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RESEARCH PAPER · Journal of the American Chemical Society · 2021

Large Second-Harmonic Response and Giant Birefringence of CeF 2 (SO 4 ) Induced by Highly Polarizable Polyhedra

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Large Second-Harmonic Response and Giant Birefringence of CeF 2 (SO 4 ) Induced by Highly Polarizable PolyhedraOriginalDeep-ultraviolet transparent alkali metal–rare earth metal sulfate NaY(SO 4 ) 2 ·H 2 O as a nonlinear optical crystal: synthesis and characterization28From Ce(IO 3 ) 4 to CeF 2 (IO 3 ) 2 : fluorinated homovalent substitution simultaneously enhances SHG response and bandgap for mid-infrared nonlinear optics26Hg 3 (Te 3 O 8 )(SO 4 ): a new sulfate tellurite with a novel structure and large birefringence explored from d 10 metal compounds39In situ hydrothermal synthesis of polar second-order nonlinear optical selenate Na 5 (SeO 4 )(HSeO 4 ) 3 (H 2 O) 219RbMo 2 P 3 O 14 with large birefringence mainly induced by highly distorted [MoO 6 ] in uncommon [Mo 2 P 3 O 14 ] ∞ layers9Systematic 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 ]8Two bismuth iodate sulfates with enhanced optical anisotropy17Zn(NH 3 )CO 3 : a “three-in-one” UV nonlinear optical crystal built by a polar molecule bonding strategy18UV Solar‐Blind‐Region Phase‐Matchable Optical Nonlinearity and Anisotropy in a π‐Conjugated Cation‐Containing Phosphate196UV Solar‐Blind‐Region Phase‐Matchable Optical Nonlinearity and Anisotropy in a π‐Conjugated Cation‐Containing Phosphate28Hydrogen‐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 Generation19Cs2ZnSn3S8: A Sulfide Compound Realizes a Large Birefringence by Modulating the Dimensional Structure24A2MoO2F3(IO2F2) (A = Rb, Cs): Strong Nonlinear Optical Responses and Enlarged Band Gaps through Fluorine Incorporation50Mg 2 In 3 Si 2 P 7 : A Quaternary Diamond-like Phosphide Infrared Nonlinear Optical Material Derived from ZnGeP 2130KCs2[Pb2Br5(HCOO)2]: A Polar 3D Lead‐Bromide Framework Exhibiting Strong Second‐Harmonic Generation Response10Linear and Nonlinear Optical Properties of Centrosymmetric Sb 4 O 5 SO 4 and Noncentrosymmetric Sb 4 O 4 (SO 4 )(OH) 2 Induced by Lone Pair Stereoactivity55Heterobimetallic Cluster‐Based Coordination Polymers: Assembly, Structures and Third‐Order Nonlinear Optical Properties4A Congruent‐Melting Mid‐Infrared Nonlinear Optical Vanadate Exhibiting Strong Second‐Harmonic Generation22A Congruent‐Melting Mid‐Infrared Nonlinear Optical Vanadate Exhibiting Strong Second‐Harmonic Generation63Giant Second-Harmonic Generation Response and Large Band Gap in the Partially Fluorinated Mid-Infrared Oxide RbTeMo 2 O 8 F149Synthesis, Crystal Structure, and Nonlinear Optical Property of an Anhydrous Sulfate KTb(SO4)216Strong SHG Responses in a Beryllium‐Free Deep‐UV‐Transparent Hydroxyborate via Covalent Bond Modification89Strong SHG Responses in a Beryllium‐Free Deep‐UV‐Transparent Hydroxyborate via Covalent Bond Modification9A Lead Mixed Halide with Three Different Coordinated Anions and Strong Second‐Harmonic Generation Response10From CeF2(SO4)·H2O to Ce(IO3)2(SO4): Defluorinated Homovalent Substitution for Strong Second-Harmonic-Generation Effect and Sufficient Birefringence53CsCu 3 SbS 4 : rational design of a two-dimensional layered material with giant birefringence derived from Cu 3 SbS 442K 3 V 2 O 3 F 4 (IO 3 ) 3 : a high-performance SHG crystal containing both five and six-coordinated V 5+ cations33NaSb3O2(SO4)3·H2O: A New Alkali-Metal Antimony(III) Sulfate with a Unique Sb6O20H4 Unit and Moderate Birefringence19A Lanthanum Ammonium Sulfate Double Salt with a Strong SHG Response and Wide Deep‐UV Transparency15A Lanthanum Ammonium Sulfate Double Salt with a Strong SHG Response and Wide Deep‐UV Transparency96A 2 P 2 S 6 (A = Ba and Pb): a good platform to study the polymorph effect and lone pair effect to form an acentric structure28An 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 polyhedra2BaSc 2 (HPO 3 ) 4 (H 2 O) 2 : a new nonlinear optical phosphite exhibiting a 3D {[Sc 2 (HPO 3 ) 4 ] 2− } ∞ anionic framework and phase-matchable SHG effect32Broad transparency and wide band gap achieved in a magnetic infrared nonlinear optical chalcogenide by suppressing d–d transitions41CaCe(IO 3 ) 3 (IO 3 F)F: a promising nonlinear optical material containing both IO 3 − and IO 3 F 2− anions22CsB 3 O 4 (OH) 2 : a new deep-ultraviolet birefringent crystal with [B 3 O 4 (OH) 2 ] anionic group8First polar quaternary sulphide CsLiGa 6 S 10 with mixed ordered alkali cations displaying excellent infrared nonlinear optical properties16Giant in-plane optical and electronic anisotropy of tellurene: a quantitative exploration25Hexameric poly-fluoroberyllophosphate Na 4 Be 2 PO 4 F 5 with moderate birefringence and deep-ultraviolet transmission as a potential zero-order-waveplate crystal17Hg 2 (SeO 3 )(SO 4 ): the first sulfate selenite with large birefringence explored from d 10 transition metal compounds36K 2 S 4 O 6 : improving birefringence and nonlinear optical properties with the [O 3 S–S–S–SO 3 ] 2− group5KPb 3 ( o -C 5 H 4 NCOO) 2 Cl 5 : a brand-new stable lead chloride with good comprehensive nonlinear optical performance5Li-Free ternary sulphide Cs 5 Ga 9 S 16 with excellent nonlinear optical performance similar to classic LiGaS 213Nain(C2o4)(Hpo4)(H2o)5: An Ultraviolet Transparent Nonlinear Optical Oxalate-Phosphate with Large Birefringence0Synergistic effect of 2 [V 2 P 2 O 14 ] ∞ layers and hydrogen bonds inducing large birefringence in M(VO) 2 (PO 4 ) 2 ·4H 2 O (M = Ca, Sr, Ba) systems4Wide bandgaps and strong SHG responses of hetero-oxyfluorides by dual-fluorination-directed bandgap engineering28High‐Performance Sulfate Optical Materials Exhibiting Giant Second Harmonic Generation and Large Birefringence21High‐Performance Sulfate Optical Materials Exhibiting Giant Second Harmonic Generation and Large Birefringence199Lead Tellurite Crystals BaPbTe2O6 and PbVTeO5F with Large Nonlinear-/Linear-Optical Responses due to Active Lone Pairs and Distorted Octahedra20Switching the Nonlinear Optical Absorption of Titanium Carbide MXene by Modulation of the Surface Terminations106Crystal Structure and Theoretical Analysis of Cs2Ca3(SO4)47Synthesis, linear and non-linear optical properties of “push-pull” chromophores based on 9,9-dimethyl-9H-fluoren-2-amine10Explorations of New SHG Materials in Mercury Iodate Sulfate System**9Two Indium Iodate–Nitrates with Large Birefringence Induced by Hybrid Anionic Functional Groups and Their Favorable Arrangements22Advances in second-order nonlinear optical sulfates38CsY(SO4)2·4H2O: A Deep-Ultraviolet Birefringent Crystal Induced by an Edge-Sharing Connection26Strong Nonlinearity Induced by Coaxial Alignment of Polar Chain and Dense [BO3] Units in CaZn2(BO3)212Strong Nonlinearity Induced by Coaxial Alignment of Polar Chain and Dense [BO3] Units in CaZn2(BO3)2212Ultrawide Bandgap and Outstanding Second‐Harmonic Generation Response by a Fluorine‐Enrichment Strategy at a Transition‐Metal Oxyfluoride Nonlinear Optical Material51Ultrawide Bandgap and Outstanding Second‐Harmonic Generation Response by a Fluorine‐Enrichment Strategy at a Transition‐Metal Oxyfluoride Nonlinear Optical Material12Synthesis, Crystal and Electronic Structures, and Nonlinear Optical Properties of Y4Si3S1212Cs2Bi2OSi2O7: A Promising Bismuth Silicate Nonlinear Optical Crystal with Face-Sharing BiO5 Polyhedra Exhibiting Strengthened Second Harmonic Generation Response and Birefringence43Enhanced Second-Harmonic-Generation Efficiency and Birefringence in Melillite Oxychalcogenides Sr2MGe2OS6 (M = Mn, Zn, and Cd)97Noncentrosymmetric Rare-Earth Borate Fluoride La2B5O9F3: A New Ultraviolet Nonlinear Optical Crystal with Enhanced Linear and Nonlinear Performance48Maximizing the linear and nonlinear optical responses of alkaline tricyanomelaminate28An Optimized KBe2BO3F2‐Like Structure: The Unity of Deep‐Ultraviolet Transparency, Nonlinear Optical Property, and Ferroelectricity22Cooperative Enhancement of Second Harmonic Generation in an Organic–Inorganic Hybrid Antimony Halide63Enhancement of Birefringence in Borophosphate Pushing Phase-Matching into the Short-Wavelength Region150The Kurtz-Perry powder technique revisited: A case study on the importance of reference quality and broadband nonlinear optical measurements using LiInSe232Modulating Two Pairs of Chiral Dy III Enantiomers by Distinct β-Diketone Ligands to Show Giant Differences in Single-Ion Magnet Performance and Nonlinear Optical Response35Cation-anion synergetic interactions achieving tunable birefringence in quasi-one-dimensional antimony(III) fluoride oxalates58Additive‐Triggered Polar Polymorph Formation: β‐Sc(IO 3 ) 3 , a Promising Next‐Generation Mid‐Infrared Nonlinear Optical Material42Additive‐Triggered Polar Polymorph Formation: β‐Sc(IO3)3, a Promising Next‐Generation Mid‐Infrared Nonlinear Optical Material3[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 Orbitals22A Hybrid Antiperovskite with Strong Linear and Second‐Order Nonlinear Optical Responses15A Hybrid Antiperovskite with Strong Linear and Second‐Order Nonlinear Optical Responses96Design of a new ultraviolet nonlinear optical material KNO3SO3NH3 exhibiting an unexpected strong second harmonic generation response44Three polar indium phosphites exhibiting diverse structural networks and SHG-activity9Organic–Inorganic Hybrid Antimony(III) Halides for Second Harmonic Generation34SbHPO3F: 2D van der Waals Layered Phosphite Exhibiting Large Birefringence32ZrF2(IO3)2 and RbGaF3(IO3): Two Promising Birefringent Crystals Featuring 1D Metal-Fluoride Cationic Chains and Wide Bandgaps22AIB3IIC3IIIQ8VI: A New Family for the Design of Infrared Nonlinear Optical Materials by Coupling Octahedra and Tetrahedra Units152(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 Cation-Driven Approach toward Deep-Ultraviolet Nonlinear Optical Materials17A pair of ionic 1D Cu( ii ) chain enantiomers simultaneously displaying large second- and third-harmonic generation responses12Accurate design and synthesis of nonlinear optical crystals employing KBe2BO3F2 as structural template55Ce 3 F 4 (SO 4 ) 4 : cationic framework assembly for designing polar nonlinear optical material through fluorination degree modulation23Enhancing birefringence of non-π-conjugated sulfate systems through rare-earth metal-centered polyhedra10From H 12 C 4 N 2 CdI 4 to H 11 C 4 N 2 CdI 3 : a highly polarizable CdNI 3 tetrahedron induced a sharp enhancement of second harmonic generation response and birefringence50Two pairs of chiral Yb III enantiomers presenting distinct NIR luminescence and circularly polarized luminescence performances with giant differences in second-harmonic generation responses20Two temperature-induced 1D Cu II chain enantiomeric pairs showing different magnetic properties and nonlinear optical responses14β-(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 groups35Intense d‐p Hybridization in Nb3O15 Tripolymer Induced the Largest Second Harmonic Generation Response and Birefringence in Germanates51Intense d‐p Hybridization in Nb3O15 Tripolymer Induced the Largest Second Harmonic Generation Response and Birefringence in Germanates7Toward Large Second-Harmonic Generation and Deep-UV Transparency in Strongly Electropositive Transition Metal Sulfates112A Rare‐Earth Selenite with Unexpectedly Well‐Balanced Ultraviolet Nonlinear Optical Functionality, Sc(HSeO 3 ) 331Recent Development of Sn II , Sb III ‐based Birefringent Material: Crystal Chemistry and Investigation of Birefringence130Recent Development of SnII, SbIII‐based Birefringent Material: Crystal Chemistry and Investigation of Birefringence6Two Mixed-Alkali-Metal Selenates as Short-Wave Ultraviolet Nonlinear-Optical Materials10Nonlinear optical crystals KPb3(3-C5H4NCOO)2Br5 and KPb3(3-C5H4NCOO)2Cl3Br2 with new Pb-centered nitrogen-halide polyhedrons obtained by the halide anionic substitution4Host–Guest Symmetry Matching in Two Crystalline Magnesium Sulfate Oxalates Obtained Via a Solvent-Free Route8Four New Sb‐based Orthophosphates: Cation Regulation to Investigate Diversified Structural Architecture1Remarkable phase-matchable second-harmonic generation realized by strong polarities of [PbSe3] and [GaSe4] functional motifs in PbGa4Se718Sb4O3(TeO3)2(HSO4)(OH): An Antimony Tellurite Sulfate Exhibiting Large Optical Anisotropy Activated by Lone Pair Stereoactivity30A solution processible single-crystal porous organic polymer55Theoretical Prediction‐Assisted Synthesis and Characterization of Infrared Nonlinear Optical Material NaSrBS324A BBO-like trithiocyanate with significantly enhanced birefringence and second-harmonic generation39A Hydrogen Bonded Supramolecular Framework Birefringent Crystal89A Hydrogen Bonded Supramolecular Framework Birefringent Crystal13Host–Guest Symmetry and Charge Matching in Glycine-Templated Metal Sulfate–Oxalates Obtained by a Solvent-Free Method9Hg3(SeO3)2(SO4): A UV Nonlinear Optical Mercury Selenite Sulfate Constructed by Neat [Hg6O8(SeO3)4]∞ Layers and SO4 Tetrahedra27Li2.9Cs1.1(SO4)2: An Ultraviolet Transparent Sulfate as a Nonlinear Optical Crystal16Quartz‐Like Structure, Optical Activity, and High Stability in the First Chiral Cation‐Coordinated Perovskite Semiconductor11Improved Birefringence Activated by Tetrahedra Decorated with a Single Linear Unit38Improved Birefringence Activated by Tetrahedra Decorated with a Single Linear Unit1Fluorooxoborate Promoting the Exploration of Short-Wavelength Linear and Nonlinear Optical Crystals with Expected Properties and Versatile Structures27Cs4Zn5P6S18I2: the Largest Birefringence in Chalcohalide Achieved by Highly Polarizable Nonlinear Optical Functional Motifs21Nonlinear optical inorganic sulfates: The improvement of the phase matching ability driven by the structural modulation41Quadruple‐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 Birefringence2Ce(IO3)3F and Ce(IO3)2(NO3): Two Mixed-Anion Cerium Iodates with Good Nonlinear Optical and Birefringent Properties14YSO4F·H2O: A Deep-Ultraviolet Birefringent Rare-Earth Sulfate Fluoride with Enhanced Birefringence Induced by Fluorinated Y-Centered Polyhedra19Design, Synthesis, Crystal Structure, and Thermal Studies of Ni0.779SbF3(SO4): A New Electrode Material for Electrochemical Supercapacitors8Sr(NH2SO3)(NO3)·H2O: An Ultraviolet Nonlinear Optical Material Exhibiting Strong Second-Harmonic Generation Response and Sufficient Birefringence10Designing Sulfate Crystals with Strong Optical Anisotropy through π‐Conjugated Tailoring51Designing Sulfate Crystals with Strong Optical Anisotropy through π‐Conjugated Tailoring11Ultrashort Phase‐Matching Wavelength and Strong Second‐Harmonic Generation in Deep‐UV‐Transparent Oxyfluorides by Covalency Reduction33Ultrashort Phase‐Matching Wavelength and Strong Second‐Harmonic Generation in Deep‐UV‐Transparent Oxyfluorides by Covalency Reduction3Na 10 Zn(NO 3 ) 4 (SO 3 S) 4 : a nonlinear optical crystal combining inorganic π-conjugated and non-π-conjugated heteroanion groups8Na 2 CeF 6 : A Highly Laser Damage‐Tolerant Double Perovskite Type Ce(IV) Fluoride Exhibiting Strong Second‐Harmonic Generation Effect30A2Hgx(SeO3)y (A = K, Rb, Cs): Three Alkali Metal Mercury Selenites Featuring Unique 1D [HgOm(SeO3)n]∞ Chains13Rational Design of the Alkali Metal Sn‐Based Mixed Halides with Large Birefringence and Wide Transparent Range44Synthesis, crystal and electronic structures, linear and nonlinear optical properties, and photocurrent response of oxyhalides CeHaVIO 4 (Ha = Cl, Br; VI = Mo, W)10Secondary‐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 Birefringence41“Three‐in‐One”: A New Hg‐Based Selenide Hg 7 P 2 Se 12 Exhibiting Wide Infrared Transparency Range and Strong Nonlinear Optical Effect80A chiral sodium lanthanum sulfate for second-order nonlinear optics and proton conduction6Equivalent cation-tuning to realize a new Ce( iv ) fluoride with excellent comprehensive nonlinear optical performances12Large optical anisotropy in noncentrosymmetric phosphate with pseudo 2D intercalated layer16N 2 H 4 Zn(HC 3 N 3 O 3 ): exceptionally strong second harmonic generation and ultra-long phosphorescence16Novel cesium cerium( iv ) iodate Cs 2 Ce(IO 3 ) 6 : hydrothermal synthesis, crystal structures and thermal stability2Pb 2 Ga 3 F 6 (SeO 3 ) 2 X 3 ·2H 2 O (X = Cl, Br): two new HTO-type members exhibiting large NLO effects mediated by ionic mixing and substitution strategies10Giant Optical Anisotropy in a Covalent Molybdenum Tellurite via Oxyanion Polymerization43AYSO4F2 (A = K, Rb): [YO4F4] Polyhedra Enhancement of Birefringence in Non-π-Conjugated Sulfate Systems9Record Second-Harmonic Generation and Birefringence in an Ultraviolet Antimonate by Bond Engineering157

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