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RESEARCH PAPER · Science China Materials · 2020

Enhanced nonlinear optical functionality in birefringence and refractive index dispersion of the deep-ultraviolet fluorooxoborates

Zhihua Yang, Abudukadi Tudi, Bing‐Hua Lei, Shilie Pan

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Enhanced nonlinear optical functionality in birefringence and refractive index dispersion of the deep-ultraviolet fluorooxoboratesOriginalFluorooxoborate layers: second harmonic generation and Raman spectra anisotropy2The functionality of tetrahedral units in fluoroxoiodates: fluorine-modulating effects in iodates with lone pair electrons3Volume Modulation of Nonlinear Optical Properties by Cation Substitution8Deep-ultraviolet nonlinear optical crystals by design: A computer-aided modeling blueprint from first principles45Advanced optical gain materials keep on giving4LiGaF2(IO3)2: A mixed-metal gallium iodate-fluoride with large birefringence and wide band gap39Cs3B3O3F6 with a Deep-Ultraviolet Cutoff Edge and a Suitable Birefringence as the Potential Zero-Order Waveplate Material31Different mechanism of response of asymmetric lone pair electrons around ns2 cations to birefringence and second harmonic generation7Series of Crystals with Giant Optical Anisotropy: A Targeted Strategic Research19Series of Crystals with Giant Optical Anisotropy: A Targeted Strategic Research140Role of Fluorooxo-Functional Units in Symmetry Breaking and Second Harmonic Generation Response Contribution in Fluorooxoborate Nonlinear Optical Crystals15Intriguing Dimensional Transition Inducing Variable Birefringence in K2Na2Sn3S8 and Rb3NaSn3Se828Synergism of multiple functional chromophores significantly enhancing the birefringence in layered non-centrosymmetric chalcohalides20The synthesis, characterization, and theoretical analysis of (NH 4 ) 3 PbCl 52Computationally assisted multistage design and prediction driving the discovery of deep-ultraviolet nonlinear optical materials41Distinctive modulation of optical anisotropy by halogens in α/β-Cd–P–X (X = Cl, Br, and I)2Enhanced birefringence and suppressed second harmonic generation response mechanism in nonlinear optical materials via structural fine-tuning9From BaCl 2 to Ba(NO 3 )Cl: significantly enhanced birefringence derived from π-conjugated [NO 3 ]14K 3 Na(TaF 7 )(SiF 6 ): a mixed-anion pentanary fluoride with zero-dimensional anions exhibiting a large band gap14Li 5 Cs(SO 4 ) 3 : a potential zero-order wave plate material with short deep-ultraviolet cutoff edge20Na 7 (IO 3 )(SO 4 ) 3 : the first noncentrosymmetric alkaline-metal iodate-sulfate with isolated [IO 3 ] and [SO 4 ] units28Two deep-ultraviolet nonlinear optical monolayers obtained by a template-optimized design strategy2Finding Short-Wavelength Birefringent Crystals with Large Optical Anisotropy Activated by π-Conjugated [C(NH2)3] Units45Effect of boron incorporation into the carbon-site in Nb2SC MAX phase: Insights from DFT77Borosilicate Crystal LaBSiO5: A New Promising Ultraviolet Quasiphase Matching Material31Designing a Family of Aluminum-Containing Fluoroborate Crystals with Enhanced Birefringence and Second-Harmonic Generation Coefficients Based on the First-Principles Methods4Molecular Engineering toward an Enlarged Optical Band Gap in a Bismuth Sulfate via Homovalent Cation Substitution26Fluorine‐Driven Enhancement of Birefringence in the Fluorooxosulfate: A Deep Evaluation from a Joint Experimental and Computational Study139SrAlB3O6F2: A Fluoroaluminoborate with [Al2B6O14F4] Units and Large Birefringence22Synthesis, Structure, Characterization, and Calculation of a Noncentrosymmetric Fluorine-Containing Indium Iodate, Ba[InF3(IO3)2]10Enhancement of band gap and birefringence induced via π -conjugated chromophore with “tail effect”28NaSb3O2(SO4)3·H2O: A New Alkali-Metal Antimony(III) Sulfate with a Unique Sb6O20H4 Unit and Moderate Birefringence19Na4B8O9F10: A Deep‐Ultraviolet Transparent Nonlinear Optical Fluorooxoborate with Unexpected Short Phase‐Matching Wavelength Induced by Optimized Chromatic Dispersion133Na4B8O9F10: A Deep‐Ultraviolet Transparent Nonlinear Optical Fluorooxoborate with Unexpected Short Phase‐Matching Wavelength Induced by Optimized Chromatic Dispersion13AZn 2 (BO 3 )Si 2 O 5 (A = Rb, Cs): first examples of KBe 2 BO 3 F 2 structure type in the borosilicate family exhibiting a deep-ultraviolet cutoff edge25Hierarchical Modulation of Optical Anisotropy Driven by Metal Cation Polyhedra in Fluorooxoborates MIIB4O6F2 (MII=Be, Mg, Pb, Zn, Cd)6CsAB 8 O 12 F 2 ·CsI (A = K + , NH 4 + ): design of two fluorooxoborates with benign layered structures via a salt-inclusion strategy28First theoretical probe for efficient enhancement of optical nonlinearity via structural modifications into phenylene based D–π–A configured molecules43Li 7 SrScB 12 O 24 and Li 7 Ba 0.6 Ca 0.4 ScB 12 O 24 : two new quaternary rare-earth borates with short UV cutoff edges4Linear unit BN 2 : a novel birefringence-enhanced fundamental module with sp orbital hybridization9LiSrSbS 3 : parallel configurations of lone pair electrons inducing a large birefringence16Performance of optical materials with the derivative of planar π-conjugated groups: Recent advances and future prospects37First-principles study of the influence of lone pair electrons and molecular groups on the birefringence of phosphate and fluorophosphate13Potential optical functional crystals with large birefringence: Recent advances and future prospects322LiB5O5F2(OH)4: A new deep-ultraviolet birefringent crystal with [B5O5F2(OH)4] anionic group28Uncovering the Structural Diversity and Excellent Performance of a Deep Ultraviolet Nonlinear Optical System Li(B2O3)nF (n= 1, 1.5, 2, and 3) by Multicomponent Prediction26Molecular Structure Design, Crystal Growth, and Characterization of New Types of Organic Nonlinear Optical Chalcone Crystals24Design of New Borates with Deep Ultraviolet Transparency Inspired by the Flexibility of Unusual Triple-Layered Frameworks3NaB3O4F(OH): A Hydroxyfluorooxoborate with One-Dimensional Chain Featuring Large Birefringence and Short Ultraviolet Cutoff Edge5Design of novel deep-UV nonlinear optical materials with one-dimensional functional module [BO2]∞ chain and fluorine-driven short phase-matching43CaBO2F: A novel deep-UV structural template with high nonlinear optical performance induced by electron delocalization25Syntheses, structures, and characterization of new heteroanionic chalcohalides: Na2Ba17In8Q21F18 (Q = S, Se), KBa2InQ3F2 (Q = S, Se)5LiNaB6O9F2: A Promising UV NLO Crystal Having Fluorine‐Directed Optimal Performances and Double Interpenetrating 3[B6O9F2]∞ Networks33Design of deep-ultraviolet nonlinear optical materials based on fundamental building blocks with excellent microscopic properties1Enhancement of birefringence and refractive index dispersion optimization from iodates to fluorooxoiodates1Li2AB5O8F2 (A = Na and K): two new deep-ultraviolet transparent fluorooxoborates with moderate birefringence designed by targeted dimensional modulation7Linear π-conjugated units of the D ∞h point group as superior ultraviolet birefringent units1Shedding light on intrinsic characteristics and optical properties of novel selenite and tellurite crystals ZrSe 2 O 6 , HfSe 2 O 6 and HfTe 3 O 87Rational Design of the First Ammonium Magnesium Borate with Deep-Ultraviolet Cutoff Edge and Moderate Birefringence and Further Investigation into the Nature of Ammonium in the Borate System15An interlinked prediction-experiment paradigm discovering deep-ultraviolet fluorooxoborates with desired optical nonlinearity and birefringence76Na2BaB12O18F4: A Mixed Alkali/Alkaline-Earth Metal Fluorooxoborate with Two Unprecedented Interpenetrating Three-Dimensional B–O/F Anionic Networks and a Short Ultraviolet Cutoff Edge9CaB2O2F4: A Novel [BOF2]∞-Based Structural Template with a Strong Second Harmonic Generation Response and Large Band Gap2Li4AAl(SO4)2F4 (A = Cs, Rb): two deep-UV fluoroaluminosulfates with special motif [AlS2O8F4]1Quantum Chemical Approach of Hexaammine (NH3)6 complexant with alkali and alkaline earth metals for their potential use as NLO materials7“Cation Activation”: An Effective Strategy for the Enhancement of Birefringence36Birefringence Regulation by Clarifying the Relationship Between Stereochemically Active Lone Pairs and Optical Anisotropy in Tin‐based Ternary Halides56Birefringence Regulation by Clarifying the Relationship Between Stereochemically Active Lone Pairs and Optical Anisotropy in Tin‐based Ternary Halides2First-principles study on AgBi(CrO4)2:An effective infrared nonlinear optical compound3A theoretical approach for exploration of non-linear optical amplification of fused azacycle donor based thiophene polymer functionalized chromophores9Li2RbSO4Cl with a Short Ultraviolet Absorption Edge and an Acentric Structure through Assembling Heteroleptic [LiO3Cl] Tetrahedra2Three Borates Belonging to the A(I)7Ae(II)Re(III)2B15O30 Family as Promising Nonlinear Optical Crystals12Birefringent Dispersion Optimization to Achieve Superior Nonlinear Optical Phase Matching in Deeper Solar‐Blind UV Band from KH 2 PO 4 to BeH 3 PO 516Achieving great optical anisotropy with the well-directed alignment of π-conjugated groups due to hydrogen bonds9A-site cation manipulation of exemplary second harmonic generation response and optical anisotropy in rare-earth borates18Exploration of antimony( iii ) oxyhalides via single-site substitution in quest of large birefringence10NaB(OH) 3 CH 3 : a deep-ultraviolet optical crystal with unprecedented methyl-modified [B(OH) 3 CH 3 ] units6Reticular chemistry-aided effective design of new second-order nonlinear optical selenites11Simple aliovalent cation substitution to induce strong optical anisotropy enhancement in a rare thioantimonate( v ) family3Synthesis, structures and properties of two new nitrate optical materials: Rb3ZnNO3Cl4 and Rb5Na(NO3)4Cl24Toward the ultraviolet (UV) or deep-UV nonlinear optical crystals: The combination of π-conjugated planar [XY3] and tetrahedral [XY4]80A perspective on deep-ultraviolet nonlinear optical materials13Enhanced Birefringence in Phosphates via “Two Steps in One”: d0 Transition Metal Regulation and Fluorination Synergistic Strategy7SC-XRD structural characterization, insights of key electronic, and nonlinear optical properties of dimethoxybenzenesulfonate crystals: A combine experimental and DFT approach2Review on birefringence in borates based on birefringence-active functional groups and arrangements57Fluorine-driven materials design of novel deep-ultraviolet nonlinear optical crystal materials: Research progress and challenges6Breaking through the ‘‘200 nm deep-ultraviolet wall’’ of phase matching region by cation structural modulation27Sulfate 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 Ordering4Graph neural network guided design of novel deep-ultraviolet optical materials with high birefringence23Computer‐Aided Development of New Nonlinear Optical Materials38Computer‐Aided Development of New Nonlinear Optical Materials14(CN 4 H 7 ) 2 SO 4 ·H 2 O: high-performance metal-free ultraviolet birefringent crystal with KBBF-like configuration5Anion ratio-directed design of CaB 4 O 5 F 4 and CaB 6 O 8 F 4 : [BO 3 ]/[BO 2 F 2 ] hybridization tailoring deep-ultraviolet nonlinear optical performance2Structural chemistry of antimony( iii ) oxalates with lone pairs: polyhedral distortion [SbO 4 F 2 ], π-conjugation [C 2 O 4 ], and birefringence tuning1The impact of anionic group arrangement on the optical properties of the arsenate series0Can Low Structural Anisotropy Produce High Optical Anisotropy? Anomalous Giant Optical Birefringent Effect in PI4AlI4 in Focus11Prediction of New Functional Fluorooxoborates with Expected Anionic Framework: A Case of CaB3O5F4Exploration of promising key electronic and nonlinear optical properties of bifluorenylidene based chromophores: a TD-DFT/DFT approach14Symmetry Breaking via Anion-Molecule Synergy: Fluorine and Crystalline Water Directed Construction of Noncentrosymmetric Sr(IO2F2)2·2H2O0NH4B5O7(OH)2 and CsRbB10O14(OH)4·H2O: Two Hydroxyborates Feature Significant Optical Anisotropy and Contain 1∞[B5O7(OH)2] Chains1A strategy to achieve giant optical anisotropy via integrating linear pseudohalogen and stereochemical active lone pair cation6Bromine for iodine: Unlocking short-wavelength UV phase matching in nonlinear optical metal halides6Synthesis, spectral characterization and nonlinear optical exploration of potent fluorene-based compounds: A DFT refine experimental study4K 2 GdB 3 O 6 F 2 : A Promising Short-Wave UV Birefringent Crystal via Optimized Assembly of π-Conjugated [B 3 O 6 ] Groups8High‐Throughput Discovery of Large Birefringence Materials in Mixed‐N Hf‐O Systems0[C(NH 2 ) 3 ] 2 PO 3 (OH): A Deep-Ultraviolet Birefringent Crystal Enabled by Synergy of π-Conjugated Cations and Heteroleptic Tetrahedra2Novel [BO 2 ] superhalogen module-enabled deep-ultraviolet nonlinear optical material: rational design for tailored birefringence and phase matching0Asymmetry-driven organic–inorganic hybrid strategy for constructing structures with exceptional organofunctionalized B–O units2Achieving an optimal performance balance in UV nonlinear optical crystals via hydrogen-bond regulation1Chirality-induced second harmonic generation in supramolecular 4-nitro- d -phenylalanine hybrid crystals2Covalent hybrid cadmium halides with heteroleptic tetrahedral units exhibiting a wideband nonlinear optical response0KTeOPO 4 and NH 4 SnClSO 4 : two new KTiOPO 4 derivatives as birefringent crystals featuring enhanced optical anisotropy0Functional Unit Design of Deep‐UV NLO Crystals With Short Phase‐Matching and Large SHG Response22Boosting Ultraviolet Phase‐Matching Performance of B 3 O 7 ‐Based Systems via Synergistic Fluorination and Organic Modification Strategy1Minimizing Oscillator Strength: A Strategy for Engineering Deep-Ultraviolet Nonlinear Optical Crystals with Optimized Refractive-Index Dispersion0F−/OH− terminal modification of [B3O6] clusters: Constructing deep-ultraviolet hydroxyfluorooxoborates with tunable optical performance0Breakthrough in High Quality LaBGeO 5 Crystal for Deep Ultraviolet Quasi-Phase Matching Application0Toward the vacuum-ultraviolet frontier in nonlinear optical frequency conversion: phase-matching mechanisms across dimensions and architectures2Prediction of deep-ultraviolet nonlinear optical material in borosilicate system: a case of RbSiB3O70A Chemically Interpretable and Leakage‐Safe Machine Learning Framework for Predicting Molecular Refractive Index ( n D )0Exceptional Solar‐Blind Birefringence Engineered by Complementary Hydrogen‐Bond Ordering of π‐Conjugated Units0Accelerating the Discovery of Deep-Ultraviolet Nonlinear Optical Materials by Combining Machine Learning Interatomic Potentials with First-Principles Calculations: A Case of LiB2O3F0Borophosphate-based second-order nonlinear optical materials: Advances in structural diversity and optical performance0

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  1. Fluorooxoborate layers: second harmonic generation and Raman spectra anisotropy

    New Journal of Chemistry · 2020-01-01

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  2. The functionality of tetrahedral units in fluoroxoiodates: fluorine-modulating effects in iodates with lone pair electrons

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  3. Volume Modulation of Nonlinear Optical Properties by Cation Substitution

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  4. Deep-ultraviolet nonlinear optical crystals by design: A computer-aided modeling blueprint from first principles

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  5. Advanced optical gain materials keep on giving

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  6. LiGaF2(IO3)2: A mixed-metal gallium iodate-fluoride with large birefringence and wide band gap

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  7. Cs3B3O3F6 with a Deep-Ultraviolet Cutoff Edge and a Suitable Birefringence as the Potential Zero-Order Waveplate Material

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  8. Different mechanism of response of asymmetric lone pair electrons around ns2 cations to birefringence and second harmonic generation

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  9. Series of Crystals with Giant Optical Anisotropy: A Targeted Strategic Research

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  10. Series of Crystals with Giant Optical Anisotropy: A Targeted Strategic Research

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  11. Role of Fluorooxo-Functional Units in Symmetry Breaking and Second Harmonic Generation Response Contribution in Fluorooxoborate Nonlinear Optical Crystals

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  12. Intriguing Dimensional Transition Inducing Variable Birefringence in K2Na2Sn3S8 and Rb3NaSn3Se8

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  13. Synergism of multiple functional chromophores significantly enhancing the birefringence in layered non-centrosymmetric chalcohalides

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  14. The synthesis, characterization, and theoretical analysis of (NH 4 ) 3 PbCl 5

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  15. Computationally assisted multistage design and prediction driving the discovery of deep-ultraviolet nonlinear optical materials

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  16. Distinctive modulation of optical anisotropy by halogens in α/β-Cd–P–X (X = Cl, Br, and I)

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  17. Enhanced birefringence and suppressed second harmonic generation response mechanism in nonlinear optical materials via structural fine-tuning

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  18. From BaCl 2 to Ba(NO 3 )Cl: significantly enhanced birefringence derived from π-conjugated [NO 3 ]

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  19. K 3 Na(TaF 7 )(SiF 6 ): a mixed-anion pentanary fluoride with zero-dimensional anions exhibiting a large band gap

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  20. Li 5 Cs(SO 4 ) 3 : a potential zero-order wave plate material with short deep-ultraviolet cutoff edge

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  21. Na 7 (IO 3 )(SO 4 ) 3 : the first noncentrosymmetric alkaline-metal iodate-sulfate with isolated [IO 3 ] and [SO 4 ] units

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  22. Two deep-ultraviolet nonlinear optical monolayers obtained by a template-optimized design strategy

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  23. Finding Short-Wavelength Birefringent Crystals with Large Optical Anisotropy Activated by π-Conjugated [C(NH2)3] Units

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  24. Effect of boron incorporation into the carbon-site in Nb2SC MAX phase: Insights from DFT

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  26. Designing a Family of Aluminum-Containing Fluoroborate Crystals with Enhanced Birefringence and Second-Harmonic Generation Coefficients Based on the First-Principles Methods

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  27. Molecular Engineering toward an Enlarged Optical Band Gap in a Bismuth Sulfate via Homovalent Cation Substitution

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  28. Fluorine‐Driven Enhancement of Birefringence in the Fluorooxosulfate: A Deep Evaluation from a Joint Experimental and Computational Study

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  29. SrAlB3O6F2: A Fluoroaluminoborate with [Al2B6O14F4] Units and Large Birefringence

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  30. Synthesis, Structure, Characterization, and Calculation of a Noncentrosymmetric Fluorine-Containing Indium Iodate, Ba[InF3(IO3)2]

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  31. Enhancement of band gap and birefringence induced via π -conjugated chromophore with “tail effect”

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  32. NaSb3O2(SO4)3·H2O: A New Alkali-Metal Antimony(III) Sulfate with a Unique Sb6O20H4 Unit and Moderate Birefringence

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  33. Na4B8O9F10: A Deep‐Ultraviolet Transparent Nonlinear Optical Fluorooxoborate with Unexpected Short Phase‐Matching Wavelength Induced by Optimized Chromatic Dispersion

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  34. Na4B8O9F10: A Deep‐Ultraviolet Transparent Nonlinear Optical Fluorooxoborate with Unexpected Short Phase‐Matching Wavelength Induced by Optimized Chromatic Dispersion

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  35. AZn 2 (BO 3 )Si 2 O 5 (A = Rb, Cs): first examples of KBe 2 BO 3 F 2 structure type in the borosilicate family exhibiting a deep-ultraviolet cutoff edge

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  36. Hierarchical Modulation of Optical Anisotropy Driven by Metal Cation Polyhedra in Fluorooxoborates MIIB4O6F2 (MII=Be, Mg, Pb, Zn, Cd)

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  37. CsAB 8 O 12 F 2 ·CsI (A = K + , NH 4 + ): design of two fluorooxoborates with benign layered structures via a salt-inclusion strategy

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  38. First theoretical probe for efficient enhancement of optical nonlinearity via structural modifications into phenylene based D–π–A configured molecules

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  39. Li 7 SrScB 12 O 24 and Li 7 Ba 0.6 Ca 0.4 ScB 12 O 24 : two new quaternary rare-earth borates with short UV cutoff edges

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  40. Linear unit BN 2 : a novel birefringence-enhanced fundamental module with sp orbital hybridization

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  41. LiSrSbS 3 : parallel configurations of lone pair electrons inducing a large birefringence

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

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  43. First-principles study of the influence of lone pair electrons and molecular groups on the birefringence of phosphate and fluorophosphate

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  44. Potential optical functional crystals with large birefringence: Recent advances and future prospects

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  45. LiB5O5F2(OH)4: A new deep-ultraviolet birefringent crystal with [B5O5F2(OH)4] anionic group

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  46. Uncovering the Structural Diversity and Excellent Performance of a Deep Ultraviolet Nonlinear Optical System Li(B2O3)nF (n= 1, 1.5, 2, and 3) by Multicomponent Prediction

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  47. Molecular Structure Design, Crystal Growth, and Characterization of New Types of Organic Nonlinear Optical Chalcone Crystals

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  48. Design of New Borates with Deep Ultraviolet Transparency Inspired by the Flexibility of Unusual Triple-Layered Frameworks

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