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RESEARCH PAPER · Journal of the American Chemical Society · 2012

Noncentrosymmetric Inorganic Open-Framework Chalcohalides with Strong Middle IR SHG and Red Emission: Ba3AGa5Se10Cl2 (A = Cs, Rb, K)

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Noncentrosymmetric Inorganic Open-Framework Chalcohalides with Strong Middle IR SHG and Red Emission: Ba3AGa5Se10Cl2 (A = Cs, Rb, K)OriginalCadmium-rare earth oxyborates Cd4ReO(BO3)3 (Re = Y, Gd, Lu): congruently melting compounds with large SHG responses65Cationic quaternary chalcohalide nanobelts: Hg4In2Q3Cl8 (Q = S, Se, Te)12Synthesis and characterization of cobalt(iii) cyanide complexes: cobalt participation in the decomposition of radical anion of TCNQ4ChemInform Abstract: Noncentrosymmetric Inorganic Open‐Framework Chalcohalides with Strong Middle IR SHG and Red Emission: Ba3AGa5Se10Cl2 (A: Cs, Rb, K).0A New Mixed Halide, Cs2HgI2Cl2: Molecular Engineering for a New Nonlinear Optical Material in the Infrared Region145Sulfides with Strong Nonlinear Optical Activity and Thermochromism: ACd4Ga5S12 (A = K, Rb, Cs)172Na3Cd3B(PO4)4: A New Noncentrosymmetric Borophosphate with Zero-Dimensional Anion Units81Role of Hydrogen-Bonding in the Formation of Polar Achiral and Nonpolar Chiral Vanadium Selenite Frameworks26CsHgInS3: a New Quaternary Semiconductor for γ-ray Detection60Ba6Sn6Se13: a new mixed valence selenostannate with NLO property50Ionothermal synthesis and characterization of two cluster chalcohalides: [Cr7S8Cl2(NH3)14.5(H2O)1.5]Cl3·H2O and [Emim]2[Sn2As2S4(S2)2Br2.43Cl1.56]28New compounds and structures in the solid state0Two phases of Ga2S3: promising infrared second-order nonlinear optical materials with very high laser induced damage thresholds288Cs2B4SiO9: A Deep‐Ultraviolet Nonlinear Optical Crystal278Cs2B4SiO9: A Deep‐Ultraviolet Nonlinear Optical Crystal224Designing a Deep-Ultraviolet Nonlinear Optical Material with a Large Second Harmonic Generation Response597New Metal Chalcogenides Ba4CuGa5Q12 (Q = S, Se) Displaying Strong Infrared Nonlinear Optical Response118Effect of Rigid Units on the Symmetry of the Framework: Design and Synthesis of Centrosymmetric NaBa4(B5O9)2F2Cl and Noncentrosymmetric NaBa4(AlB4O9)2Br350Large 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 Materials680Five New Chalcohalides, Ba3GaS4X (X = Cl, Br), Ba3MSe4Cl (M = Ga, In), and Ba7In2Se6F8: Syntheses, Crystal Structures, and Optical Properties50Quaternary Supertetrahedra-Layered Telluride CsMnInTe3: Why Does This Type of Chalcogenide Tilt?31Ba13Si6Sn8As22: A Quaternary Zintl Phase Containing Adamantane-Like [Si4As10] Clusters13Noncentrosymmetric Cubic CsCdBO3 with Bichromophore23Crystal growth and calculation of the electronic band structure and density of states of Li3Cs2B5O1013Deep-Ultraviolet Nonlinear Optical Crystals: Ba3P3O10X (X = Cl, Br)459Noncentrosymmetric chalcohalide NaBa 4 Ge 3 S 10 Cl with large band gap and IR NLO response104Synthesis, Structure and Bonding, Optical Properties of Ba4MTrQ6 (M=Cu, Ag; Tr=Ga, In; Q=S, Se)18Thermoelectric, band structure, chemical bonding and dispersion of optical constants of new metal chalcogenides Ba4CuGa5Q12 (Q=S, Se)4Ag 3 Ga 3 SiSe 8 : a new infrared nonlinear optical material with a chalcopyrite structure34Ba3GeS5 and Ba3InS4Cl: Interesting size effects originated from the tetrahedral anions26Solvothermal syntheses of lanthanide thiogermanates displaying three new structural moieties17Surfactant-Thermal Syntheses, Structures, and Magnetic Properties of Mn–Ge–Sulfides/Selenides45Synthesis, structures, optical properties and electronic structures of PbGa2Q4 (Q=S, Se) crystals13Synthesis and structural characterization of a new rubidium borosulfate, Rb5BS4O1616An investigation of new infrared nonlinear optical material: BaCdSnSe 4 , and three new related centrosymmetric compounds: Ba 2 SnSe 4 , Mg 2 GeSe 4 , and Ba 2 Ge 2 S 696Assembly of noncentrosymmetric coordination polymers by the integration of acentric Ba( ii )/Sr( ii ) and Li( i ) coordination polyhedra8Ba 2 GeS 4 and Mg 2 SnS 4 : synthesis, structures, optical properties and electronic structures41Second Harmonic Generation Response Optimized at Various Optical Wavelength Ranges through a Series of Cubic Chalcogenides Ba6Ag2.67+4δSn4.33−δS16–xSex41Mono and digallium selenide clusters as potential superhalogens8Strong IR NLO Material Ba4MGa4Se10Cl2: Highly Improved Laser Damage Threshold via Dual Ion Substitution Synergy97Syntheses, crystal structures, and NLO properties of the quaternary sulfides RE3Sb0.33SiS7 (RE=La, Pr)24Four new chalcohalides, NaBa2SnS4Cl, KBa2SnS4Cl, KBa2SnS4Br and CsBa2SnS4Cl: Syntheses, crystal structures and optical properties18Supercubooctahedron (Cs6Cl)2Cs5[Ga15Ge9Se48] Exhibiting Both Cation and Anion Exchange13Polar Polymorphism: α-, β-, and γ-Pb2Ba4Zn4B14O31–Synthesis, Characterization, and Nonlinear Optical Properties79Synthesis, crystal structure and optical property of a novel metal chalcohalide: ZnHg3Se2Cl47Pb2Ba3(BO3)3Cl: A Material with Large SHG Enhancement Activated by Pb-Chelated BO3 Groups279Synthesis, crystal and electronic structure, and optical property of the pentanary chalcohalide Ba3KSb4S9Cl17Metal Thiophosphates with Good Mid-infrared Nonlinear Optical Performances: A First-Principles Prediction and Analysis441Syntheses, crystal structures and physical properties of three new chalcogenides: NaGaGe 3 Se 8 , K 3 Ga 3 Ge 7 S 20 , and K 3 Ga 3 Ge 7 Se 2018Sm3S3BO3: The First Sulfide Borate without S–O and B–S Bonds46Synthesis, crystal and electronic structure, and optical properties of two new chalcogenide-iodides: Ba 3 Q 4 I 2 (Q = S, Se)5Synthesis, crystal structure, and optical property of the quaternary chalcohalide Ba4Sb3S8Cl14Bidenticity-Enhanced Second Harmonic Generation from Pb Chelation in Pb3Mg3TeP2O14169Crystal and electronic structures, and photoluminescence and photocatalytic properties of α-EuZrS 326KPb 2 (PO 3 ) 5 : a novel nonlinear optical lead polyphosphate with a short deep-UV cutoff edge109Pb 5 Ga 6 ZnS 15 : a noncentrosymmetric framework with chains of T2-supertetrahedra41Synthesis, crystal structure and second-order nonlinear optical property of a novel pentanary selenide (K 3 I)[InB 12 (InSe 4 ) 3 ]48The effect of indium substitution on the structure and NLO properties of Ba 6 Cs 2 Ga 10 Se 20 Cl 446(Cs6Cl)6Cs3[Ga53Se96]: A Unique Long Period-Stacking Structure of Layers Made from Ga2Se6 Dimers via Cis or Trans Intralayer Linking12Na 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 Thresholds186Hierarchical active factors to band gap and nonlinear optical response in Ag-containing quaternary-chalcogenide compounds9Strong Infrared NLO Tellurides with Multifunction: CsXII4In5Te12 (XII = Mn, Zn, Cd)58Na 2 ZnGe 2 S 6 : A New Infrared Nonlinear Optical Material with Good Balance between Large Second-Harmonic Generation Response and High Laser Damage Threshold302Top-Seeded Solution Crystal Growth, Morphology, Optical and Thermal Properties of Ba3(ZnB5O10)PO442Direct Gap Semiconductors Pb2BiS2I3, Sn2BiS2I3, and Sn2BiSI544A High Laser Damage Threshold and a Good Second-Harmonic Generation Response in a New Infrared NLO Material: LiSm3SiS725Syntheses, 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 Properties47Phase Transition and Second Harmonic Generation in Thiophosphates Ag2Cd(P2S6) and AgCd3(PS4)S2 Containing Two Second-Order Jahn–Teller Distorted Cations47Infrared SHG Materials CsM3Se6 (M = Ga/Sn, In/Sn): Phase Matchability Controlled by Dipole Moment of the Asymmetric Building Unit102Recent 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 photoluminescence54Li 3 Ge 3 Se 6 : the first ternary lithium germanium selenide with interesting ∞ [Ge 6 Se 12 ] n chains constructed by ethane-like [Ge 2 Se 6 ] 6− clusters8Low-temperature-flux syntheses of ultraviolet-transparent borophosphates Na 4 MB 2 P 3 O 13 (M = Rb, Cs) exhibiting a second-harmonic generation response23Tailored 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 252Thioborates: potential nonlinear optical materials with rich structural chemistry51Two excellent phase-matchable infrared nonlinear optical materials based on 3D diamond-like frameworks: RbGaSn 2 Se 6 and RbInSn 2 Se 639Facile Syntheses of Ba2[B4O7(OH)2] and Na[B5O7(OH)2](H2O) Borate Salts Exhibiting Nonlinear Optical Activity in the Ultraviolet50Superpolyhedron-Built Second Harmonic Generation Materials Exhibit Large Mid-Infrared Conversion Efficiencies and High Laser-Induced Damage Thresholds101Water Stability Studies of Hybrid Iodoargentates Containing N-Alkylated or N-Protonated Structure Directing Agents: Exploring Noncentrosymmetric Hybrid Structures33Mid-Infrared Nonlinear Optical Materials Based on Metal Chalcogenides: Structure–Property Relationship338Li2HgMS4 (M = Si, Ge, Sn): New Quaternary Diamond-Like Semiconductors for Infrared Laser Frequency Conversion64An ABX 3 organic–inorganic perovskite-type material with the formula (C 5 N 2 H 9 )CdCl 3 : Application for detection of volatile organic solvent molecules21Syntheses, crystal structures, and optical properties of CsBa5Ti2Se9Cl and CsBa2Cl53A review of the structural chemistry and physical properties of metal chalcogenide halides147AgGa2PS6: A New Mid‐Infrared Nonlinear Optical Material with a High Laser Damage Threshold and a Large Second Harmonic Generation Response78Synthesis and characterization of two lead-containing metal chalcogenides: Ba5Pb2Sn3S13 and Ba6PbSn3Se137LiGaGe2S6: A Chalcogenide with Good Infrared Nonlinear Optical Performance and Low Melting Point56Li7(TeO3)3F: A Lithium Fluoride Tellurite with Large Second Harmonic Generation Responses and a Short Ultraviolet Cutoff Edge39Cs 3 VO(O 2 ) 2 CO 3 : an exceptionally thermostable carbonatoperoxovanadate with an extremely large second-harmonic generation response130Four new quaternary chalcogenides A 2 Ba 7 Sn 4 Q 16 (A = Li, Na; Q = S, Se): syntheses, crystal structures determination, nonlinear optical performances investigation26Na 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 performances31NaBaM III Q 3 (M III = Al, Ga; Q = S, Se): first quaternary chalcogenides with isolated edge-sharing (MIII2Q 6 ) 6− dimers8The first investigation of europium silicate melilite for second-order nonlinear optical application: experimental and theoretical studies29Synthesis, Structure, and Optical Properties of Antiperovskite-Derived Ba2MQ3X (M = As, Sb; Q = S, Se; X = Cl, Br, I) Chalcohalides27SnI 4 ⋅(S 8 ) 2 : A Novel Adduct‐Type Infrared Second‐Order Nonlinear Optical Crystal184SnI4⋅(S8)2: A Novel Adduct‐Type Infrared Second‐Order Nonlinear Optical Crystal45Strong SHG Response via High Orientation of Tetrahedral Functional Motifs in Polyselenide A2Ge4Se10 (A = Rb, Cs)31LiGa 2 PS 6 and LiCd 3 PS 6 : Molecular Designs of Two New Mid-Infrared Nonlinear Optical Materials88MgSiAs: An Unexplored System with Promising Nonlinear Optical Properties53Prediction and Characterization of NaGaS2, A High Thermal Conductivity Mid-Infrared Nonlinear Optical Material for High-Power Laser Frequency Conversion38Second-order nonlinear optical crystals with mixed anions250Modifying Disordered Sites with Rational Cations to Regulate Band-Gaps and Second Harmonic Generation Responses Markedly: Ba6Li2ZnSn4S16 vs Ba6Ag2ZnSn4S16 vs Ba6Li2.67Sn4.33S1625Intriguing Structural Transition Inducing Variable Birefringences in ABa2MS4Cl (A = Rb, Cs; M = Ge, Sn)32Rational Design of a LiNbO3-like Nonlinear Optical Crystal, Li2ZrTeO6, with High Laser-Damage Threshold and Wide Mid-IR Transparency Window152An unprecedented pentanary chalcohalide with Mn atoms in two chemical environments: unique bonding characteristics and magnetic properties29Experimental study on nonlinear−optical property of Ag4P2Se66Combined experimental and theoretical investigations of Ba 3 GaS 4 I: interesting structural transformation originated from halogen substitution16From CuFeS 2 to Ba 6 Cu 2 FeGe 4 S 16 : rational band gap engineering achieves large second-harmonic-generation together with high laser damage threshold22Investigation on two new antimony-based quaternary chalcogenides: Na 6 CdSb 4 S 10 and Na 3 CdSbSe 41Partial substitution induced centrosymmetric to noncentrosymmetric structure transformation and promising second-order nonlinear optical properties of (K 0.38 Ba 0.81 )Ga 2 Se 495Quaternary semiconductor Ba 8 Zn 4 Ga 2 S 15 featuring unique one-dimensional chains and exhibiting desirable yellow emission24SrCdSnQ 4 (Q = S and Se): infrared nonlinear optical chalcogenides with mixed NLO-active and synergetic distorted motifs69Synthesis and nonlinear optical properties of new gallium thiophosphate Rb 2 Ga 2 P 2 S 913BaV2O6·H2O: A nonlinear optical crystal with a large bandgap7Ba10In6Zn7S26-nZnS: An Inorganic Composite System with Interface Phase-Matching Tuned for High-Performance Infrared Nonlinear Optical Materials13Sr 6 Cd 2 Sb 6 O 7 S 10 : Strong SHG Response Activated by Highly Polarizable Sb/O/S Groups124Sr6Cd2Sb6O7S10: Strong SHG Response Activated by Highly Polarizable Sb/O/S Groups22[(Ba19Cl4)(Ga6Si12O42S8)]: a Two-Dimensional Wide-Band-Gap Layered Oxysulfide with Mixed-Anion Chemical Bonding and Photocurrent Response20Ba10In6Zn7S10Se16 and Ba10In6Zn7Se26: Two new infrared nonlinear optical materials with T2 super tetrahedron6Mixed-Anion Inorganic Compounds: A Favorable Candidate for Infrared Nonlinear Optical Materials140Synthesis, characterization and theoretical calculation of a noncentrosymmetric compound, Cs0.92B0.92Si5.08O122Synthesis, crystal structure, and optical properties of Ba2SbO2SX (X = Br, I) oxy-chalcohalides4LiBa2MIIIQ4 (MIII = Al, Ga, In; Q = S, Se): A Series of Metal Chalcogenides with a Structural Transition12Ionothermal Synthesis of Metal Chalcogenides M2Ag3Sb3S7 (M = Rb, Cs) Displaying Nonlinear Optical Activity in the Infrared Region33Antiferromagnetic Semiconductor BaFMn0.5Te with Unique Mn Ordering and Red Photoluminescence13Li[LiCs2Cl][Ga3S6]: A Nanoporous Framework of GaS4 Tetrahedra with Excellent Nonlinear Optical Performance172Li[LiCs2Cl][Ga3S6]: A Nanoporous Framework of GaS4 Tetrahedra with Excellent Nonlinear Optical Performance40Rational design of infrared nonlinear optical chalcogenides by chemical substitution287A new type of novel salt-inclusion chalcogenide with ultralow thermal conductivity14A review of the AI2B II C IV DVI4 family as infrared nonlinear optical materials: the effect of each site on the structure and optical properties59Salt-inclusion chalcogenides: an emerging class of IR nonlinear optical materials54Sr 4 Pb 1.5 Sb 5 O 5 Se 8 : a new mid-infrared nonlinear optical material with a moderate SHG response22Ultraviolet nonlinear optical crystal: (NH4)ZnPO47One-Dimensional Chains in Pentanary Chalcogenides A2Ba3Cu2Sb2S10 (A = K, Rb, Cs) Displaying a Photocurrent Response44Designing Silicates as Deep‐UV Nonlinear Optical (NLO) Materials using Edge‐Sharing Tetrahedra147Designing Silicates as Deep‐UV Nonlinear Optical (NLO) Materials using Edge‐Sharing Tetrahedra43[ABa2Cl][Ga4S8] (A = Rb, Cs): Wide-Spectrum Nonlinear Optical Materials Obtained by Polycation-Substitution-Induced Nonlinear Optical (NLO)-Functional Motif Ordering270Partial Isovalent Anion Substitution to Access Remarkable Second-Harmonic Generation Response: A Generic and Effective Strategy for Design of Infrared Nonlinear Optical Materials114First non-centrosymmetric antimony chalcogenides containing mixed cations of alkali and alkaline-Earth: Ba14Na4Sb11S31Cl3 featuring unique disorded 43 helical chains of [Sb5S18]21–5Evaluation of nonlinear optical properties of quaternary chalcogenide halides Ba4Si3Se9Br2 and Ba4Ge3Se9Br222Salt-Inclusion Chalcogenide [Ba4Cl2][ZnGa4S10]: Rational Design of an IR Nonlinear Optical Material with Superior Comprehensive Performance Derived from AgGaS2134Two Mixed-Anion Units of [GeOSe3] and [GeO3S] Originating from Partial Isovalent Anion Substitution and Inducing Moderate Second Harmonic Generation Response and Large Birefringence55From AgGaS 2 to AgHgPS 4 : vacancy defects and highly distorted HgS 4 tetrahedra double-induced remarkable second-harmonic generation response68Recent Achievements in Lone-Pair Cation-Based Infrared Second-Order Nonlinear Optical Materials95[GaF(H 2 O)][IO 3 F]: a promising NLO material obtained by anisotropic polycation substitution42From thiophosphate to chalcohalide: mixed-anion AgS x Cl y ligands concurrently enhancing nonlinear optical effects and laser-damage threshold10Heterovalent cations substitution to design asymmetric chalcogenides with promising nonlinear optical performances44

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  4. ChemInform Abstract: Noncentrosymmetric Inorganic Open‐Framework Chalcohalides with Strong Middle IR SHG and Red Emission: Ba3AGa5Se10Cl2 (A: Cs, Rb, K).

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