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RESEARCH PAPER · Angewandte Chemie International Edition · 2020

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

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Series of Crystals with Giant Optical Anisotropy: A Targeted Strategic ResearchOriginalAn Antimony(III) Fluoride Oxalate with Large Birefringence45Synergism of multiple functional chromophores significantly enhancing the birefringence in layered non-centrosymmetric chalcohalides20A new rare-earth borate birefringent crystal with quasi-two-dimensional [BO 3 ] layers23An organic–inorganic hybrid birefringent material with diverse functional groups38Computationally assisted multistage design and prediction driving the discovery of deep-ultraviolet nonlinear optical materials41Design and synthesis of Ba 3 SiSe 5 with suitable birefringence modulated via M IV atoms in the Ba–M IV –Q (M IV = Si, Ge; Q = S, Se) system3Distinctive 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 centrosymmetric to noncentrosymmetric: effect of the cation on the crystal structures and birefringence values of (NH 4 ) n−2 AE(PO 2 F 2 ) n (AE = Mg, Sr and Ba; n = 2, 3 and 4)9Two metal-free cyanurate crystals with a large optical birefringence resulting from the combination of π-conjugated units17Finding Short-Wavelength Birefringent Crystals with Large Optical Anisotropy Activated by π-Conjugated [C(NH2)3] Units45LiZn(OH)CO3: A Deep‐Ultraviolet Nonlinear Optical Hydroxycarbonate Designed from a Diamond‐like Structure180LiZn(OH)CO3: A Deep‐Ultraviolet Nonlinear Optical Hydroxycarbonate Designed from a Diamond‐like Structure10K‐Ion Battery Cathode Design Utilizing Trigonal Prismatic Ligand Field80Cs2ZnSn3S8: A Sulfide Compound Realizes a Large Birefringence by Modulating the Dimensional Structure24AZn4(OH)4(C3N3O3)2 (A = Mg, Zn): Two Zn-Based Cyanurate Crystals with Various Cation Coordination and Large Birefringence22Machine Learning with Multilevel Descriptors for Screening of Inorganic Nonlinear Optical Crystals35Unusual ferroelectric-dependent birefringence in 2D trilayered perovskite-type ferroelectric exploited by dimensional tailoring63NH4Sb2(C2O4)F5: A novel UV nonlinear optical material synthesized in deep eutectic solvents38Hierarchical Modulation of Optical Anisotropy Driven by Metal Cation Polyhedra in Fluorooxoborates MIIB4O6F2 (MII=Be, Mg, Pb, Zn, Cd)6(C 3 N 6 H 7 ) 2 SiF 6 ·H 2 O: an ultraviolet birefringent crystal exceeding the intrinsic energy gap of an organic reagent38(N 2 H 6 )[HPO 3 F] 2 : maximizing the optical anisotropy of deep-ultraviolet fluorophosphates33Ba 2 Zn 2 B 6 O 13 : coplanar [B 2 O 5 ] in unnoted U-shaped [B 6 O 13 ] groups achieving large birefringence6Hg 2 (SeO 3 )(SO 4 ): the first sulfate selenite with large birefringence explored from d 10 transition metal compounds36KRE(CO 3 ) 2 (RE = Eu, Gd, Tb): new mixed metal carbonates with strong photoluminescence and large birefringence15Li 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 hybridization9Nain(C2o4)(Hpo4)(H2o)5: An Ultraviolet Transparent Nonlinear Optical Oxalate-Phosphate with Large Birefringence0Performance 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 prospects322CsY(SO4)2·4H2O: A Deep-Ultraviolet Birefringent Crystal Induced by an Edge-Sharing Connection26Finding the First Squarates Nonlinear Optical Crystal NaHC4O4·H2O with Strong Second Harmonic Generation and Giant Birefringence56A Hybrid Halide Perovskite Birefringent Crystal14A Hybrid Halide Perovskite Birefringent Crystal149Nonlinear Optical Benzoindolium-Based Single Crystals: H-Contacts Induced Noncentrosymmetric Alignment Approaching Efficient Terahertz-Wave Generation17Yin–Yang Complementarity Strategy Achieving Giant Optical Anisotropy in a Metal-free Birefringent Material C(NH2)3(HC4O4)14Cation-anion synergetic interactions achieving tunable birefringence in quasi-one-dimensional antimony(III) fluoride oxalates58Difluoro(oxalato)borates as Short-Wavelength Optical Crystals with Bifunctional [BF 2 C 2 O 4 ] Units38Sharp Enhancement of Birefringence in Antimony Oxalates Achieved by the Cation–Anion Synergetic Interaction Strategy38An Optically Anisotropic Crystal with Large Birefringence Arising from Cooperative π Orbitals81An Optically Anisotropic Crystal with Large Birefringence Arising from Cooperative π Orbitals22From Phosphate Fluoride to Fluorophosphate: Design of Novel Ultraviolet/Deep-Ultraviolet Nonlinear Optical Materials for BePO3F with Optical Property Enhancement34(C3N6H7)2SbF5·H2O Exhibiting Strong Optical Anisotropy from the Optimal Arrangement of π-Conjugated (C3N6H7)+ Groups31Li0.5Na0.5AlB2O4F2: Fluoroaluminoborate with Aligned 1∞[BO2] Chain Induced by Unprecedented [AlO3F3]6− Species Features Enhanced Birefringence30Design of deep-ultraviolet nonlinear optical materials based on fundamental building blocks with excellent microscopic properties1C 10 H 10 ClNO 3 : exploration of birefringent crystals in an isoquinoline system20Dramatically improved optical anisotropy by realizing stereochemically active lone pairs in a sulfate system, K 2 SO 4 ·HIO 323Linear π-conjugated units of the D ∞h point group as superior ultraviolet birefringent units1Polar and non-polar stacking of perfectly aligned parallel beloamphiphile monolayers (PBAMs) of (PhO, F)-azine. The interplay of non-covalent interlayer interactions and unit cell polarity4Solvent-free synthesis of magnesium phosphite-oxalates that show second-harmonic generation responses5The transformation of a zero-dimensional cluster into a one-dimensional chain structure achieving a dramatically enhanced birefringence in tin( ii )-based oxalates33β-(C 3 H 7 N 6 ) 2 Cl 2 ·H 2 O and (C 3 H 7 N 6 )F·H 2 O: two UV birefringent crystals induced by uniformly aligned structural groups35Target‐Driven Design of Deep‐UV Nonlinear Optical Materials via Interpretable Machine Learning125Chain‐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 Materials5Host–Guest Symmetry Matching in Two Crystalline Magnesium Sulfate Oxalates Obtained Via a Solvent-Free Route8Stereochemically Active Tin(II)‐Induced Enhancement of Birefringence in SnIISnIV(PO4)2 and SrSn(PO4)PO2(OH)23“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 Halides2KHC 2 O 4 · B ( OH ) 3 : A nonlinear optical crystal with large birefringence in the short‐wavelength ultraviolet region9Mixed Alkali Metal and Alkaline Earth Metal Scandium Borate Birefringence Material with Layered Structure and Short Ultraviolet Cutoff Edge17Tunable multicolor luminescence in vanadates from yttrium to indium with enhanced luminous efficiency and stability for its application in WLEDs and indoor photovoltaics12Centrosymmetric Rb2Sb(C2O4)2.5(H2O)3 and Noncentrosymmetric RbSb2(C2O4)F5: Two Antimony (III) Oxalates as UV Optical Materials20C14H10BrNO2: A Birefringent Crystal with an Expanded π-Conjugated Group13NaCl·CH4N2O·H2O: An Organic–Inorganic Hybrid Ultraviolet Nonlinear Optical Crystal with Optimized Comprehensive Properties8Cs2Pb4Br10: A layered perovskite shows large birefringence11Designing Sulfate Crystals with Strong Optical Anisotropy through π‐Conjugated Tailoring51Designing Sulfate Crystals with Strong Optical Anisotropy through π‐Conjugated Tailoring11Positive and Negative Contribution from Lead–Oxygen Groups and Halogen Atoms to Birefringence: A First Principles Investigation4Achieving great optical anisotropy with the well-directed alignment of π-conjugated groups due to hydrogen bonds9C(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 3 N 6 H 7 )BF 4 ·H 2 O and (C 3 N 6 H 7 )SO 3 CH 3 ·H 2 O with large birefringence induced by coplanar π-conjugated [C 3 N 6 H 7 ] + groups33A highly birefringent metal-free crystal assembled by cooperative non-covalent interactions30Exploration of antimony( iii ) oxyhalides via single-site substitution in quest of large birefringence10Exploring short-wavelength birefringent crystals via triggering cooperative arrangement between different π-conjugated groups8Solvent-free synthesis and optical properties of two open-framework metal oxalates with zeolitic ABW and diamondoid topologies3Design of Deep-Ultraviolet Zero-Order Waveplate Materials by Rational Assembly of [AlO2F4] and [SO4] Groups9Screening Large Birefringent Materials via Halogen Regulation in Ternary d0-Transition Metal Oxyhalides8The Birefringence Modulation in Short‐Wave Ultraviolet Sulfates with Functional π‐Conjugated Cations and Polymerized Heteroleptic Tetrahedral Anions18Perfect Polar Alignment of Parallel Beloamphiphile Layers: Improved Structural Design Bias Realized in Ferroelectric Crystals of the Novel “Methoxyphenyl Series of Acetophenone Azines”3Enhancement of Birefringence in π-Conjugated Oxyfluorides Achieved via van der Waals Layered Structural Optimization10Layered (C5H6ON)2[Sb2O(C2O4)3] with a large birefringence derived from the uniform arrangement of π-conjugated units11Enhanced Birefringence in Phosphates via “Two Steps in One”: d0 Transition Metal Regulation and Fluorination Synergistic Strategy7Na3K6(CO3)3(NO3)2X·6H2O (X = NO3, Cl, Br): Exploring High-Performance UV Birefringent Crystals Induced by Coplanar π-Conjugated CO3 and NO3 Groups15A Highly Optical Anisotropic Hybrid Perovskite for Efficient Manipulation of Light Polarization64C9H7NBrX (X = Cl, Br, NO3): Three Excellent Birefringent Crystals with Distinct Optical Anisotropy Regulated by Anions34Homoatomic Polychalcogenide Nonlinear Optical Anionic Groups with Ultra-Large Optical Anisotropy31Bi(SO4)F·H2O and Bi(SO4)(NO3)·3H2O: Chemical Substitution-Induced Birefringence Enhancement in Bismuth Sulfates6Gradual Increase in Birefringence of Antimony Oxalates through Precise Tuning of the Sb3+/[C2O4]2– Ratio7Colossal in-plane optical anisotropy in a two-dimensional van der Waals crystal74Polar Stacking of Dipole Parallel-Aligned Monolayers of Unsymmetrical 1,4-Diphenyl-1,3-butadienes Creates Nonlinear Optical Materials: Insights from Experiments Guide Structure Assignments0C2H12N6C4O4·2H2O and Na2C4O4·3H2O: Two Ultraviolet Birefringent Compounds with the [C4O4]2– Group3A novel sodium manganese fluorooxalate crystal Na2Mn2(C2O4)2.5F·2H2O: Synthesis, structure, optical and thermal properties2A Highly Optical Anisotropic Hybrid Metal Halide for Modulation and Generation of Polarized Light44Pb2TeV2O10: A Lead Vanadate Tellurate with Wide Mid-IR Transparency and Large Birefringence Induced by Multiple Birefringence-Active Groups11Graph neural network guided design of novel deep-ultraviolet optical materials with high birefringence23Synthesis, structure and characterizations of the first alkali-metal/alkaline-earth-metal oxalatophosphate Na4Mg3(HPO4)4(C2O4)·2H2O3Unveiling Noncentrosymmetric Pyridine Carboxylates from Centrosymmetric Templates through Motif Configuration Modulation in Zero-Dimensional System7BaPb2(CO3)2F2: Enhancing Birefringence by a Multiunit Synergy Effect9Exploring ultra-high optical anisotropy in polyiodides7Structural 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 series0新型非线性光学晶体和双折射晶体的研究进展(特邀)4Birefringence Modulation by Phenyl and Acyl Groups in Urea-Based Crystals3Efficient photocatalytic removal of typical water pollutants synergized by nitrogen defects and Fe-Ti alloy2Giant Birefringence Enabled by the Highly Anisotropic Linear IX 2 − (X = Cl, Br) Building Blocks6Giant Birefringence Enabled by the Highly Anisotropic Linear IX 2 − (X = Cl, Br) Building Blocks32A transparent crystal with giant birefringence arising from π-electron anisotropy32Improving the Performance of Birefringent Crystals by Molecular Assembly Strategy in the Solar‐Blind UV Region14[C( NH2 )3] 2SiF6 : Design of Deep Ultraviolet Crystals with Large Birefringence Based on a Fluorination‐Oriented Strategy13Designing High-Performance Short-Wave UV Tellurium-Based Mixed Halides Birefringent Crystals via Halogen Substitution Engineering4Breaking the Birefringence Barrier in B–O Crystals via B–C π-scaffolding36Three-In-One: A Guanidinium-Containing Niobium Oxyfluoride with a Perovskite-like Structure Revealing Multifunctional Optical Properties2Four Benzoguanamine-Based Birefringent Crystals with Excellent Optical Anisotropy5Hydrogen Bond-Assisted Structural Regulation Enables Large Birefringence in Two Antimony Oxalofluoride Crystals5Achieving large birefringence in oxalate crystals by a hydrogen bond-directed strategy1Giant Birefringence Induced by Intermolecular Aromatic Interactions in Hydrogen‐Bonded Organic Frameworks37Enhancing Birefringence via a Planar‐Conformation‐Locking Strategy3Five-Membered [C 5 O 5 ] 2 – Rings as Birefringence-Active Genes for Ultrabirefringent Crystals27Hydrogen‐Bond‐Driven Metal‐Free Crystal (C 6 H 7 N 2 O)(NH 2 SO 3 ) with Giant Birefringence and Solar‐Blind Ultraviolet Transmission0Achieving 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) Groups3Achieving record birefringence in metal-free semiorganic sulfate crystals via tetrahedral anionic group substitution0Design of borate-squarate hybrid crystals with large birefringence by synergistic assembly of planar π-conjugated groups0Molecular pseudo-halogen engineering enables remarkable birefringence enhancement in hybrid perovskites0Synthesis and characterization of mixed carbonate and bicarbonate materials as candidates for deep-UV applications1Truss bridge-like anhydrous stacking in hybrid crystals triggers ultra-high stability and robust birefringence0Unit Symmetry‐Breaking and Layered Linear Ordering Enabling Superior Short‐Wave Ultraviolet Birefringent Crystal8Unveiling the Superior Birefringence Property of a Record‐Birefringent Crystal with Unique Building Block12V-Shaped Pseudo-Chains Coupled with Lone-Pair-Distorted [GeX 3 ] − Units Enable Large Birefringence in Ge(II) Hybrid Halides2Structural Anion Geometry-Regulated Molecular Alignment in [C 10 H 8 NO 2 ]-Based Crystals for Enhancing Ultraviolet Birefringence0Bio-inspired proton-conformation-coupled hydrogen-bond network reconfiguration for adaptive optical anisotropy0[CN4H8]SiF6: Fluorination-guided design of deep-UV crystal with large birefringence0Decoupling Contributions of Distinct Strategies for Enhancing Polarizability Anisotropy in Crystals Containing π-Conjugated Groups0Reversible Symmetry Switching, Giant Birefringence, and UV Second‐Harmonic Generation in Hybrid Niobium Oxyfluorides0Reversible Symmetry Switching, Giant Birefringence, and UV Second‐Harmonic Generation in Hybrid Niobium Oxyfluorides0Configurational entropy-driven electronic reconstruction in five-component phthalocyanine frameworks: A transferable modulation route for sacrificial-agent-free solar-to-chemical H2O2 production0Short-UV Metal Halide Nitrates: Moderate SHG in K3Sb(NO3)3F3 and Enhanced Optical Anisotropy in K3Zn(NO3)X4 (X = Cl, Br)0Record‐High Birefringence Achieved by Linearly Extended π‑Conjugated Building Blocks in Metal‐Free Sulfate0

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