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RESEARCH PAPER · Angewandte Chemie International Edition · 2019

Prediction of Fluorooxoborates with Colossal Second Harmonic Generation (SHG) Coefficients and Extremely Wide Band Gaps: Towards Modulating Properties by Tuning the BO 3 /BO 3 F Ratio in Layers

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Prediction of Fluorooxoborates with Colossal Second Harmonic Generation (SHG) Coefficients and Extremely Wide Band Gaps: Towards Modulating Properties by Tuning the BO 3 /BO 3 F Ratio in LayersOriginalFunctional layered materials with heavy metal lone pair cations, Pb 2+ , Bi 3+ , and Te 4+90LiMg(IO 3 ) 3 : an excellent SHG material designed by single-site aliovalent substitution68Designing excellent mid-infrared nonlinear optical materials with fluorooxo-functional group of d0 transition metal oxyfluorides63Effect of anion dimensionality on optical properties: the ∞ [B 7 O 10 (OH) 2 ] layer in CsB 7 O 10 (OH) 2 vs. the ∞ [B 7 O 12 ] framework in CsBaB 7 O 1219Coinage metalides: a new class of excess electron compounds with high stability and large nonlinear optical responses36Li 3 CaB 2 O 5 F: a unique sandwich-like structure with diverse and wide Li ion diffusion pathways5Optimal arrangement of π-conjugated anionic groups in hydro-isocyanurates leads to large optical anisotropy and second-harmonic generation effect42Prediction of ternary fluorooxoborates with coplanar triangular units [BO x F 3−x ] x− from first-principles13Designing Sulfide Borate as a Novel Type of Second-Order Nonlinear-Optical Material91A Promising Fluorooxoborate Framework with Flexibile Capability for Diverse Cations to Enhance the Second Harmonic Generation14CsVO2F(IO3): An Excellent SHG Material Featuring an Unprecedented 3D [VO2F(IO3)]− Anionic Framework132CsVO2F(IO3): An Excellent SHG Material Featuring an Unprecedented 3D [VO2F(IO3)]− Anionic Framework22Noncentrosymmetric Fluorooxoborates A10B13O15F19 (A = K and Rb) with Unexpected [B10O12F13]7– Units and Deep-Ultraviolet Cutoff Edges26PbB5O7F3: A High-Performing Short-Wavelength Nonlinear Optical Material120Alignment of Polar Moieties Leading to Strong Second Harmonic Response in KCsMoP2O951Enhanced nonlinear optical functionality in birefringence and refractive index dispersion of the deep-ultraviolet fluorooxoborates123Li4Ca2B8O16: A Borate with a Unique Fundamental Building Block and a Short Cutoff Edge14Second-Harmonic Generation and Photoluminescence Properties of Sn(II)- and Bi(III)-Based Lone Pair Cation–Pyridine Dicarboxylate Coordination Compounds17The second-order NLO property of a photoswitchable heteroditpioc ion-pair receptor based on 2-pyridyl acylhydrazone linking with 2,6-pyridine bisamide: The impacts of metal cations and anions3Structure-property survey and computer-assisted screening of mid-infrared nonlinear optical chalcohalides113Zn3B7O13Cl: A New Deep-Ultraviolet Transparency Nonlinear Optical Crystal with Boracite Structure24Different mechanism of response of asymmetric lone pair electrons around ns2 cations to birefringence and second harmonic generation7Crystal growth, characterization and theoretical studies of the noncentrosymmetric compound Al3(IO3)9·(HIO3)6·18H2O4Cs 2 AlB 5 O 10 : a short-wavelength nonlinear optical crystal with moderate second harmonic generation response12A new rare-earth borate birefringent crystal with quasi-two-dimensional [BO 3 ] layers23Computationally assisted multistage design and prediction driving the discovery of deep-ultraviolet nonlinear optical materials41From thiophosphate to chalcohalide: mixed-anion AgS x Cl y ligands concurrently enhancing nonlinear optical effects and laser-damage threshold10M 6 PS 5 X (M = Ag, Cu; X = Cl, Br) chalcohalides exhibiting strong nonlinear optical responses and high laser damage resistances9Na 4 SnS 4 and Na 4 SnSe 4 exhibiting multifunctional physicochemical performances as potential infrared nonlinear optical crystals and sodium ion conductors27NaKB 6 O 9 F 2 : a new complex alkali metal fluorooxoborate with puckered layers10RbMo 2 P 3 O 14 with large birefringence mainly induced by highly distorted [MoO 6 ] in uncommon [Mo 2 P 3 O 14 ] ∞ layers9Prediction of Novel van der Waals Boron Oxides with Superior Deep‐Ultraviolet Nonlinear Optical Performance43Prediction of Novel van der Waals Boron Oxides with Superior Deep‐Ultraviolet Nonlinear Optical Performance6Borosilicate 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 Methods4Tin Chloride Sulfates A3Sn2(SO4)3–xCl1+2x (A = K, Rb, Cs; x = 0, 1) as Multifunctional Optical Materials33Hydrogen‐Bond‐Driven Synergistically Enhanced Hyperpolarizability: Chiral Coordination Polymers with Nonpolar Structures Exhibiting Unusually Strong Second‐Harmonic Generation87Hydrogen‐Bond‐Driven Synergistically Enhanced Hyperpolarizability: Chiral Coordination Polymers with Nonpolar Structures Exhibiting Unusually Strong Second‐Harmonic Generation19LiB2O3F: A Beryllium-Free Deep-Ultraviolet Nonlinear Optical Material Designed Based on a Boron-Rich Strategy61Structure and Origin of the Second-Harmonic Generation Response of Nonlinear Optical Material Sr2Be2B2O713A 2 B 6 O 9 F 2 (A = NH 4 , K): new members of A 2 B 6 O 9 F 2 family with deep-UV cutoff edges and moderate birefringence17Construction of coral-like architectures of boron-containing compounds: coral-like boric acid and its application performances3Na 2 SrB 16 O 26 : a new borate with independent interpenetrating B–O networks and deep-ultraviolet cutoff edge4Performance of optical materials with the derivative of planar π-conjugated groups: Recent advances and future prospects37Phosphogermanate Crystal: A New Ultraviolet–Infrared Nonlinear Optical Crystal with Excellent Optical Performances16Uncovering 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 Prediction26A Framework for Biosensors Assisted by Multiphoton Effects and Machine Learning77Mg 2 Pb 2 Si 2 O 7 F 2 : a new lead-containing alkali earth metal silicate fluoride with a short cutoff edge2Tetrahedron-based deep-ultraviolet nonlinear optical crystal with optimized KBe 2 BO 3 F 2 -like structure and disordered cations2Structure and Characterization of K2Na3B2P3O13, a New Nonlinear Optical Borophosphate with One-Dimensional Chain Structure and Short Ultraviolet Cutoff Edge13Fluorooxoborates: A precious treasure of deep-ultraviolet nonlinear optical materials24Unbiased Screening of Novel Infrared Nonlinear Optical Materials with High Thermal Conductivity: Long‐neglected Nitrides and Popular Chalcogenides12Unbiased Screening of Novel Infrared Nonlinear Optical Materials with High Thermal Conductivity: Long‐neglected Nitrides and Popular Chalcogenides48Ba2B9O13F4·BF4: first fluorooxoborate with unprecedented infinite [B18O26F8] tubes and deep-ultraviolet cutoff edge14The 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)47Na2BaB12O18F4: A Mixed Alkali/Alkaline-Earth Metal Fluorooxoborate with Two Unprecedented Interpenetrating Three-Dimensional B–O/F Anionic Networks and a Short Ultraviolet Cutoff Edge9Heteroanionic LaBrVIO4 (VI = Mo, W): Excellence in Both Nonlinear Optical Properties and Photoluminescent Properties11Heterologous Isomorphic Substitution Induces Optical Property Enhancement for Deep-UV Crystals: a Case in Rb[B3O3F2(OH)2]10Four UV Transparent Linear and Nonlinear Optical Materials Explored from Pure Selenite Compounds22Sr(NO 3 )(NH 2 SO 3 )·H 2 O: First Nitrate Sulfamate Revealing Remarkable Second Harmonic Generation and Optimized Birefringence25(SO3CF3)−: A Non‐π‐Conjugated Motif for Nonlinear Optical Crystals Transparent into the Deep‐Ultraviolet Region23Fluorination Strategy Towards Symmetry Breaking of Boron‐centered Tetrahedron for Poly‐fluorinated Optical Crystals15Fluorination Strategy Towards Symmetry Breaking of Boron‐centered Tetrahedron for Poly‐fluorinated Optical Crystals70Fluorination strategy toward chemical and functional modification65Ca 3 Al 2 B 8 O 18 : borate with a graphene-like layer featuring two types of topological six-membered rings induced by [AlO 4 ] units7Recent 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 bonds34Soaking the Rare-Earth Carbonates for a Change: An Alternative Approach to Explore Carbonate Nonlinear Optical Crystals2A Universal Design Strategy Achieving Large Birefringence and Short Phase‐Matching Capability of Optical Materials via Dissimilating Non‐π‐Conjugated Units6Enhanced Birefringence in Phosphates via “Two Steps in One”: d0 Transition Metal Regulation and Fluorination Synergistic Strategy7Two Short-Wave UV Beryllium Selenites Exhibiting Diverse Optical Properties Stemming from Functional Group Arrangements8Structure‐Prediction‐Oriented Synthesis of Thiophosphates as Promising Infrared Nonlinear Optical Materials24Structure‐Prediction‐Oriented Synthesis of Thiophosphates as Promising Infrared Nonlinear Optical Materials1Sb2O2SeO3 and Sb2O(SeO3)2: Two-Layered Antimony(III) Selenites with Enhanced Birefringence10Second Harmonic Generation in β-K2TeW3O12: An Acentric Crystal Designed from Centric Phase via Pressure Modulation4Fluorine-driven materials design of novel deep-ultraviolet nonlinear optical crystal materials: Research progress and challenges6LiNa2Ca8B12O24F6Cl and Li1.2Na2.8B6O11: A Case of Cation-Induced Birefringence Enhancement via Dimensional Changes of Highly Polymerized [B12O24] Motifs10Lanthanide Contraction Eliminates Disorder while Holding Robust Second Harmonic Generation in a Series of Polyiodates13Structural Evolution and Optical Properties of Hydroxyfluorooxoborates MM′2n-1[B3O3F4(OH)]n (M = K, Cs, and Rb; M′ = K, NH4, and Cs; n = 1, 2, and 3)12MgPO2F3: An Ultraviolet Nonlinear Optical System with an Extremely Short Phase-Matching Wavelength Achieved by Introducing Dual-Type Fluorine via Structure Prediction1Computer‐Aided Development of New Nonlinear Optical Materials38Computer‐Aided Development of New Nonlinear Optical Materials14Emergent Mid‐Infrared Nonlinear Optical Candidates With Targeted Balance Performances17A tri-alkali/alkaline-earth metal fluorophosphate deep-ultraviolet birefringent crystal with coexisting PO 3 F and PO 2 F 24CN 4 H 7 B 3 O 3 F 2 (OH) 2 : short-wave UV hydroxyfluorooxyborate crystals with large birefringence2Pb 2 B 10 O 16 (OH) 2 ·B(OH) 3 ·H 2 O: significantly enhanced second harmonic generation via substituting metal cations in isostructural compounds with Pb 2+2K2PbB5P3O17: A Mixed-Coordinated Borophosphate with Enhanced Birefringence Driven by the [B2O5] Unit5Prediction of New Functional Fluorooxoborates with Expected Anionic Framework: A Case of CaB3O5F4Design of rare earth borate short-wave UV nonlinear optical crystals with strengthened second harmonic generation activities via cationic modification strategy11Na2MP3O9 (M = K, Rb): Two Potential Zero-Order Waveplate Materials with DUV Cutoff Edges2Reversal Enhancement of Birefringence by Stereochemically Active Lone Pairs in Sn(II)-Based Mixed Halides0Effect of Cd2+ Doping on Laser Damage Threshold and Optical Performance of KDP Crystals1Novel [BO 2 ] superhalogen module-enabled deep-ultraviolet nonlinear optical material: rational design for tailored birefringence and phase matching0Navigating the Landscape of Next-Generation Nonlinear Optical Materials Discovery: Opportunities and Challenges Driven by Artificial Intelligence4Computational design of new DUV NLO fluorooxoborates with [BO 3 ] : [BO 3 F] = 2 : 1 via an anionic framework dimensionality-fixed strategy0The Achievement of a Strong Second Harmonic Generation Response and a Large Birefringence in Sulfates4High‐Performance Infrared Nonlinear Optical Crystals Discovery Guided by High‐Throughput Computation, Machine Learning, and Experimental Verification6Computational prediction of promising deep-UV nonlinear optical borate fluorides SrBO2F and BaBO2F0

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