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RESEARCH PAPER · Journal of the American Chemical Society · 2016

Na 2 ZnGe 2 S 6 : A New Infrared Nonlinear Optical Material with Good Balance between Large Second-Harmonic Generation Response and High Laser Damage Threshold

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Na 2 ZnGe 2 S 6 : A New Infrared Nonlinear Optical Material with Good Balance between Large Second-Harmonic Generation Response and High Laser Damage ThresholdOriginalKPb 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-supertetrahedra41The mechanism of large second harmonic generation enhancement activated by Zn 2+ substitution35ChemInform Abstract: Na2ZnGe2S6: A New Infrared Nonlinear Optical Material with Good Balance Between Large Second‐Harmonic Generation Response and High Laser Damage Threshold.2Analysis and prediction of mid-IR nonlinear optical metal sulfides with diamond-like structures335Non‐centrosymmetric Selenides AZn4In5Se12 (A=Rb, Cs): Synthesis, Characterization and Nonlinear Optical Properties47Multitopic ligand directed assembly of low-dimensional metal-chalcogenide organic frameworks5Infrared 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 materials433Ba 6 Li 2 CdSn 4 S 16 : lithium substitution simultaneously enhances band gap and SHG intensity44BaCu 2 M IV Q 4 (M IV = Si, Ge, and Sn; Q = S, Se): synthesis, crystal structures, optical performances and theoretical calculations54Li 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− clusters8Na 2 CdGe 2 Q 6 (Q = S, Se): two metal-mixed chalcogenides with phase-matching abilities and large second-harmonic generation responses77Na 6 Si 3 S 8 O: the first example of a sulfide silicate exhibiting unusual tri-polymerized [Si 3 S 8 O] 6− units without S–O bonds8Screening novel candidates for mid-IR nonlinear optical materials from I 3 –V–VI 4 compounds51The first quaternary diamond-like semiconductor with 10-membered LiS 4 rings exhibiting excellent nonlinear optical performances104Two 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 Thresholds101The Role of Ionic Liquid Electrolyte in an Aluminum–Graphite Electrochemical Cell97First-principles study lone-pair effects of Sb (III)-S chromophore influence on SHG response in quaternary potassium containing silver antimony sulfides12Mid-Infrared Nonlinear Optical Materials Based on Metal Chalcogenides: Structure–Property Relationship338Li3VO4: A Promising Mid-Infrared Nonlinear Optical Material with Large Laser Damage Threshold51Li2HgMS4 (M = Si, Ge, Sn): New Quaternary Diamond-Like Semiconductors for Infrared Laser Frequency Conversion64Spin-polarized Second Harmonic Generation from the Antiferromagnetic CaCoSO Single Crystal148Growth, Properties, and Theoretical Analysis of M2LiVO4 (M = Rb, Cs) Crystals: Two Potential Mid-Infrared Nonlinear Optical Materials36Na2ZnSn2S6: A mixed-metal thiostannate with large second-harmonic generation response activated by penta-tetrahedral [ZnSn4S14]10− clusters10Ba 6 Zn 7 Ga 2 S 16 : A Wide Band Gap Sulfide with Phase-Matchable Infrared NLO Properties110Coexistence 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 Bandgap36AgGa2PS6: 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 Ba6PbSn3Se137New Compressed Chalcopyrite-like Li2BaMIVQ4 (MIV = Ge, Sn; Q = S, Se): Promising Infrared Nonlinear Optical Materials245LiGaGe2S6: A Chalcogenide with Good Infrared Nonlinear Optical Performance and Low Melting Point56A Polyselenide with a Novel Se78– Unit: the Structure of Sr19–xPbxGe11Se44 with x = 5.0 and 6.44Nonlinear Optical Crystal Rb 4 Sn 3 Cl 2 Br 8 : Synthesis, Structure, and Characterization32Experimental and theoretical studies on the NLO properties of two quaternary non-centrosymmetric chalcogenides: BaAg 2 GeS 4 and BaAg 2 SnS 468Crystal structures, phase transitions and thermal expansion properties of NaZr 2 (PO 4 ) 3 –SrZr 4 (PO 4 ) 6 solid solutions21Design and synthesis of a nonlinear optical material BaAl 4 S 7 with a wide band gap inspired from SrB 4 O 763First principle study of nonlinear optical crystals15New strategy for designing promising mid-infrared nonlinear optical materials: narrowing the band gap for large nonlinear optical efficiencies and reducing the thermal effect for a high laser-induced damage threshold142Oxyhalides: prospecting ore for optical functional materials with large laser damage thresholds76Remarkable multimember-ring configurations in a new family of Na 7 M II Sb 5 S 12 (M II = Zn, Cd, Hg) exhibiting various three-dimensional tunnel structures25Sr 5 ZnGa 6 S 15 : a new quaternary non-centrosymmetric semiconductor with a 3D framework structure displaying excellent nonlinear optical performance60Structural 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 Response134Effect of Element Substitution on Structural Transformation and Optical Performances in I2BaMIVQ4 (I = Li, Na, Cu, and Ag; MIV = Si, Ge, and Sn; Q = S and Se)63Electronic, bonding, linear, and nonlinear optical properties of Na2MGe2Q6 (M=Cd, Zn, Hg; Q=S, Se), Na2ZnSi2S6, and Na2ZnSn2S6 two metal-mixed chalcogenide compounds: Insights from an ab initio study21LiGa 2 PS 6 and LiCd 3 PS 6 : Molecular Designs of Two New Mid-Infrared Nonlinear Optical Materials88Strong Infrared Nonlinear Optical Efficiency and High Laser Damage Threshold Realized in Quaternary Alkali Metal Sulfides Na2Ga2MS6 (M = Ge, Sn) Containing Mixed Nonlinear Optically Active Motifs48Nonbonding Electrons Driven Strong SHG Effect in Hg2GeSe4: Experimental and Theoretical Investigations60K2ZnGe3S8: A Congruent-Melting Infrared Nonlinear-Optical Material with a Large Band Gap41Ternary Mixed-Metal Cd4GeS6: Remarkable Nonlinear-Optical Properties Based on a Tetrahedral-Stacking Framework41Mo6+ Cation Enrichment of the Structure Chemistry of Iodates: Syntheses, Structures, and Calculations of Ba(MoO2)2(IO3)4O, Ba3[(MoO2)2(IO3)4O(OH)4]·2H2O, and Sr[(MoO2)6(IO4)2O4]·H2O24Module-Guided Design Scheme for Deep-Ultraviolet Nonlinear Optical Materials195Synthesis, Crystal Structure, and Optical Properties of Noncentrosymmetric Na2ZnSnS434Modifying Disordered Sites with Rational Cations to Regulate Band-Gaps and Second Harmonic Generation Responses Markedly: Ba6Li2ZnSn4S16 vs Ba6Ag2ZnSn4S16 vs Ba6Li2.67Sn4.33S1625Adduct-Type IR Nonlinear-Optical Crystal SbI 3 ·(S 8 ) 3 with a Large Second-Harmonic Generation and a High Laser-Induced Damage Threshold59Intriguing Structural Transition Inducing Variable Birefringences in ABa2MS4Cl (A = Rb, Cs; M = Ge, Sn)32Second-order nonlinear optical properties of CuGa In1-Se2 (x = 0.54): Experimental and theoretical investigations4A review on structure-performance relationship toward the optimal design of infrared nonlinear optical materials with balanced performances252Cu2EuMQ4 (M = Si, Ge; Q = S, Se): Syntheses, structure study and physical properties determination26Lead-based crystal luminophores: Tuning emissive crystals and application for recording high temperature history with ratiometric and colorimetric signals12BaB2S4: An Efficient and Air-Stable Thioborate as Infrared Nonlinear Optical Material with High Laser Damage Threshold85Recent advances and future perspectives on infrared nonlinear optical metal halides223A review on the development of infrared nonlinear optical materials with triangular anionic groups38Noncentrosymmetric cubic RbBSi2O6 polymorph with deep ultraviolet cut-off edge4Experimental study on nonlinear−optical property of Ag4P2Se66Ba10Zn7M6Q26: Two New Mid-infrared Nonlinear Optical Crystals with T2 Supertetrahedron 3D Framework11Recent progress on new infrared nonlinear optical materials with application prospect133ABaSbQ 3 (A = Li, Na; Q = S, Se): diverse arrangement modes of isolated SbQ 3 ligands regulating the magnitudes of birefringences50Adjustable optical nonlinearity in d 10 cations containing chalcogenides via dp hybridization interaction13Ba 4 (BS 3 S) 2 S 4 : a new thioborate with unprecedented [BS 3 -S] and [S 4 ] fundamental building blocks19From 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 threshold22Impressive second harmonic generation response in a novel phase-matchable NLO-active MOF derived from achiral precursors38Investigation on two new antimony-based quaternary chalcogenides: Na 6 CdSb 4 S 10 and Na 3 CdSbSe 41Li 2 ZnGeS 4 : a promising diamond-like infrared nonlinear optical material with high laser damage threshold and outstanding second-harmonic generation response43Metal-cation substitutions induced the enhancement of second harmonic generation in A 8 BS 6 (A = Cu, and Ag; B = Si, Ge, and Sn)14Mn-Based tin sulfide Sr 3 MnSn 2 S 8 with a wide band gap and strong nonlinear optical response30Monoclinic gallium selenide: an AgGaS 2 -type structure variant with balanced infrared nonlinear optical performance43Partial substitution induced centrosymmetric to noncentrosymmetric structure transformation and promising second-order nonlinear optical properties of (K 0.38 Ba 0.81 )Ga 2 Se 495Pb 7 F 12 Cl 2 : a promising infrared nonlinear optical material with high laser damage threshold19Rational design of a new chalcogenide with good infrared nonlinear optical performance: SrZnSnS 452SrCdSnQ 4 (Q = S and Se): infrared nonlinear optical chalcogenides with mixed NLO-active and synergetic distorted motifs68Synthesis and nonlinear optical properties of new gallium thiophosphate Rb 2 Ga 2 P 2 S 913Synthesis, crystal structures and nonlinear optical properties of β-RbCdI 3 ·H 2 O and CsCdI 3 ·H 2 O8SrCdGeS4 and SrCdGeSe4: Promising Infrared Nonlinear Optical Materials with Congruent-Melting Behavior74Artificial Second-Order Nonlinear Optics in a Centrosymmetric Optical Material BiVO4: Breaking the Prerequisite for Nonlinear Optical Materials11ASbF3Cl (A = Rb, Cs): Structural Evolution from Centrosymmetry to Noncentrosymmetry16Theoretical Design of Layered AlGaS3 as a New Nonlinear Optical Material with a Strong Second Harmonic Generation Response5MnSiP2: A New Mid-IR Ternary Phosphide with Strong SHG Effect and Ultrabroad Transparency Range66Synthesis, growth and characterization of semi-organic nonlinear optical L-threnoninum sodium fluoride (LTSF) crystal for photonics application25Ba10In6Zn7S26-nZnS: An Inorganic Composite System with Interface Phase-Matching Tuned for High-Performance Infrared Nonlinear Optical Materials13[Ge2S5(S2)]4−, A NLO‐Active Unit Leading to an Asymmetric Structure Discovered in Li2Cs4Ge2S5(S2)Cl2: An Experimental and Theoretical study18Balanced Second-Order Nonlinear Optical Properties of Adducts CHI3·(S8)3 and AsI3·(S8)3: A Systematic Survey48Large 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, Structure, and Characterization of Two Mixed-Cation Quaternary Chalcogenides K2BaSnQ4 (Q = S, Se)19Ba10In6Zn7S10Se16 and Ba10In6Zn7Se26: Two new infrared nonlinear optical materials with T2 super tetrahedron6Mixed-Anion Inorganic Compounds: A Favorable Candidate for Infrared Nonlinear Optical Materials140Syntheses, structural variants and characterization of A2CdSn2S6 (A = Cs, Rb and K) compounds13Rb10Zn4Sn4S17: A Chalcogenide with Large Laser Damage Threshold Improved from the Mn-Based Analogue27Complex magnetic structure and related thermodynamic properties of Mn2SnS49Vibration uncoupling of germanium with different valence states lowers thermal conductivity of Cs2Ge3Ga6Se1410Li[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 Performance40Solvothermal Syntheses and Characterizations of Four Quaternary Copper Sulfides BaCu3MS4 (M = In, Ga) and BaCu2MS4 (M = Sn, Ge)27BaGe 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 Effects54A new iodate-phosphate Pb 2 (IO 3 )(PO 4 ) achieving great improvement in birefringence activated by (IO 3 ) − groups53Rational design of infrared nonlinear optical chalcogenides by chemical substitution287Li2K4TiOGe4O12: A Stable Mid-Infrared Nonlinear Optical Material69A review of the AI2B II C IV DVI4 family as infrared nonlinear optical materials: the effect of each site on the structure and optical properties59Abnormal bandgap enlargement resulted in a promising mid-infrared nonlinear optical material Rb 2 CdBrI 3 with an ultrahigh laser damage threshold10Ba 6 In 6 Zn 4 Se 19 : a high performance infrared nonlinear optical crystal with [InSe 3 ] 3− trigonal planar functional motifs22Experimental and theoretical studies of the ternary thiophosphate PbPS 3 featuring ethane-like [P 2 S 6 ] 4− units15Li 2 CdSiS 4 , a promising IR NLO material with a balanced E g and SHG response originating from the effect of Cd with d 10 configuration36Mixed-metal thiophosphate CuCd 3 PS 6 : an infrared nonlinear optical material activated by its three-in-one tetrahedra-stacking architecture33New quaternary chalcogenide Ba 4 HgAs 2 S 10 originating from the combination of linear [HgS 2 ] 2− and tetrahedral [AsS 4 ] 3− modules8Strong nonlinear optical effect attained by atom-response-theory aided design in the Na 2 M II MIV2Q 6 (M II = Zn, Cd; M IV = Ge, Sn; Q = S, Se) chalcogenide system27Molecular Construction from AgGaS 2 to CuZnPS 4 : Defect-Induced Second Harmonic Generation Enhancement and Cosubstitution-Driven Band Gap Enlargement96Cd4SiQ6 (Q = S, Se): Ternary Infrared Nonlinear Optical Materials with Mixed Functional Building Motifs21Lead 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 Materials55Hexagonal In2Se3: A Defect Wurtzite-Type Infrared Nonlinear Optical Material with Moderate Birefringence Contributed by Unique InSe5 Unit75A2SnS5: A Structural Incommensurate Modulation Exhibiting Strong Second‐Harmonic Generation and a High Laser‐Induced Damage Threshold (A=Ba, Sr)30A2SnS5: A Structural Incommensurate Modulation Exhibiting Strong Second‐Harmonic Generation and a High Laser‐Induced Damage Threshold (A=Ba, Sr)86HgCuPS4: An Exceptional Infrared Nonlinear Optical Material with Defect Diamond-like Structure145Crystal chemistry, second-order nonlinear optical, and magnetic properties of Eu8Sn4Se2014Functional Chalcogenide Na2HgSn2Se6 and K2MnGe2Se6 Exhibiting Flexible Chain Structure and Intriguing Birefringence Tunability16Inherent laws between tetrahedral arrangement pattern and optical performance in tetrahedron-based mid-infrared nonlinear optical materials130Evaluation of nonlinear optical properties of quaternary chalcogenide halides Ba4Si3Se9Br2 and Ba4Ge3Se9Br222Syntheses, structural variants and characterization of A2ZnSn3S8 (A = Cs, Rb) and A2CdSn3S8 (A = Cs, Rb, K, Na) compounds18α‑Li2ZnGeS4: A Wide-Bandgap Diamond-like Semiconductor with Excellent Balance between Laser-Induced Damage Threshold and Second Harmonic Generation Response157Enhancement of one- and two-photon absorption and visualization of intramolecular charge transfer of pyrenyl-contained derivatives33Pb 18 O 8 Cl 15 I 5 : A Polar Lead Mixed Oxyhalide with Unprecedented Architecture and Excellent Infrared Nonlinear Optical Properties165Pb18O8Cl15I5: A Polar Lead Mixed Oxyhalide with Unprecedented Architecture and Excellent Infrared Nonlinear Optical Properties29Hierarchical Contribution of Anions to Second Harmonic Generation in A2HgI4 (A = Na, Ag, Cu) Regulated Dramatically by Metal Cations4Recent Advances in Oxide‐based Nonlinear Optical Materials with Wide Infrared Transparency Beyond 6 μm38Chalcophosphates: A Treasure House of Infrared Nonlinear Optical Materials75Two Mixed-Anion Units of [GeOSe3] and [GeO3S] Originating from Partial Isovalent Anion Substitution and Inducing Moderate Second Harmonic Generation Response and Large Birefringence55Na4CdGe2S7: A Sodium-Rich Quaternary Wide-Band-Gap Chalcogenide with Two-Dimensional [Ge2CdS7]∞ Layers6Bi 32 Cd 3 P 10 O 76 : a new congruently melting nonlinear optical crystal with a large SHG response and a wide transparent region24Synthesis, Crystal Structures, Spectroscopic Characterization, and Thermal Analyses of the New Bismuth Sulfates NaBi(SO4)2·H2O and ABi(SO4)2 (A = K, Rb, Cs)5Sr6(Li2Cd)A4S16 (A = Ge, Sn): How to Go beyond the Band Gap Limitation via Site-Specific Modification40AMnAs3S6 (A = Cs, Rb): Phase-Matchable Infrared Nonlinear Optical Functional Motif [As3S6]3– Obtained via Surfactant–Thermal Method32Phase Matching, Strong Frequency Doubling, and Outstanding Laser-Induced Damage Threshold in the Biaxial, Quaternary Diamond-like Semiconductor Li 4 CdSn 2 S 779EuHgGeSe 4 and EuHgSnS 4 : Two Quaternary Eu-Based Infrared Nonlinear Optical Materials with Strong Second-Harmonic-Generation Responses55From AgGaS 2 to AgHgPS 4 : vacancy defects and highly distorted HgS 4 tetrahedra double-induced remarkable second-harmonic generation response67A novel promising infrared nonlinear optical selenide KAg 3 Ga 8 Se 14 designed from benchmark AgGaQ 2 (Q = S, Se)55

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