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RESEARCH PAPER · Angewandte Chemie International Edition · 2022

High‐Performance Sulfate Optical Materials Exhibiting Giant Second Harmonic Generation and Large Birefringence

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High‐Performance Sulfate Optical Materials Exhibiting Giant Second Harmonic Generation and Large BirefringenceOriginalAAg 2 PS 4 (A = K, Na/K): the first-type of noncentrosymmetric alkali metal Ag-based thiophosphates exhibiting excellent second-order nonlinear optical performances21An excellent lead oxyiodide with a strong second-harmonic generation response and a large birefringence induced by the oriented arrangement of highly distorted [PbO 4 I 2 ] polyhedra13APb 2 (C 7 H 3 NO 4 ) 2 I (A = K, Rb, Cs): rare stable nonlinear optical crystals with second-harmonic generation response and highly distorted lead core coordination polyhedra2Halogen regulation triggers structural transformation from centrosymmetric to noncentrosymmetric switches in tin phosphate halides Sn 2 PO 4 X (X = F, Cl)47Hg 2 (SeO 3 )(SO 4 ): the first sulfate selenite with large birefringence explored from d 10 transition metal compounds36KLi 2 CO 3 F: a beryllium-free KBBF-type deep-UV carbonate with an enhanced interlayer interaction and large birefringence20Large optical anisotropy differentiation induced by the anion-directed regulation of structures29Mg(H 2 O) 6 [(IO 2 (OH)) 2 (IO 3 )] 2 : a new iodate with a very large band gap and optical anisotropy13NaGa3Se5: An Infrared Nonlinear Optical Material with Balanced Performance Contributed by Complex {[Ga3Se5]−}∞ Anionic Network14Enhanced Second-Harmonic-Generation Efficiency and Birefringence in Melillite Oxychalcogenides Sr2MGe2OS6 (M = Mn, Zn, and Cd)97Alkali metal sulfate: A new non-π-conjugated deep-ultraviolet quasi-phase matching crystal27Lone Pair-Driven Enhancement of Birefringence in Polar Alkali Metal Antimony Phosphates46RbBiP2S6: A Promising IR Nonlinear Optical Material with a Giant Second-Harmonic Generation Response Designed by Aliovalent Substitution80AgGaSe2-Inspired Nonlinear Optical Materials: Tetrel Selenides of Alkali Metals and Mercury34Homochiral Hybrid Organic–Inorganic Cadmium Chlorides Directed by Enantiopure Amino Acids30Organic Cation Modulation Triggered Second Harmonic Response in Manganese Halides with Bright Fluorescence46[C(NH2)3]2Zn(CO3)2: A Guanidinium-Templated Ultraviolet Nonlinear Optical Material20Sharp 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 Orbitals22(Na0.74Ag1.26)BaSnS4: A New AgGaS2‐Type Nonlinear Optical Sulfide with a Wide Band Gap and High Laser Induced Damage Threshold14[C(NH2)3]2MoO2F4·H2O: Unique Chinese-Knot Structure Revealing Superior Nonlinear-Optical Properties19Ternary AGa5S8 (A = K, Rb, Cs): Promising infrared nonlinear optical materials rationally realized by “one-for-multiple substitution” strategy37BaSb(H2PO2)3Cl2: An excellent UV nonlinear optical hypophosphite exhibiting strong second-harmonic generation response32Chalcohalides: A Rising Type of Second‐Order Nonlinear Optical Materials28SbHPO3F: 2D van der Waals Layered Phosphite Exhibiting Large Birefringence32Achieving effective balance between bandgap and birefringence by confining π-conjugation in an optically anisotropic crystal39Li0.5Na0.5AlB2O4F2: Fluoroaluminoborate with Aligned 1∞[BO2] Chain Induced by Unprecedented [AlO3F3]6− Species Features Enhanced Birefringence30Syntheses, structures, and characterization of new heteroanionic chalcohalides: Na2Ba17In8Q21F18 (Q = S, Se), KBa2InQ3F2 (Q = S, Se)5AeMg6Ga6S16 (Ae = Ca, Sr, Ba): The First Double Alkaline‐Earth Metal Chalcogenides with Excellent Performances29Rb 2 CdSi 4 S 10 : novel [Si 4 S 10 ] T2-supertetrahedra-contained infrared nonlinear optical material with large band gap79Rb 3 B 5 O 8 F 2 and K 0.6 Rb 2.4 B 5 O 8 F 2 : two new deep-ultraviolet transparent nonlinear optical fluorooxoborates designed by cation regulation13d6versus d10, Which Is Better for Second Harmonic Generation Susceptibility? A Case Study of K2TGe3Ch8 (T = Fe, Cd; Ch = S, Se)18(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 new stable polymorph of Li 2 TeMo 3 O 12 with wide mid-infrared transparency and a large Raman response17From BPS 4 to AB 3 P 2 S 10 (A = Na, K): cations inducing dimension reduction and bandgap enlargement7Heteroanion-introduction-driven birefringence enhancement in oxychalcogenide Ba 3 M II Ge 3 O 2 S 8 (M II = Mn, Cd)19Hg 3 O 2 (NO 3 )F: a mercury nitrate oxyfluoride with an unprecedented [(Hg 3 O 2 F) + ] ∞ cationic framework and excellent optical anisotropy21LaAeAl 3 S 7 (Ae = Ca, Sr): Cairo pentagonal layered thioaluminates achieving a good balance between a strong second harmonic generation response and a wide bandgap23Low temperature molten salt synthesis of noncentrosymmetric (NH 4 ) 3 SbF 3 (NO 3 ) 3 and centrosymmetric (NH 4 ) 3 SbF 4 (NO 3 ) 234Na 7 (SeO 4 ) 3 (IO 3 ) and K 2 (SeO 4 )[IO 2 (OH)]: two new iodate-selenates with short-wave UV cutoff edge and large birefringence8Pb2Cl2(HPO3)(H2O) and Pb3Br2(HPO3)2: Two Phosphite Halides with 3D Structural Networks and Enlarged Birefringence18Deep Eutectic Solvents Synthesis of A2Sb(C2O4)Cl3 (A = NH4, K, Rb) with Superior Optical Performance26A Rare‐Earth Selenite with Unexpectedly Well‐Balanced Ultraviolet Nonlinear Optical Functionality, Sc(HSeO 3 ) 331Controlling the Nonlinear Optical Behavior and Structural Transformation with A‐Site Cation in α‐AZnPO4 (A = Li, K)20[K2PbX][Ga7S12] (X = Cl, Br, I): The First Lead‐Containing Cationic Moieties with Ultrahigh Second‐Harmonic Generation and Band Gaps Exceeding the Criterion of 2.33 eV46Two Mixed-Alkali-Metal Selenates as Short-Wave Ultraviolet Nonlinear-Optical Materials102D Perovskite Mn 2+ ‐Doped Cs 2 CdBr 2 Cl 2 Scintillator for Low‐Dose High‐Resolution X‐ray Imaging127Unveiling the Superior Optical Properties of Novel Melamine‐Based Nonlinear Optical Material with Strong Second‐Harmonic Generation and Giant Optical Anisotropy74Host–Guest Symmetry Matching in Two Crystalline Magnesium Sulfate Oxalates Obtained Via a Solvent-Free Route8Optimal Design of Mid-Infrared Nonlinear-Optical Crystals: From SrZnSnSe 4 to SrZnSiSe 422Stereochemically Active Tin(II)‐Induced Enhancement of Birefringence in SnIISnIV(PO4)2 and SrSn(PO4)PO2(OH)23A Hydrogen Bonded Supramolecular Framework Birefringent Crystal89A Hydrogen Bonded Supramolecular Framework Birefringent Crystal13Y(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 compounds20Cd2Nb2Te4O15: A Novel Pseudo‐Aurivillius‐Type Tellurite with Unprecedented Nonlinear Optical Properties and Excellent Stability40Hg3(SeO3)2(SO4): A UV Nonlinear Optical Mercury Selenite Sulfate Constructed by Neat [Hg6O8(SeO3)4]∞ Layers and SO4 Tetrahedra27All-organic polymeric materials with high refractive index and excellent transparency126Improved Birefringence Activated by Tetrahedra Decorated with a Single Linear Unit38Improved Birefringence Activated by Tetrahedra Decorated with a Single Linear Unit1From Centrosymmetry to Noncentrosymmetry: Precise Structural Regulation and Characterization on ZnHPO3·2H2O Polymorphs13Ultraviolet Crystal with Strong Optical Nonlinearity by Creating Halogen-Centered Secondary Building Blocks15Centrosymmetric Rb2Sb(C2O4)2.5(H2O)3 and Noncentrosymmetric RbSb2(C2O4)F5: Two Antimony (III) Oxalates as UV Optical Materials20Quadruple‐Bidentate Nitrate‐Ligated A 2 Hg(NO 3 ) 4 (A=K, Rb): Strong Second‐Harmonic Generation and Sufficient Birefringence59Quadruple‐Bidentate Nitrate‐Ligated A 2 Hg(NO 3 ) 4 (A=K, Rb): Strong Second‐Harmonic Generation and Sufficient Birefringence2Li2RbSO4Cl with a Short Ultraviolet Absorption Edge and an Acentric Structure through Assembling Heteroleptic [LiO3Cl] Tetrahedra2Giant Mid‐Infrared Second‐Harmonic Generation Response in a Densely‐Stacked Van Der Waals Transition‐Metal Oxychloride39Giant Mid‐Infrared Second‐Harmonic Generation Response in a Densely‐Stacked Van Der Waals Transition‐Metal Oxychloride8ASn(C10H12N2O8)Cl·H2O (A = K, Rb): Nonlinear optical crystals with new distorted Sn(IV)-centered nitrogen-oxygen-chloride polyhedron and wide band gaps6Four UV Transparent Linear and Nonlinear Optical Materials Explored from Pure Selenite Compounds22Mixed Anionic Tetrahedra Guided Design of New Infrared Nonlinear Optical Material Cs 3 Ga 8 S 13 Cl with High Laser‐Induced Damage Threshold26Excellent Nonlinear Optical M[M4Cl][Ga11S20] (M = A/Ba, A = K, Rb) Achieved by Unusual Cationic Substitution Strategy20A Two‐Dimensional Hybrid Perovskite With Heat Switching Birefringence47A Two‐Dimensional Hybrid Perovskite With Heat Switching Birefringence7Theoretical investigations on ternary defective diamond-like infrared nonlinear optical materials in Be-Ga-Se system18Second-Harmonic Generation in Homochiral Antimony Halides Directed by l -Histidine24A potassium lead 2-methylmalonate-iodide nonlinear optical crystal with strong second-harmonic generation response and large birefringence2Designing Sulfate Crystals with Strong Optical Anisotropy through π‐Conjugated Tailoring51Designing Sulfate Crystals with Strong Optical Anisotropy through π‐Conjugated Tailoring11Two van der Waals Layered Antimony(III) Phosphites as UV Optical Materials11Free Halogen Substitution of Chiral Hybrid Metal Halides for Activating the Linear and Nonlinear Chiroptical Properties140A2Hgx(SeO3)y (A = K, Rb, Cs): Three Alkali Metal Mercury Selenites Featuring Unique 1D [HgOm(SeO3)n]∞ Chains13C(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 Properties14Secondary‐Bond‐Driven Construction of a Polar Material Exhibiting Strong Broad‐Spectrum Second‐Harmonic Generation and Large Birefringence9Secondary‐Bond‐Driven Construction of a Polar Material Exhibiting Strong Broad‐Spectrum Second‐Harmonic Generation and Large Birefringence41K(NH4)Zn2(PO4)2: a Beryllium-Free Sr2Be2B2O7 Derivative with Enhanced Interlayer Connectivity7A chiral sodium lanthanum sulfate for second-order nonlinear optics and proton conduction6A highly birefringent metal-free crystal assembled by cooperative non-covalent interactions30Achieving strong second harmonic generation effects induced via dimensional increase of PbX 6 octahedra and halogen substitutes in (C 10 H 11 N 3 )PbX 4 (X = Cl or Br)26Ba 2 GeF 2 Q 3 (Q = S, Se) and Ba 3 GeF 2 Se 4 : new F-based chalcohalides with enhanced birefringence9Designing excellent UV birefringent materials through the synergistic interaction of two highly distorted functional groups23KBa 3 M 2 F 14 Cl (M = Zr, Hf): novel short-wavelength mixed metal halides with the largest second-harmonic generation responses contributed by mixed functional moieties37New ultraviolet transparent rare-earth borates with enhanced birefringence induced by cation chemical substitution15Novel antimony phosphates with enlarged birefringence induced by lone pair cations4Partial substitution with a significant effect: coexistence of a wide band gap and large birefringence in the oxychalcogenide AEGe 2 O 4 Se (AE = Sr and Ba)17Reconstructing nearly isotropic microstructures to construct a one-dimensional framework causing record birefringence in thiophosphates13Wide band gap selenide infrared nonlinear optical materials A II Mg 6 Ga 6 Se 16 with strong SHG responses and high laser-induced damage thresholds31Synthesis and Characterization of Metal Iso-cyamelurate K0.5In0.5(H2C6N7O3)2·9H2O with Large Birefringence8Giant Optical Anisotropy in a Covalent Molybdenum Tellurite via Oxyanion Polymerization43C(NH2)3MoO3(IO3): A Molybdenyl Iodate with Giant Birefringence Designed via a Cation–Anion Synergetic Interaction Strategy36Hg4(Te2O5)(SO4): A Giant Birefringent Sulfate Crystal Triggered by a Highly Selective Cation153From Cd(SCN) 2 (CH 4 N 2 S) 2 to Cd(SCN) 2 (C 4 H 6 N 2 ) 2 : Controlling Sulfur Content in Thiocyanate Systems Significantly Improves the Overall Performance of UV Nonlinear Optical Materials9From Cd(SCN) 2 (CH 4 N 2 S) 2 to Cd(SCN) 2 (C 4 H 6 N 2 ) 2 : Controlling Sulfur Content in Thiocyanate Systems Significantly Improves the Overall Performance of UV Nonlinear Optical Materials50A2Pb3[H2N(CH2COO)2]3Cl5 (A = K, Rb): Porous Crystals Constructed on [Pb3Cl5O6] Clusters with Comprehensive Nonlinear Optical Performance3Polysubstitution Induced Centrosymmetric-to-Noncentrosymmetric Structural Transformation and Nonlinear-Optical Behavior: The Case of Na0.45Ag0.55Ga3Se52Hg16O12(NO3)6F2(H2O): A Mercury-Rich Nitrate Oxyfluoride with Diverse Triple-Coordinated Mercury-Based Units That Exhibits an Unparalleled [(Hg16O12F2(H2O))6+]∞ Cationic Framework and a Large Birefringence12Mixed Anionic M(S/X)6 Polyhedra as Symmetry-Breaking Motifs to Enhance the Infrared Nonlinear Optical Response in Y–M–S–X (M = Ga, Ge; X = Cl, Br)5Edge-Sharing Tetrahedra Realizing Superior Birefringence and High Deep-Ultraviolet Transmittance in α-Be3(H2O)2(PO4)2 Crystal Synthesized by Mild Chemistry14Two Short-Wave UV Beryllium Selenites Exhibiting Diverse Optical Properties Stemming from Functional Group Arrangements8Sb2O2SeO3 and Sb2O(SeO3)2: Two-Layered Antimony(III) Selenites with Enhanced Birefringence10Old tree blossoms anew: Research progress on the structures and optical properties of ultraviolet selenites56A3Sc(SO4)3 (A = K, Rb, Cs): Three Deep‐Ultraviolet Transparent Alkali‐Scandium Sulfates with Strong Second‐Harmonic Generation Response and High Thermal Stability14Optimization of Functional Building Blocks Generates a Substantial Improvement in Birefringence from Sn2OSO4 to Sn3O2(OH)(HSO4)6The Directional Design of the Quasi‐Phase‐Matching Short‐Wave Ultraviolet Nonlinear Optical Crystal25Achieving the Birefringence Optimization by Methyl Modulation in Organic Nonlinear Optical Crystals15Unusual Triple-State Switching of Thermally Induced Birefringence in a Two-Dimensional Perovskite Ferroelectric45Li2NaB3S2O12: A Deep-UV Transparent Borosulfate with Moderate Birefringence Derived from the [B3S2O12]∞ Infinite Chain Designed by the High Boron-to-Sulfur Ratio Strategy6SbO(OH)2(IO3): The First Polar Sb5+‐Iodate with a Strong Second‐Harmonic Generation Response and a Wide Bandgap8Achieving Phase‐Matching in Nonlinear Optical Materials CsM 2 In 2 S 6 (M = Cd/In, Hg/In) by the Incorporation of Unprecedented Trigonal Planar MS 3 Motifs6The New Paradigm of Ligand Substitution-Driven Enhancement of Anisotropy from SO4 Units in Short-Wavelength Region14Birefringence Disparity Induced by Synergistic Effects of Stereochemically Active Lone Pairs19Rational Design and Controlled Synthesis of High-Performance Inorganic Short-Wave UV Nonlinear Optical Materials150Cationic Coordination Modification Drives Birefringence and Nonlinear Effect Double Lifting in Sulfate4(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 Substitution38A strongly birefringent sulfate crystal with a wide second-harmonic generation phase-matching range4A tri-alkali/alkaline-earth metal fluorophosphate deep-ultraviolet birefringent crystal with coexisting PO 3 F and PO 2 F 24Achieving balanced UV SHG responses, optical band gaps and birefringence in rare earth compounds Ln(IO 3 )(SO 4 )·3H 2 O (Ln = Y, Gd, Er, Ho, Dy, Eu)4An excellent ultraviolet nonlinear optical crystal derived from the polar methylphosphonate unit8Bazn2(Hpo3)3: A New Barium Zincophosphite with Short Ultraviolet Cutoff Edge0Different p-block elements induce C 3 [111] octahedral distortion in titanium to generate an intense nonlinear effect14Exploring Novel Mixed Metal Sulfate Hydrates with Short UV Cut-Off Edges0Greatly enhancing birefringence of fluorosilicates through the synergetic effect of functional units13Harnessing the dual role of DMSO in the synthesis of SbOCl·DMSO: an excellent nonlinear optical crystal with unique 1D spiral chain10Hg 2 (HTe 2 O 5 )(PO 4 ): a novel phosphate crystal with enhanced birefringence enabled by the synergistic modification of multiple functional groups12Hg[CS(NH 2 ) 2 ] 4 (SiF 6 ): a fluorosilicate crystal with large birefringence achieved via multi-functional group modification6K 2 SO 4 (NH 3 SO 3 ) 2 and Cs 2 SO 4 (NH 3 SO 3 ) 3 : two deep-UV transparent sulfamate-sulfates with moderate birefringence2Structure modulation by cationic modification of sulfates using planar CS(NH 2 ) 25Birefringence Modulation by Phenyl and Acyl Groups in Urea-Based Crystals3Dual Lone Pair Strategy for High Birefringence in Antimony(III)-Based Tellurite Sulfates with Short-Wave UV Transparency10New Ways to Discover Novel Nonlinear Optical Materials: Scaling Machine Learning with Chemical Descriptors Information20Mn(II)-Doped Perovskites with Carboxylic Acid Dimers Exhibiting Scintillation5Series of New Alkali Metal Hafnium-Based Iodates A2Hf(IO3)6 (A = K, Rb, Cs) and Isomorphic Ba2Zn(IO3)6 with Large Birefringence1Polar [ NH ( CH2SO3 )2]2− Dimers Enable the First Promising Iminodimethanesulfonate with Nonlinear Optical Properties and Wide UV Transparency19Ultra‐High Optical Anisotropy with UV Transmission Achieved by Rational Arrangement of Extended π‐Conjugated Groups5Ultra‐High Optical Anisotropy with UV Transmission Achieved by Rational Arrangement of Extended π‐Conjugated Groups46Metal Cation Engineered UV Birefringent Crystals in π‐Conjugated Sulfonates with Record‐High Optical Anisotropy17Synthesis, Crystal, and Electronic Structures, and Second Harmonic Generation of La4Ge3S121Hg3(TeO3)2(NO3)2 and Hg3(Te2O5)2(NO3)2: The First Two Hg‐Based Tellurite Nitrate Unit‐Mixed Crystals with Large Optical Anisotropy16Halogen-Driven Structural Engineering in Tellurium Oxyhalides: Enhanced SHG Response and Broad Optical Transparency6From AgHgI(SO4) to AgHg3I3.2Cl1.8(SO4): Symmetry Breaking of the Belousovite‐Type Topology by Mixed Halides to Achieve Strong Nonlinear Optical Effect14

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  2. An excellent lead oxyiodide with a strong second-harmonic generation response and a large birefringence induced by the oriented arrangement of highly distorted [PbO 4 I 2 ] polyhedra

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  12. Lone Pair-Driven Enhancement of Birefringence in Polar Alkali Metal Antimony Phosphates

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  23. Ternary AGa5S8 (A = K, Rb, Cs): Promising infrared nonlinear optical materials rationally realized by “one-for-multiple substitution” strategy

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