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RESEARCH PAPER · Science China Materials · 2021

[C(NH2)3]3PO4·2H2O: A new metal-free ultraviolet nonlinear optical phosphate with large birefringence and second-harmonic generation response

Xin Wen, Chensheng Lin, Min Luo, Huixin Fan, Kaichuang Chen, Ning Ye

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[C(NH2)3]3PO4·2H2O: A new metal-free ultraviolet nonlinear optical phosphate with large birefringence and second-harmonic generation responseOriginalSystematic centricity control using a chiral template: novel noncentrosymmetric polar niobium oxyfluorides and tantalum fluorides directed by chiral histidinium cations, [( l -hisH 2 )NbOF 5 ], [( d -hisH 2 )NbOF 5 ], [( l -hisH 2 )TaF 7 ], and [( d -hisH 2 )TaF 7 ]8The application and development of the first principles calculation in nonlinear optical materials1Synthesis, Crystal Structure, and Nonlinear Optical Property of an Anhydrous Sulfate KTb(SO4)216Synergistic Effect of π-Conjugated [C(NH 2 ) 3 ] Cation and Sb(III) Lone Pair Stereoactivity on Structural Transformation and Second Harmonic Generation58[C(NH 2 ) 3 ] 2 S 2 O 8 : combining delocalized and localized π-conjugate units to achieve strong optical anisotropy21[C(NH 2 ) 3 ]BiCl 2 SO 4 : an excellent birefringent material obtained by multifunctional group synergy40A novel 2-(aminomethyl)pyridineH 2 PO 4 crystal with second-order nonlinear optical performance8Performance of optical materials with the derivative of planar π-conjugated groups: Recent advances and future prospects37CsY(SO4)2·4H2O: A Deep-Ultraviolet Birefringent Crystal Induced by an Edge-Sharing Connection26Yin–Yang Complementarity Strategy Achieving Giant Optical Anisotropy in a Metal-free Birefringent Material C(NH2)3(HC4O4)14Two Metal Phosphate Nonlinear Optical Materials Simultaneously Exhibiting Ultraviolet Transparence and a Large Birefringence50Directional Construction of New Nonlinear Optical Bifunctional Units through Molecular Engineering Design Inspired by the B 3 O 7 -Typed Configuration23Sharp Enhancement of Birefringence in Antimony Oxalates Achieved by the Cation–Anion Synergetic Interaction Strategy38[C(NH2)3]2MoO2F4·H2O: Unique Chinese-Knot Structure Revealing Superior Nonlinear-Optical Properties19Phosphites: A Nonlinear Optical Materials System with a Wide Band Gap and Moderate Second-Harmonic Generation Effect27Characteristics of structure, thermal stability and optical properties for a novel NLO crystal (C5H12NO)H2PO48A lithium–scandium sulfate with second-harmonic generation response and deep-ultraviolet transparency7Recent advances of inorganic phosphates with UV/DUV cutoff edge and large second harmonic response7Chain‐like [S x ] ( x =2–6) Units Realizing Giant Birefringence with Transparency in the Near‐Infrared for Optoelectronic Materials53Chain‐like [S x ] ( x =2–6) Units Realizing Giant Birefringence with Transparency in the Near‐Infrared for Optoelectronic Materials5Recent progress of newly developed functional building units and corresponding nonlinear optical materials14NaCl·CH4N2O·H2O: An Organic–Inorganic Hybrid Ultraviolet Nonlinear Optical Crystal with Optimized Comprehensive Properties8Deep-ultraviolet (DUV) nonlinear optical (NLO) crystals: An application in photonic technologies29A review of the relationship between the structure and nonlinear optical properties of organic-inorganic hybrid materials149New Functional Groups Design toward High Performance Ultraviolet Nonlinear Optical Materials95Chiral amino acid-templated tin fluorides tailoring nonlinear optical properties, birefringence, and photoluminescence17Designing promising ultraviolet (UV) birefringent crystals with different hydrogen-bonded phosphate frameworks18Halide-driven polarity tuning and optimized SHG-bandgap balance in (C 4 H 11 N 2 )ZnX 3 (X = Cl, Br, I)34Large optical anisotropy in noncentrosymmetric phosphate with pseudo 2D intercalated layer16Recent advances in rational structure design for nonlinear optical crystals: leveraging advantageous templates153Research 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 Birefringence8[C(NH2)3]6Mo7O24: A Guanidinium Molybdate as a UV Nonlinear Optical Crystal with Large Birefringence17[C(NH2)3][B(C2O2H4)2]: An Organic–Inorganic Hybrid Borate Containing Nonlinear-Optical Active Unit [B(C2O2H4)2]− with Solar-Blind-Region Optical Nonlinearity16Enhancement of Birefringence in π-Conjugated Oxyfluorides Achieved via van der Waals Layered Structural Optimization10Strong Second-Harmonic Generation Induced by a Triphenylamine-Based Bismuth–Organic Framework for Photocatalytic Activity Enhancement8A Noncentrosymmetric Metal‐Free Borophosphate: Achieving a Large Birefringence and Excellent Stability by Covalent‐Linkage27(C4H6N3O)(HSO4): A Cytosinium Bisulfate with Large Birefringence and Moderate Second Harmonic Generation Effect Produced via Combining a Promising Planar Nonlinear Optical-Active Motif with a Tetrahedral Group13[C(NH2)3]10(MoO3)10(PO4)2(HPO4)2·5H2O: Synergy effect of multiple functional units results in significant birefringence10Noncentrosymmetric Crystal [C10H8NO2]2SiF6·H2O with Large Birefringence12Sulfate Derivatives with Heteroleptic Tetrahedra: New Deep‐Ultraviolet Birefringent Materials in which Weak Interactions Modulate Functional Module Ordering61Sulfate Derivatives with Heteroleptic Tetrahedra: New Deep‐Ultraviolet Birefringent Materials in which Weak Interactions Modulate Functional Module Ordering4(C10N2H10)(HI2O6)(HIO3)(IO3): A Birefringent Material Featuring Large π-Conjugated Organic Cation and Two Types of Iodate Anions2Functional assembly and modification of nonlinear optical fundamental motifs in phosphates27[C(NH2)3]2S2O6: A SBBO-Like Dithionate Crystal with Large Optical Anisotropy14Emergent Mid‐Infrared Nonlinear Optical Candidates With Targeted Balance Performances17An excellent ultraviolet nonlinear optical crystal derived from the polar methylphosphonate unit8Y(C 6 H 5 SO 3 ) 3 ·9H 2 O: strategic integration of ligand substitution and π-conjugated group linkage in sulfates for enhanced ultraviolet nonlinear optical properties4Electron density distribution in bis(guanidinium) disodium hypodiphosphate heptahydrate, (CH 6 N 3 ) 2 Na 2 (P 2 O 6 )·7H 2 O1Highly Polarizable Phosphorus‐Centered Tetrahedra and π‐Conjugated Carbon‐Centered Triangular Moieties Inducing Large Anisotropy and Short‐Wavelength Phase‐Matching23[C 2 N 4 H 7 O][NH 2 SO 3 ]: High‐Performance Ultraviolet Nonlinear Optical Crystal with Ditrigon Coupled Guanylurea Group9[C 2 N 4 H 7 O][NH 2 SO 3 ]: High‐Performance Ultraviolet Nonlinear Optical Crystal with Ditrigon Coupled Guanylurea Group48Chiral-Unit-Oriented Design of Non-π-Conjugated Noncentrosymmetric Phosphates with Short Absorption Edges4Inch‐sized K[NH2(CH2COO)2]: a High‐Performance UV Nonlinear Optical Crystal Enabled by Novel Flexible π‐Conjugated Building Units, [NH2(CH2COO)2]−13Hg3(TeO3)2(NO3)2 and Hg3(Te2O5)2(NO3)2: The First Two Hg‐Based Tellurite Nitrate Unit‐Mixed Crystals with Large Optical Anisotropy16[C(NH2)3]Y(HCOO)4: Constructing 3D Framework for Guanidine-Based UV Nonlinear Optical Crystals with Good Performance8[C( NH2 )3] 2SiF6 : Design of Deep Ultraviolet Crystals with Large Birefringence Based on a Fluorination‐Oriented Strategy13Three-In-One: A Guanidinium-Containing Niobium Oxyfluoride with a Perovskite-like Structure Revealing Multifunctional Optical Properties2Designing hybrid zinc-based ultraviolet nonlinear optical crystal with strong NLO response and dual-color luminescence via the integration of two different SHG-active genes6Strongly Polar [H2PO3]− Induced π-Conjugated Group Arrangement for Balanced UV Nonlinear Optical Performance3[C(NH2)3]Pb(C2O4)Cl·H2O: A halogen- and lone-pair-tuned UV crystal with large birefringence originated from cooperative π-conjugation6Sulfonated Module Aggregation for Ultrahigh Birefringence in Aqueous-Processable Crystals26Remarkable Birefringence Enhancement Enabled by π-Conjugated Cyanoguanidine Group Based on Anisotropic Molecule Coordination Approach8[C(NH 2 ) 3 ] 2 PO 3 (OH): A Deep-Ultraviolet Birefringent Crystal Enabled by Synergy of π-Conjugated Cations and Heteroleptic Tetrahedra2Strategically designed deep-ultraviolet optical crystals with balanced properties by small heteroatom substitution1Synergistic dual-modification strategy of π-conjugated cations and tetrahedra: rational design of ultraviolet high-birefringence monofluorophosphates0Hybrid Cd 2+ -Based Halide Birefringent Crystals Achieving Tunable Dual-Color Emission for Multifunctional LED and Anticounterfeiting Applications2Enhanced tripling-performance in [C(NH2)3]4P2O7·H2O as UV nonlinear optical material due to π-conjugated cation and hydrogen bonding intervention1An Ultraviolet Transparent Nonlinear Optical Crystal Assembled from a Polarizable Tetrahedral Unit1Steric hindrance and hydrogen-bond networks synergistically directing molecular alignment for high-performance ultraviolet birefringent1

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  1. Systematic centricity control using a chiral template: novel noncentrosymmetric polar niobium oxyfluorides and tantalum fluorides directed by chiral histidinium cations, [( l -hisH 2 )NbOF 5 ], [( d -hisH 2 )NbOF 5 ], [( l -hisH 2 )TaF 7 ], and [( d -hisH 2 )TaF 7 ]

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  2. The application and development of the first principles calculation in nonlinear optical materials

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  3. Synthesis, Crystal Structure, and Nonlinear Optical Property of an Anhydrous Sulfate KTb(SO4)2

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    Qi Wu, Can Yang, Jie Ma, Fei Liang, Chunlin Teng, Yeshuang Du

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  4. Synergistic Effect of π-Conjugated [C(NH 2 ) 3 ] Cation and Sb(III) Lone Pair Stereoactivity on Structural Transformation and Second Harmonic Generation

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    Man Zhang, Bingbing Zhang, Daqing Yang, Ying Wang

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  5. [C(NH 2 ) 3 ] 2 S 2 O 8 : combining delocalized and localized π-conjugate units to achieve strong optical anisotropy

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  6. [C(NH 2 ) 3 ]BiCl 2 SO 4 : an excellent birefringent material obtained by multifunctional group synergy

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  7. A novel 2-(aminomethyl)pyridineH 2 PO 4 crystal with second-order nonlinear optical performance

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  8. Performance of optical materials with the derivative of planar π-conjugated groups: Recent advances and future prospects

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  9. CsY(SO4)2·4H2O: A Deep-Ultraviolet Birefringent Crystal Induced by an Edge-Sharing Connection

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  10. Yin–Yang Complementarity Strategy Achieving Giant Optical Anisotropy in a Metal-free Birefringent Material C(NH2)3(HC4O4)

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  11. Two Metal Phosphate Nonlinear Optical Materials Simultaneously Exhibiting Ultraviolet Transparence and a Large Birefringence

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  12. Directional Construction of New Nonlinear Optical Bifunctional Units through Molecular Engineering Design Inspired by the B 3 O 7 -Typed Configuration

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  13. Sharp Enhancement of Birefringence in Antimony Oxalates Achieved by the Cation–Anion Synergetic Interaction Strategy

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  14. [C(NH2)3]2MoO2F4·H2O: Unique Chinese-Knot Structure Revealing Superior Nonlinear-Optical Properties

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  15. Phosphites: A Nonlinear Optical Materials System with a Wide Band Gap and Moderate Second-Harmonic Generation Effect

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  16. Characteristics of structure, thermal stability and optical properties for a novel NLO crystal (C5H12NO)H2PO4

    Optical Materials · 2022-11-27

    Duanliang Wang, Xiangsheng Meng, Nana Zhang, Defu Sun, Ruoxian Hou, Hanzhang Chen, Xiaobing Liu

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

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  18. Recent advances of inorganic phosphates with UV/DUV cutoff edge and large second harmonic response

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

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

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  21. Recent progress of newly developed functional building units and corresponding nonlinear optical materials

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  22. NaCl·CH4N2O·H2O: An Organic–Inorganic Hybrid Ultraviolet Nonlinear Optical Crystal with Optimized Comprehensive Properties

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  23. Deep-ultraviolet (DUV) nonlinear optical (NLO) crystals: An application in photonic technologies

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  24. A review of the relationship between the structure and nonlinear optical properties of organic-inorganic hybrid materials

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  25. New Functional Groups Design toward High Performance Ultraviolet Nonlinear Optical Materials

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  26. Chiral amino acid-templated tin fluorides tailoring nonlinear optical properties, birefringence, and photoluminescence

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  27. Designing promising ultraviolet (UV) birefringent crystals with different hydrogen-bonded phosphate frameworks

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  33. [C(NH2)3]6Mo7O24: A Guanidinium Molybdate as a UV Nonlinear Optical Crystal with Large Birefringence

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  34. [C(NH2)3][B(C2O2H4)2]: An Organic–Inorganic Hybrid Borate Containing Nonlinear-Optical Active Unit [B(C2O2H4)2]− with Solar-Blind-Region Optical Nonlinearity

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  35. Enhancement of Birefringence in π-Conjugated Oxyfluorides Achieved via van der Waals Layered Structural Optimization

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  36. Strong Second-Harmonic Generation Induced by a Triphenylamine-Based Bismuth–Organic Framework for Photocatalytic Activity Enhancement

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  37. A Noncentrosymmetric Metal‐Free Borophosphate: Achieving a Large Birefringence and Excellent Stability by Covalent‐Linkage

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  38. (C4H6N3O)(HSO4): A Cytosinium Bisulfate with Large Birefringence and Moderate Second Harmonic Generation Effect Produced via Combining a Promising Planar Nonlinear Optical-Active Motif with a Tetrahedral Group

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  39. [C(NH2)3]10(MoO3)10(PO4)2(HPO4)2·5H2O: Synergy effect of multiple functional units results in significant birefringence

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  40. Noncentrosymmetric Crystal [C10H8NO2]2SiF6·H2O with Large Birefringence

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  41. Sulfate Derivatives with Heteroleptic Tetrahedra: New Deep‐Ultraviolet Birefringent Materials in which Weak Interactions Modulate Functional Module Ordering

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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. Functional assembly and modification of nonlinear optical fundamental motifs in phosphates

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  45. [C(NH2)3]2S2O6: A SBBO-Like Dithionate Crystal with Large Optical Anisotropy

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  46. Emergent Mid‐Infrared Nonlinear Optical Candidates With Targeted Balance Performances

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  47. An excellent ultraviolet nonlinear optical crystal derived from the polar methylphosphonate unit

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  48. Y(C 6 H 5 SO 3 ) 3 ·9H 2 O: strategic integration of ligand substitution and π-conjugated group linkage in sulfates for enhanced ultraviolet nonlinear optical properties

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  49. Electron density distribution in bis(guanidinium) disodium hypodiphosphate heptahydrate, (CH 6 N 3 ) 2 Na 2 (P 2 O 6 )·7H 2 O

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