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RESEARCH PAPER · Journal of the American Chemical Society · 2012

Strong Kleinman-Forbidden Second Harmonic Generation in Chiral Sulfide: La 4 InSbS 9

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Strong Kleinman-Forbidden Second Harmonic Generation in Chiral Sulfide: La 4 InSbS 9OriginalExploration of New Second-Order Nonlinear Optical Compounds Containing Main Group Elements4Synthesis, Crystal Structure, and Optical Properties of a Three-Dimensional Quaternary Hg–In–S–Cl Chalcohalide: Hg7InS6Cl539ChemInform Abstract: Strong Kleinman‐Forbidden Second Harmonic Generation in Chiral Sulfide: La4InSbS9.0Syntheses, Structures, Optical and Magnetic Properties of Ba2MLnSe5(M = Ga, In;Ln= Y, Nd, Sm, Gd, Dy, Er)54Sulfides with Strong Nonlinear Optical Activity and Thermochromism: ACd4Ga5S12 (A = K, Rb, Cs)172Ba3LnInS6 (Ln = Pr, Sm, Gd, Yb) and Ba2LnGaS5 (Ln = Pr, Nd): Syntheses, Structures, and Magnetic and Optical Properties35Syntheses, Structures, Physical Properties, and Electronic Structures of Ba2MLnTe5(M = Ga and Ln = Sm, Gd, Dy, Er, Y; M = In and Ln = Ce, Nd, Sm, Gd, Dy, Er, Y)38Molecular Germanium Selenophosphate Salts: Phase-Change Properties and Strong Second Harmonic Generation85Evolutionary search for BiInS3 crystal structure and predicting its second-order nonlinear optical property7Electronic Structures and Optical Properties of Organic DAST and DSTMS Crystal Materials6New compounds and structures in the solid state0Syntheses and characterizations of compounds Ba4F4XGa2S6 (X = Cr, Mn, Fe) and Ba4F4MnIn2S6 with 2D layered structures16Synthesis, structure, optical property, and electronic structure of Ba7AgGa5Se159Large Mid-IR Second-Order Nonlinear-Optical Effects Designed by the Supramolecular Assembly of Different Bond Types without IR Absorption33Functionalization Based on the Substitutional Flexibility: Strong Middle IR Nonlinear Optical Selenides AXII4XIII5Se12219Metal Chalcogenides: A Rich Source of Nonlinear Optical Materials680Bulk growth and physical properties of diguanidinium phosphate monohydrate (G2HP) as a multi-functional crystal41Deep-Ultraviolet Nonlinear Optical Crystals: Ba3P3O10X (X = Cl, Br)459New Quaternary Rare-Earth Chalcogenides BaLnSn2Q6 (Ln = Ce, Pr, Nd, Q = S; Ln = Ce, Q = Se): Synthesis, Structure, and Magnetic Properties30Synthesis, Structure and Bonding, Optical Properties of Ba4MTrQ6 (M=Cu, Ag; Tr=Ga, In; Q=S, Se)18Syntheses, structures, optical properties, and electronic structures of KBaMSe 3 (M = As, Sb)22Syntheses and characterization of one-dimensional alkali metal antimony(III) thiostannates(IV), A2Sb2Sn3S10 (A=K, Rb, Cs)21Syntheses, structures, and optical properties of Ba 4 Ga 4 SnSe 12 and Ba 6 Ga 2 SnSe 1119A series of lanthanoid selenidoantimonates( v ): rare examples of lanthanoid selenidoantimonates based on dinuclear lanthanide complexes19A series of new lanthanoid thioarsenates: insights into the influence of lanthanide contraction on the formation of new lanthanoid thioarsenates25Assembly of noncentrosymmetric coordination polymers by the integration of acentric Ba( ii )/Sr( ii ) and Li( i ) coordination polyhedra8Bulk crystal growth and characterization of semi-organic nonlinear optical crystal tri-diethylammonium hexachlorobismuthate (TDCB)36PbGa2MSe6 (M = Si, Ge): Two Exceptional Infrared Nonlinear Optical Crystals131A Series of Noncentrosymmetric Antimony Sulfides Ln8Sb2S15 (Ln = La, Pr, Nd) – Syntheses, Crystal and Electronic Structures, and NLO Properties26Recent advances on second-order NLO materials based on metal iodates328Syntheses, crystal structures, and NLO properties of the quaternary sulfides RE3Sb0.33SiS7 (RE=La, Pr)24Synthesis, Crystal, and Electronic Structure of Ba3Sb2Q7 (Q = S, Se)18Synthesis, crystal and electronic structure, and optical property of the pentanary chalcohalide Ba3KSb4S9Cl17Hydrazine-Hydrothermal Synthesis and Characterization of the Two New Quaternary Thioantimonates(III) BaAgSbS3 and BaAgSbS3·H2O40Metal Thiophosphates with Good Mid-infrared Nonlinear Optical Performances: A First-Principles Prediction and Analysis441Facile surfactant-thermal syntheses and characterization of quaternary copper thioantimonates(III) ACu 2 SbS 3 (A = K, Rb, Cs)23Synthesis, crystal structure, and optical property of the quaternary chalcohalide Ba4Sb3S8Cl14(Cs6Cl)6Cs3[Ga53Se96]: A Unique Long Period-Stacking Structure of Layers Made from Ga2Se6 Dimers via Cis or Trans Intralayer Linking12Centrosymmetry vs noncentrosymmetry in La2Ga0.33SbS5 and Ce4GaSbS9 based on the interesting size effects of lanthanides: Syntheses, crystal structures, and optical properties13Ba4Ga2Se8: A ternary selenide containing chains and discrete Se22− units14Synthesis of heterometallic chalcogenides containing lanthanide and group 13–15 metal elements94Syntheses and structural characterization of non-centrosymmetric Na2M2M'S6 (M, M′=Ga, In, Si, Ge, Sn, Zn, Cd) sulfides36Hydrazine-hydrothermal syntheses, characterizations and photoelectrochemical properties of two quaternary chalcogenidoantimonates(III) BaCuSbQ3 (Q = S, Se)51Strong Infrared NLO Tellurides with Multifunction: CsXII4In5Te12 (XII = Mn, Zn, Cd)58Na 2 BaMQ 4 (M=Ge, Sn; Q=S, Se): Infrared Nonlinear Optical Materials with Excellent Performances and that Undergo Structural Transformations202Na2BaMQ4 (M=Ge, Sn; Q=S, Se): Infrared Nonlinear Optical Materials with Excellent Performances and that Undergo Structural Transformations44Facile Hydrazine‐Hydrothermal Syntheses and Characterizations of Two Quaternary Thioarsenates(III): Two‐Dimensional SrAg4As2S6⋅2 H2O and One‐Dimensional BaAgAsS320Effect of alkali cations on two-dimensional networks of two new quaternary thioarsenates (III) prepared by a facile surfactant-thermal method13Quaternary non-centrosymmetric sulfide Y 4 GaSbS 9 : Syntheses, structures, optical properties and theoretical studies16Syntheses, structures, and properties of sulfides constructed by SbS 4 teeter-totter polyhedra: Ba 3 La 4 Ga 2 Sb 2 S 15 and BaLa 3 GaSb 2 S 1013Non‐centrosymmetric Selenides AZn4In5Se12 (A=Rb, Cs): Synthesis, Characterization and Nonlinear Optical Properties47Multitopic ligand directed assembly of low-dimensional metal-chalcogenide organic frameworks5Structural, optical, electrical properties of new hybrid organic–inorganic NLO single crystal: bis(1H-benzotriazole) hexaaqua-zinc bis(sulfate) tetrahydrate (BZS)18Recent achievements on middle and far-infrared second-order nonlinear optical materials433A novel 2-D Mn selenidostannate( iv ) incorporating high-nuclear Mn clusters with spin canting behavior8Band gap tuning from an indirect EuGa 2 S 4 to a direct EuZnGeS 4 semiconductor: syntheses, crystal and electronic structures, and optical properties20Li 2 CdGeSe 4 and Li 2 CdSnSe 4 : biaxial nonlinear optical materials with strong infrared second-order responses and laser-induced damage thresholds influenced by photoluminescence54Syntheses and characterization of three new sulfides with large band gaps: acentric Ba 4 Ga 4 SnS 12 , centric Ba 12 Sn 4 S 23 and Ba 7 Sn 3 S 1327Syntheses, structures, and thermoelectric properties of ternary tellurides: RECuTe 2 (RE = Tb–Er)26Tailored synthesis of nonlinear optical quaternary chalcohalides: Ba 4 Ge 3 S 9 Cl 2 , Ba 4 Si 3 Se 9 Cl 2 and Ba 4 Ge 3 Se 9 Cl 252Two excellent phase-matchable infrared nonlinear optical materials based on 3D diamond-like frameworks: RbGaSn 2 Se 6 and RbInSn 2 Se 639Two new phases in the ternary RE–Ga–S systems with the unique interlinkage of GaS 4 building units: synthesis, structure, and properties16Superpolyhedron-Built Second Harmonic Generation Materials Exhibit Large Mid-Infrared Conversion Efficiencies and High Laser-Induced Damage Thresholds101Noncentrosymmetric chalcogenides BaZnSiSe4 and BaZnGeSe4 featuring one-dimensional structures56Discovery-Synthesis, Design, and Prediction of Chalcogenide Phases208Mid-Infrared Nonlinear Optical Materials Based on Metal Chalcogenides: Structure–Property Relationship338Noncentrosymmetric rare-earth selenides RE4InSbSe9 (RE = La–Nd)11Synthesis, crystal structure, and optical properties of the noncentrosymmetric sulfide Ce 8 Sb 2 S 1512Pb@Pb8 Basket-like-Cluster-Based Lead Tellurate–Nitrate Kleinman-Forbidden Nonlinear-Optical Crystal: Pb9Te2O13(OH)(NO3)326Magnetically Frustrated Quaternary Chalcogenides with Interpenetrating Diamond Lattices18Experimental and theoretical studies on the NLO properties of two quaternary non-centrosymmetric chalcogenides: BaAg 2 GeS 4 and BaAg 2 SnS 468Synthesis, crystal growth, physio-chemical characterization and quantum chemical calculations of NLO active metal–organic crystal: dibromo(4-hydroxy- l -proline)cadmium( ii ) for non-linear optical applications10A Series of Lanthanide Selenidogermanates: The First Coexistence of Three Types of Selenidogermanate Units in the Same Architecture10Crystal Structure and Optical Property of Quaternary Sulfide Ba2.77SnSb2.16S80Ferroelectric Property, Switchable Dielectric, and Excellent Second Harmonic Generation Response in a Homochiral Organic Salt: l -Prolinammonium 1-Adamantane Carboxylate13Cu2EuMQ4 (M = Si, Ge; Q = S, Se): Syntheses, structure study and physical properties determination26Growth, effect of protonation and hydrogen bonding interactions of L-Histidine nitrate monohydrate, a potential semi organic third order nonlinear optical material21Solid-State Preparation, Structural Characterization, Physical Properties, and Theoretical Studies of a Series of Novel Rare-Earth Metal Chalcogenides with Unprecedented Closed-Cavities15ABaSbQ 3 (A = Li, Na; Q = S, Se): diverse arrangement modes of isolated SbQ 3 ligands regulating the magnitudes of birefringences50Centric-to-acentric structure transformation induced by a stereochemically active lone pair: a new insight for design of IR nonlinear optical materials90KBi(IO 3 ) 3 (OH) and NaBi(IO 3 ) 4 : from the centrosymmetric chain to a noncentrosymmetric double layer18Quaternary semiconductor Ba 8 Zn 4 Ga 2 S 15 featuring unique one-dimensional chains and exhibiting desirable yellow emission24Solid solutions of M 2−2x In 2x S 3 (M = Bi or Sb) by solventless thermolysis13Role of f Electrons in the Optical and Photoelectrochemical Behavior of Ca(La1–xCex)2S4 (0 ≤ x ≤ 1)3Large Second Harmonic Generation (SHG) Effect and High Laser‐Induced Damage Threshold (LIDT) Observed Coexisting in Gallium Selenide188Large Second Harmonic Generation (SHG) Effect and High Laser‐Induced Damage Threshold (LIDT) Observed Coexisting in Gallium Selenide48Synthesis, Crystal Structure, and Optical Property of Ce4InSbS91BaGe 2 Pn 2 (Pn = P, As): Two Congruent-Melting Non-chalcopyrite Pnictides as Mid- and Far-Infrared Nonlinear Optical Materials Exhibiting Large Second Harmonic Generation Effects54K5(W3O9F4)(IO3): An Efficient Mid-Infrared Nonlinear Optical Compound with High Laser Damage Threshold114Rational design of infrared nonlinear optical chalcogenides by chemical substitution287A highly distorted HgS 4 tetrahedron-induced moderate second-harmonic generation response of EuHgGeS 462Sr 4 Pb 1.5 Sb 5 O 5 Se 8 : a new mid-infrared nonlinear optical material with a moderate SHG response22Three diphosphates, α-Li 2 Na 2 P 2 O 7 , Li 8 Pb 3 Ba(P 2 O 7 ) 4 and Li 7 Rb(P 2 O 7 ) 2 : influences of co-substitution on the crystal structure9Tuning the Langasite, La 3 SbZn 3 Si 2 O 14 , towards white light emission: synthesis, structure, SHG and photoluminescence studies19One-Dimensional Chains in Pentanary Chalcogenides A2Ba3Cu2Sb2S10 (A = K, Rb, Cs) Displaying a Photocurrent Response44Enhancement of Second-Order Optical Nonlinearity in a Lutetium Selenite by Monodentate Anion Partial Substitution58Crystal chemistry, second-order nonlinear optical, and magnetic properties of Eu8Sn4Se2014Discovering Conglomerates for Chiral Resolution by Crystallization0First non-centrosymmetric antimony chalcogenides containing mixed cations of alkali and alkaline-Earth: Ba14Na4Sb11S31Cl3 featuring unique disorded 43 helical chains of [Sb5S18]21–5Chiral and SHG-Active Metal–Organic Frameworks Formed in Solution and on Surfaces: Uniformity, Morphology Control, Oriented Growth, and Postassembly Functionalization56Growth, Z-scan and density functional theoretical study for investigating the nonlinear optical properties of guanidinium l-glutamate for optical limiting applications17AMnAs3S6 (A = Cs, Rb): Phase-Matchable Infrared Nonlinear Optical Functional Motif [As3S6]3– Obtained via Surfactant–Thermal Method32Ba3[LiSbS2(S2)2Cl2]: The first zero-dimensional (0D) lithium metal thioantimonate featuring molecular anions of [LiSbS2(S2)2Cl2]6–3Stuffed Tridymite Structures: Synthesis, Structure, Second Harmonic Generation, Optical, and Multiferroic Properties14EuHgGeSe 4 and EuHgSnS 4 : Two Quaternary Eu-Based Infrared Nonlinear Optical Materials with Strong Second-Harmonic-Generation Responses55Recent Achievements in Lone-Pair Cation-Based Infrared Second-Order Nonlinear Optical Materials95Aliovalent-cation-substitution-induced structure transformation: a new path toward high-performance IR nonlinear optical materials47Breaking through the “3.0 eV wall” of energy band gap in mid-infrared nonlinear optical rare earth chalcogenides by charge-transfer engineering145Facile syntheses of silver thioantimonates exhibiting second-harmonic generation responses and large birefringence18From Ce(IO 3 ) 4 to CeF 2 (IO 3 ) 2 : fluorinated homovalent substitution simultaneously enhances SHG response and bandgap for mid-infrared nonlinear optics26La 12 Sb 9 S 38 : a new semiconducting lanthanum antimony polysulfide with a mixed La/Sb site4M 2 As 2 Q 5 (M = Ba, Pb; Q = S, Se): a source of infrared nonlinear optical materials with excellent overall performance activated by multiple discrete arsenate anions70Structural diversities in centrosymmetric La 8 S 4 Cl 8 La 12 S 8 Cl 4 [SbS 3 ] 8 and non-centrosymmetric Ln 12 S 8 Cl 8 [SbS 3 ] 4 (Ln = La and Ce): syntheses, crystal and electronic structures, and optical properties10A Series of Pentanary Salt-Inclusion Chalcogenoborates Containing a B12Q12 (Q = S, Se) Cluster Exhibiting a Kleinman-Forbidden Frequency-Doubling Effect25Ternary rare-earth sulfides RE3GaS6 (RE = Ho, Er): Crystal chemistry, second-order nonlinear optical properties and theoretical investigation18Inorganic Chalcogenides: From Zero‐Dimensional Clusters to Three‐Dimensional Frameworks5Ionothermal Synthesis of Two New Thioantimonates with Transition Metal Regulation4Rb2CuSb7S12: Quaternary Antimony-Rich Semiconductor Featuring a Three-Dimensional Open Framework and Exhibiting an Intriguing Photocurrent Response31Recent advances in nonlinear optical rare earth structures63Solvothermal Syntheses of Three-Dimensional Open-Framework Thioantimonates Displaying Nonlinear Optical Responses5The Rise of Infrared Nonlinear Optical Pnictides: Advances and Outlooks36Chalcogen dependent metal vacancies and disorder in Ba2Ln1−Mn2−S5 and Ba2−Ln1−Mn2−Se5 (Ln = Pr, Nd, and Gd) structures5From Cc to P 6 3 mc : Structural Variation in La 3 S 2 Cl 2 [SbS 3 ] and La 3 OSCl 2 [SbS 3 ] Induced by the Isovalent Anion Substitution22First-principles investigations of metal chalcogenides Tl2Hg3X4(X=S,Se,Te) for advanced optoelectronic and thermoelectric applications20RbBiP2S6: A Promising IR Nonlinear Optical Material with a Giant Second-Harmonic Generation Response Designed by Aliovalent Substitution80An Effective Strategy of Introducing Chirality to Achieve Multifunctionality in Rare‐Earth Double Perovskite Ferroelectrics34Organic Cation Modulation Triggered Second Harmonic Response in Manganese Halides with Bright Fluorescence46Analytical and numerical modeling of optical second harmonic generation in anisotropic crystals using ♯SHAARP package40KREP2Se6 (RE = Sm, Gd, Tb): The First Rare‐Earth Selenophosphates with Remarkable Nonlinear Optical Activities Realized by Synergistic Effect of RE‐ and P‐Based Motifs39Enlightening the stability and optoelectronic properties of Ba2MLnSe5 (M = Ga, In; Ln = Y, Nd, Sm, Gd, Dy, Er) semiconductors: A first-principles study3AIn 3 Si 4 P 9 (A = Ca, Sr): quaternary phosphides with double-helix structures exhibiting high laser-induced damage thresholds19[Ba 4 X][In 19 S 32 ] (X = Cl, Br): two quaternary metal chalcohalides exhibiting remarkable photocurrent responses1LaAeAl 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 ) 234Polar Phosphorus Chalcogenide Cage Molecules: Enhancement of Nonlinear Optical Properties in Adducts39Polar Phosphorus Chalcogenide Cage Molecules: Enhancement of Nonlinear Optical Properties in Adducts1Rational Design of a Rare‐Earth Oxychalcogenide Nd3[Ga3O3S3][Ge2O7] with Superior Infrared Nonlinear Optical Performance64Recent advances in IR nonlinear optical chalcogenides with well-balanced comprehensive performance57Magnetic, optoelectronic, and thermoelectric characteristics of Ln2MnSe4 (Ln = Yb, Lu) spinel chalcogenides: A DFT investigation19Three-dimensional nonlinear optical materials from twisted two-dimensional van der Waals interfaces53ACu4AsS4 (A = K, Rb): Two infrared nonlinear optical crystals with strong second-harmonic generation responses originating from multiple chromophores12Rare-earth-based chalcogenides and their derivatives: an encouraging IR nonlinear optical material candidate70SHG-active luminescent thermometers based on chiral cyclometalated dicyanidoiridate( iii ) complexes4Advances, optical and electronic applications of functional materials based on rare earth sulfide semiconductors26Mixed-anion square-pyramid [SbS3I2] units causing strong second-harmonic generation intensity and large birefringence9Infrared nonlinear optical materials with multiple strongly ionic cations5A Rare Earth Chalcogenide Nonlinear Optical Crystal KLaGeS4: Achieving Good Balance among Band Gap, Second Harmonic Generation Effect, and Birefringence13Linear Dichroism Conversion in Quasi‐1D Weyl Semimetal (TaSe4)2I Crystal with Giant Optical Anisotropy6LiLnGeS 4 (Ln=La−Nd): Designing High Performance Infrared Nonlinear Optical Sulfides through “Band Reformation of AGS”37LiLnGeS 4 (Ln=La−Nd): Designing High Performance Infrared Nonlinear Optical Sulfides through “Band Reformation of AGS”5

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