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RESEARCH PAPER · Journal of the American Chemical Society · 2012

A New Mixed Halide, Cs2HgI2Cl2: Molecular Engineering for a New Nonlinear Optical Material in the Infrared Region

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A New Mixed Halide, Cs2HgI2Cl2: Molecular Engineering for a New Nonlinear Optical Material in the Infrared RegionOriginalA promising nonlinear optical material in the Mid-IR region: new results on synthesis, crystal structure and properties of noncentrosymmetric β-HgBrCl36BaClBF4: a new noncentrosymmetric pseudo-Aurivillius type material with transparency range from deep UV to middle IR and a high laser damage threshold42First principles selection and design of mid-IR nonlinear optical halide crystals132Hg2Br3I: a new mixed halide nonlinear optical material in the infrared region28New compounds and structures in the solid state0Pb2TiOF(SeO3)2Cl and Pb2NbO2(SeO3)2Cl: small changes in structure induced a very large SHG enhancement117ChemInform Abstract: A New Mixed Halide, Cs2HgI2Cl2: Molecular Engineering for a New Nonlinear Optical Material in the Infrared Region.0New Fluoride Carbonates: Centrosymmetric KPb2(CO3)2F and Noncentrosymmetric K2.70Pb5.15(CO3)5F367HgBrI: A promising nonlinear optical material in IR region18Deep-Ultraviolet Nonlinear Optical Crystals: Ba3P3O10X (X = Cl, Br)459A promising new nonlinear optical crystal with high laser damage threshold for application in the IR region: synthesis, crystal structure and properties of noncentrosymmetric CsHgBr 327Computational design of inorganic nonlinear optical crystals based on a genetic algorithm93Exploration of new second-order nonlinear optical materials of the Cs–Hg–Br–I system35Rb2CdBr2I2: A New IR Nonlinear Optical Material with a Large Laser Damage Threshold154First-principles materials applications and design of nonlinear optical crystals259Role of Acentric Displacements on the Crystal Structure and Second-Harmonic Generating Properties of RbPbCO3F and CsPbCO3F90Beryllium-free Li4Sr(BO3)2 for deep-ultraviolet nonlinear optical applications462Ag 3 Ga 3 SiSe 8 : a new infrared nonlinear optical material with a chalcopyrite structure34Strong SHG responses predicted in binary metal halide crystal HgI215Development of nonlinear optical materials promoted by density functional theory simulations32Syntheses, Structures, and Nonlinear-Optical Properties of Metal Sulfides Ba2Ga8MS16 (M = Si, Ge)94A study on K 2 SbF 2 Cl 3 as a new mid-IR nonlinear optical material: new synthesis and excellent properties55Recent advances on second-order NLO materials based on metal iodates328Electronic structure and optical properties of Cs2HgI4: Experimental study and band-structure DFT calculations29Tailored Synthesis of a Nonlinear Optical Phosphate with a Short Absorption Edge241Tailored Synthesis of a Nonlinear Optical Phosphate with a Short Absorption Edge60Strong IR NLO Material Ba4MGa4Se10Cl2: Highly Improved Laser Damage Threshold via Dual Ion Substitution Synergy97Pb17O8Cl18: A Promising IR Nonlinear Optical Material with Large Laser Damage Threshold Synthesized in an Open System223Metal Thiophosphates with Good Mid-infrared Nonlinear Optical Performances: A First-Principles Prediction and Analysis441[A 3 X][Ga 3 PS 8 ] (A = K, Rb; X = Cl, Br): promising IR non-linear optical materials exhibiting concurrently strong second-harmonic generation and high laser induced damage thresholds189RbIO3 and RbIO2F2: Two Promising Nonlinear Optical Materials in Mid-IR Region and Influence of Partially Replacing Oxygen with Fluorine for Improving Laser Damage Threshold124The structure and band gap design of high Si doping level Ag1−xGa1−xSixSe2 (x=1/2)15Electronic, Crystal Chemistry, and Nonlinear Optical Property Relationships in the Dugganite A3B3CD2O14 Family148Na 2 Hg 3 M 2 S 8 (M = Si, Ge, and Sn): New Infrared Nonlinear Optical Materials with Strong Second Harmonic Generation Effects and High Laser-Damage Thresholds186Na 2 ZnGe 2 S 6 : A New Infrared Nonlinear Optical Material with Good Balance between Large Second-Harmonic Generation Response and High Laser Damage Threshold302Crystalline Mixed Halide Halobismuthates and Their Induced Second Harmonic Generation63Top-Seeded Solution Crystal Growth, Morphology, Optical and Thermal Properties of Ba3(ZnB5O10)PO442A High Laser Damage Threshold and a Good Second-Harmonic Generation Response in a New Infrared NLO Material: LiSm3SiS725Recent studies of nonlinear chalcogenide crystals for the mid-IR148Cooperation of Three Chromophores Generates the Water‐Resistant Nitrate Nonlinear Optical Material Bi3TeO6OH(NO3)2113Cooperation of Three Chromophores Generates the Water‐Resistant Nitrate Nonlinear Optical Material Bi3TeO6OH(NO3)220Non‐centrosymmetric Selenides AZn4In5Se12 (A=Rb, Cs): Synthesis, Characterization and Nonlinear Optical Properties47Recent achievements on middle and far-infrared second-order nonlinear optical materials433Li 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 photoluminescence54The activity of lone pair contributing to SHG response in bismuth borates: a combination investigation from experiment and DFT calculation28Theoretical perspectives on the structure, electronic, and optical properties of titanosilicates Li 2 M 4 [(TiO)Si 4 O 12 ] (M = K + , Rb + )13Two excellent phase-matchable infrared nonlinear optical materials based on 3D diamond-like frameworks: RbGaSn 2 Se 6 and RbInSn 2 Se 639Wide band gap design of new chalcogenide compounds: KSrPS 4 and CsBaAsS 422Superpolyhedron-Built Second Harmonic Generation Materials Exhibit Large Mid-Infrared Conversion Efficiencies and High Laser-Induced Damage Thresholds101An alkaline tin(II) halide compound Na 3 Sn 2 F 6 Cl: Synthesis, structure, and characterization10Structure and Characterization of a Zero-Dimensional Alkali Tin Dihalides Compound Cs3Sn3F2Cl7 with the [Sn2F2Cl4]2– Clusters13Li2HgMS4 (M = Si, Ge, Sn): New Quaternary Diamond-Like Semiconductors for Infrared Laser Frequency Conversion64Synthesis, Crystal Structure and Nonlinear Optical Property of RbHgI319Coexistence of Strong Second Harmonic Generation Response and Wide Band Gap in AZn4Ga5S12 (A=K, Rb, Cs) with 3D Diamond‐like Frameworks65ABi2(IO3)2F5 (A=K, Rb, and Cs): A Combination of Halide and Oxide Anionic Units To Create a Large Second‐Harmonic Generation Response with a Wide Bandgap140ABi2(IO3)2F5 (A=K, Rb, and Cs): A Combination of Halide and Oxide Anionic Units To Create a Large Second‐Harmonic Generation Response with a Wide Bandgap36Synthesis and characterization of two lead-containing metal chalcogenides: Ba5Pb2Sn3S13 and Ba6PbSn3Se137LiGaGe2S6: A Chalcogenide with Good Infrared Nonlinear Optical Performance and Low Melting Point56Structural Evolution in BaSn2F5X (X = Cl, Br, I): A Family of Alkaline Earth Metal Tin Mixed Halides15Nonlinear Optical Crystal Rb 4 Sn 3 Cl 2 Br 8 : Synthesis, Structure, and Characterization32First principle study of nonlinear optical crystals15Four new quaternary chalcogenides A 2 Ba 7 Sn 4 Q 16 (A = Li, Na; Q = S, Se): syntheses, crystal structures determination, nonlinear optical performances investigation26K 2 MnGe 3 S 8 : a new multifunctional semiconductor featuring [MnGe 3 S 8 ] 2− layers and demonstrating interesting nonlinear optical response and antiferromagnetic properties33Na 6 Zn 3 MIII2Q 9 (M III = Ga, In; Q = S, Se): four new supertetrahedron-layered chalcogenides with unprecedented vertex-sharing T 3 -clusters and desirable photoluminescence performances31Oxyhalides: prospecting ore for optical functional materials with large laser damage thresholds76Pb 3 (SeO 3 )Br 4 : a new nonlinear optical material with enhanced SHG response designed via an ion-substitution strategy36Structural insights into T 2 -cluster-containing chalcogenides with vertex-, edge- and face-sharing connection modes of NaQ 6 ligands: Na 3 ZnM III Q 4 (M III = In, Ga; Q = S, Se)13From AgGaS2 to Li2ZnSiS4: Realizing Impressive High Laser Damage Threshold Together with Large Second-Harmonic Generation Response134Non-Centrosymmetric RbNaMgP 2 O 7 with Unprecedented Thermo-Induced Enhancement of Second Harmonic Generation239Pushing Nonlinear Optical Oxides into the Mid-Infrared Spectral Region Beyond 10 μm: Design, Synthesis, and Characterization of La3SnGa5O14145Second-order nonlinear optical crystals with mixed anions250Synthesis, crystal structures and nonlinear optical properties of polymorphism: α- and β-RbHgI3·H2O18A review on structure-performance relationship toward the optimal design of infrared nonlinear optical materials with balanced performances253Recent advances and future perspectives on infrared nonlinear optical metal halides223Ba 4 Bi 2 (Si 8−x B 4+x O 29 ) ( x = 0.09): a new acentric metal borosilicate as a promising nonlinear optical material53ABaSbQ 3 (A = Li, Na; Q = S, Se): diverse arrangement modes of isolated SbQ 3 ligands regulating the magnitudes of birefringences50Investigation on two new antimony-based quaternary chalcogenides: Na 6 CdSb 4 S 10 and Na 3 CdSbSe 41Synthesis, crystal structures and nonlinear optical properties of β-RbCdI 3 ·H 2 O and CsCdI 3 ·H 2 O8ASbF3Cl (A = Rb, Cs): Structural Evolution from Centrosymmetry to Noncentrosymmetry16The first barium lead oxychloride Ba27Pb8O8Cl54 with new isolated [Pb4O4] clusters3Bent HgI2 Molecules in the Melt and Sulfide Glasses: Implications for Nonlinear Optics20Mixed-Anion Inorganic Compounds: A Favorable Candidate for Infrared Nonlinear Optical Materials140Cs2Bi2O(Ge2O7) (CBGO): A Larger SHG Effect Induced by Synergistic Polarizations of BiO5 Polyhedra and GeO4 Tetrahedra73Cs2Bi2O(Ge2O7) (CBGO): A Larger SHG Effect Induced by Synergistic Polarizations of BiO5 Polyhedra and GeO4 Tetrahedra18Effect of DFT methods on electronic structure and K-absorption spectra of InPS4: detailed studies of the optical, thermoelectric and elastic properties4K5(W3O9F4)(IO3): An Efficient Mid-Infrared Nonlinear Optical Compound with High Laser Damage Threshold114A review of the AI2B II C IV DVI4 family as infrared nonlinear optical materials: the effect of each site on the structure and optical properties59From BiF 3 to BiF 3 ·H 2 O: diverse Bi( iii ) coordination for structural transformation and birefringence regulation14In[Ba 3 Cl 3 F 6 ]: a novel infrared-transparent molecular sieve constructed by halides6Synthesis and crystal structure of copper(I) halide complexes with 1-allyl-4-cyanopyridinium cation0Lead Mixed Oxyhalides Satisfying All Fundamental Requirements for High‐Performance Mid‐Infrared Nonlinear Optical Materials164Lead Mixed Oxyhalides Satisfying All Fundamental Requirements for High‐Performance Mid‐Infrared Nonlinear Optical Materials55A Series of Organic–Inorganic Hybrid Compounds [(C2H5)4N]InCl4–xBrx (x = 0, 2, 4): Synthesis, Crystal Structure, and Nonlinear Optical Properties37A review on phase transition and structure-performance relationship of second-order nonlinear optical polymorphs107Inherent laws between tetrahedral arrangement pattern and optical performance in tetrahedron-based mid-infrared nonlinear optical materials131Structural Evolution and Optical Property Tunability by Halogen Substitution in [N(CH3)4]MX2 (M = Ga+, In+, X = Cl, Br): A Family of Organically Templated Metal Halides8Pb 18 O 8 Cl 15 I 5 : A Polar Lead Mixed Oxyhalide with Unprecedented Architecture and Excellent Infrared Nonlinear Optical Properties166Pb18O8Cl15I5: A Polar Lead Mixed Oxyhalide with Unprecedented Architecture and Excellent Infrared Nonlinear Optical Properties29Recent Advances in Oxide‐based Nonlinear Optical Materials with Wide Infrared Transparency Beyond 6 μm38Ba(MoO2F)2(XO3)2 (X = Se and Te): First Cases of Noncentrosymmetric Fluorinated Molybdenum Oxide Selenite/Tellurite Through Unary Substitution for Enlarging Band Gaps and Second Harmonic Generation34Origin of ultra-wide IR transmission and ultra-large birefringence of mercurous halide series with one dimensional chain-like structure: An ab initio study15Balanced infrared nonlinear optical performance achieved by modulating the covalency and ionicity distributions in the electron localization function map42K 3 Na(TaF 7 )(SiF 6 ): a mixed-anion pentanary fluoride with zero-dimensional anions exhibiting a large band gap14Halonitrides Zn 2 NX (X=Cl,Br): Novel Mid-Infrared Nonlinear Optical Materials30Acentric Organic–Inorganic Hybrid Halide [N(CH3)4]2HgBr2I2 Featuring an Isolated [HgBr2I2]2– Tetrahedron and Second-Order Nonlinearity18Hierarchical molecular design of high-performance infrared nonlinear Ag2HgI4 material by defect engineering strategy128AXHg3P2S8 (A = Rb, Cs; X = Cl, Br): New Excellent Infrared Nonlinear Optical Materials with Mixed‐Anion Chalcohalide Groups of Trigonal Planar [HgS2X]3− and Tetrahedral [HgS3X]5−58Tin‐Based Chiral Perovskites with Second‐Order Nonlinear Optical Properties51A3Te(Zn2Ge)Ge2O14 (A = Sr, Ba, and Pb): New Langasite Mid-infrared Nonlinear Optical Materials by Rational Chemical Substitution32Dimensionality reduction made high-performance mid-infrared nonlinear halide crystal74Noncentrosymmetric chalcohalide K2Ba3Ge3S9Cl2: A new nonlinear optical material with remarkable laser-induced damage threshold17Recent Development of Non-π-Conjugated Deep Ultraviolet Nonlinear Optical Materials106AAg 3 Ga 8 Se 14 (A = Rb, Cs): second-harmonic generation responses realized through the parallel arrangement of AgSe 4 and GaSe 4 tetrahedrons5AIn 4 S 6 Cl (A = Rb and Cs) and Pb 5 Sn 3 Q 10 Cl 2 (Q = S and Se): quaternary chalcohalides with mixed anionic coordination exhibit photocurrent responses11Broad transparency and wide band gap achieved in a magnetic infrared nonlinear optical chalcogenide by suppressing d–d transitions41K6Sn4F12I2•0.5H2O: a zero-dimensional alkali metal tin mixed halide compound exhibiting color change due to crystal water loss0Metal oxyhalides: an emerging family of nonlinear optical materials124HgTeO2F(OH): A Nonlinear Optical Oxyfluoride Constructed of Active [TeO2F(OH)]2– Pyramids and V-Shaped [HgO2]2– Groups36Material research from the viewpoint of functional motifs103Frequency Down-Conversion of Optical Pulse to the Far Infrared and THz Frequency Ranges Due to the Cascading Process in a Medium with a Quadratic Nonlinear Response2Mid-Infrared Nonlinear Optical Halides with Diamond-like Structures: A Theoretical and Experimental Study44From CsKTaF7 to CsNaTaF7: Alkali Metal Cations Regulation to Generate SHG Activity**22[Ba2F2][Ge2O3S2]: An Unprecedented Heteroanionic Infrared Nonlinear Optical Material Containing Three Typical Anions47Ternary AGa5S8 (A = K, Rb, Cs): Promising infrared nonlinear optical materials rationally realized by “one-for-multiple substitution” strategy37LiAlS2: A promising infrared frequency-conversion material with ultrawide band gap and high laser-induced damage threshold19From Ba3Nb2O2F12(H2O)2 to Ba0.5NbO2F2(H2O): Achieving Balanced Nonlinear Optical Performance by O/F Ratio Regulation18Enhancing second harmonic generation response in infrared nonlinear optical material through Pb substitution: A study of LiPbSiS compound2Na 2 CeF 6 : A Highly Laser Damage‐Tolerant Double Perovskite Type Ce(IV) Fluoride Exhibiting Strong Second‐Harmonic Generation Effect30Photoluminescence and Nonlinear Optical Properties of Two Terpyridine-Based Hybrid Zn/Cd Halides25Rational Design of the Alkali Metal Sn‐Based Mixed Halides with Large Birefringence and Wide Transparent Range45Equivalent cation-tuning to realize a new Ce( iv ) fluoride with excellent comprehensive nonlinear optical performances12HgBr 2 : an easily growing wide-spectrum birefringent crystal38KBa 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 moieties37Theoretical Investigation of Structural, Electronic and Optical Properties of Cs3MoO4(HCO3) with NLO Active Functional Units2Theoretical insight on structure, electronic, and optical properties of two d 0–d 10 electron transition-metal oxyhalides SHG materials2The centrosymmetric to non-centrosymmetric transformation induced by alkaline-earth cations producing infrared nonlinear optical AeMn6Ga6S16 (Ae = Ca, Sr)13Novel antimony-based mixed halides exhibiting an excellent SHG response and a broad transmission range20Emergent Mid‐Infrared Nonlinear Optical Candidates With Targeted Balance Performances18Enhanced second harmonic generation in a Fdd 2 polymorph of C 12 H 8 N 2 O 4 Zn for UV nonlinear optical applications1(NH 4 ) 2 Cd 2 Cl 3 F 3 and (NH 4 ) 2 Cd 2 Br 3 F 3 : The First Fluoride‐Containing d 10 Metal Mixed Halides Exhibiting Superior Ultraviolet Nonlinear Optical Properties29One-Dimensional Perovskite RbGeI3 with Large Optical Anisotropy3From AgHgI(SO4) to AgHg3I3.2Cl1.8(SO4): Symmetry Breaking of the Belousovite‐Type Topology by Mixed Halides to Achieve Strong Nonlinear Optical Effect14[HgX 2 ] Linear Group Enabled Ultraviolet Birefringent Crystal RbHg 5 Br 11 with Strong Optical Anisotropy and Wide Bandgap12Solution-Grown Cs2HgI4 Bulk Crystals: Achieving Strong SHG and High Damage Threshold Synergistically for IR Nonlinear Optics1Laporte Selection Rule Induced the Suppression of d ‐ d Transitions and Vacancies Enhanced the Second Harmonic Generation in I 4¯‐MnGa 2 S 40

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