl(H2O)2: Two Oxalate Chlorides Obtained by Chemical Scissors Strategy Exhibiting Low-Dimensional Structural Networks and Balanced Overall Optical Properties

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  29. [(C 5 H 6 N 2 ) 2 H](Sb 4 F 13 ): a polyfluoroantimonite with a strong second harmonic generation effect

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  30. A UV non-hydrogen pure selenite nonlinear optical material for achieving balanced properties through framework-optimized structural transformation

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  31. A-site cation manipulation of exemplary second harmonic generation response and optical anisotropy in rare-earth borates

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  32. Discovery of excellent ultraviolet nonlinear optical materials in chlorates and bromates with highly stereochemically active lone pairs

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  33. N 2 H 4 Zn(HC 3 N 3 O 3 ): exceptionally strong second harmonic generation and ultra-long phosphorescence

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  34. Research progress in optical materials with cationic organic planar π-conjugated groups containing CN bonds

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  35. Synthesis and Characterization of Metal Iso-cyamelurate K0.5In0.5(H2C6N7O3)2·9H2O with Large Birefringence

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  36. Tunable Optical Anisotropy in Rare‐Earth Borates with Flexible [BO3] Clusters

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  37. PbBeB2O5: A High-Performance Ultraviolet Nonlinear-Optical Crystal with Functional [BeB2O8]8– Group

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  38. A3Sc(SO4)3 (A = K, Rb, Cs): Three Deep‐Ultraviolet Transparent Alkali‐Scandium Sulfates with Strong Second‐Harmonic Generation Response and High Thermal Stability

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  39. NaK5La2(SO4)6: Enhanced Birefringence of Multiple-Alkali Metal Sulfate Systems via Rare Earth Metal-Centered Polyhedra

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  40. (C5H12N2S)Hg(NO3)2: A Mercury Nitrate Nonlinear Optical Crystal Motivated by Heteroatom Coordination Strategy

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  41. A Robust Phosphonate‐Based Hydrogen‐Bonded Organic Framework Birefringent Crystal

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  42. Achieving the Birefringence Optimization by Methyl Modulation in Organic Nonlinear Optical Crystals

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

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  44. A Giant Optically Anisotropic Phosphate Driven by Mixed Valence Mercury Units

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  45. Two α‐SiO 2 ‐Related Deep‐Ultraviolet Phase‐Matchable Optical Nonlinear Beryllium Silicate Crystals Na 2 BeSiO 4 and Li 2 BeSiO 4 with Enhanced SHG Effect

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  46. Unveiling Charge Dependent Law to Enhance Birefringence in 2‐Aminopyrimidine Family

    Advanced Optical Materials · 2024-12-16

    Muhammad Sharjeel Arif, Xu Liu, Zi‐Jian Li, Hangwei Jia, Yansheng Jiang, Zhihua Yang, Xueling Hou, Shilie Pan

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  47. K6NaCaRe2(B5O10)3 (Re = Y, Lu): Two NLO Compounds Exhibiting a Short Absorption Edge in the A7–xA’xAeRe2(B5O10)3 (x = 0, 1) Family

    Inorganic Chemistry · 2024-12-19

    Wencong Li, Zhaowei Hu, Yanyan Ding, Yueting Zhu, Qun Jing, Lili Liu

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  48. (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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  49. “Three functions in one”: multifunctional rare-earth cyamelurates with magnetism, luminescence, and giant optical nonlinearity

    Chemical Science · 2025-01-01

    Jing Zhang, Yuxiao Liu, Fangyan Wang, Pifu Gong, Zhaoyi Li, Xinyuan Zhang, Fei Liang, Shu Hai Guo, Zhanggui Hu, Yicheng Wu

    Read original paper ↗ ·

  50. A remarkable solar-blind ultraviolet nonlinear optical crystal with comprehensive performance and enhanced thermal stability

    Materials Chemistry Frontiers · 2025-01-01

    Jialin Zeng, Shuangcheng Li, Ruibiao Fu, Zilong Geng, Yiting Luo, Senfu Lei, Zuju Ma

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