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RESEARCH PAPER · Angewandte Chemie International Edition · 2016

Na 2 BaMQ 4 (M=Ge, Sn; Q=S, Se): Infrared Nonlinear Optical Materials with Excellent Performances and that Undergo Structural Transformations

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Na 2 BaMQ 4 (M=Ge, Sn; Q=S, Se): Infrared Nonlinear Optical Materials with Excellent Performances and that Undergo Structural TransformationsOriginal[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 thresholds189BaCdSnS 4 and Ba 3 CdSn 2 S 8 : syntheses, structures, and non-linear optical and photoluminescence properties97KPb 2 (PO 3 ) 5 : a novel nonlinear optical lead polyphosphate with a short deep-UV cutoff edge109Na 2 ZnGe 2 S 6 : A New Infrared Nonlinear Optical Material with Good Balance between Large Second-Harmonic Generation Response and High Laser Damage Threshold302ChemInform Abstract: Na2BaMQ4 (M: Ge, Sn; Q: S, Se): Infrared Nonlinear Optical Materials with Excellent Performances and that Undergo Structural Transformations.0A High Laser Damage Threshold and a Good Second-Harmonic Generation Response in a New Infrared NLO Material: LiSm3SiS725[CH3NH3]2Ag4SnIV2SnIIS8: An Open-Framework Mixed-Valent Chalcogenidostannate42SrNO3(OH)·H2O: A new member in strontium nitrate hydrate family with an ultraviolet cut-off edge7Non‐centrosymmetric Selenides AZn4In5Se12 (A=Rb, Cs): Synthesis, Characterization and Nonlinear Optical Properties47Crystal structure, electronic structure and physical properties of the new quaternary chalcogenides Tl 2 NdAg 3 Se 4 and Tl 2 NdAg 3 Te 48Infrared SHG Materials CsM3Se6 (M = Ga/Sn, In/Sn): Phase Matchability Controlled by Dipole Moment of the Asymmetric Building Unit102BaCu 2 M IV Q 4 (M IV = Si, Ge, and Sn; Q = S, Se): synthesis, crystal structures, optical performances and theoretical calculations54Experimental and ab initio studies of two UV nonlinear optical materials15Li 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 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 bonds8Syntheses, crystal structures, and photocatalytic properties of two ammonium-directed Ag–Sb–S complexes30Two 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 422Syntheses, Crystal Structures, and Optical and Photocatalytic Properties of Four Small-Amine-Molecule-Directed M–Sn–Q (M = Zn, Ag; Q = S, Se) Compounds49Growth, Properties, and Theoretical Analysis of M2LiVO4 (M = Rb, Cs) Crystals: Two Potential Mid-Infrared Nonlinear Optical Materials36Two Barium Gold Iodates: Syntheses, Structures, and Properties of Polar BaAu(IO3)5 and Nonpolar HBa4Au(IO3)12 Materials5Coexistence of Strong Second Harmonic Generation Response and Wide Band Gap in AZn4Ga5S12 (A=K, Rb, Cs) with 3D Diamond‐like Frameworks65AgGa2PS6: 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 Ba6PbSn3Se137Hg-Based Infrared Nonlinear Optical Material KHg4Ga5Se12 Exhibits Good Phase-Matchability and Exceptional Second Harmonic Generation Response101Large Second-Harmonic Generation Responses Achieved by the Dimeric [Ge2Se4(μ-Se2)]4– Functional Motif in Polar Polyselenides A4Ge4Se12 (A = Rb, Cs)49A new-type composite film of cholesteric liquid crystal doped with PCBM for laser-damage prevention in both visible and near-infrared region5A Polyselenide with a Novel Se78– Unit: the Structure of Sr19–xPbxGe11Se44 with x = 5.0 and 6.44Experimental and theoretical studies on the NLO properties of two quaternary non-centrosymmetric chalcogenides: BaAg 2 GeS 4 and BaAg 2 SnS 468Design and synthesis of a nonlinear optical material BaAl 4 S 7 with a wide band gap inspired from SrB 4 O 764Four 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− dimers8New 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 threshold142Sr 5 ZnGa 6 S 15 : a new quaternary non-centrosymmetric semiconductor with a 3D framework structure displaying excellent nonlinear optical performance60CsCu5Se3: A Copper-Rich Ternary Chalcogenide Semiconductor with Nearly Direct Band Gap for Photovoltaic Application41From 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)63Six New Members of the A2MIIMIV3Q8 Family and Their Structural Relationship26Synthesis, Crystal Structures, Optical Properties and Theoretical Calculations of Two Metal Chalcogenides Ba2AlSbS5 and Ba2GaBiSe59T3 supertetrahedral cluster [Mn4Sn6S20]8−: Solvothermal syntheses, crystal structures and photocatalytic properties of Mn(II) chalcogenidostannates7Strong 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 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 Motifs48K2ZnGe3S8: A Congruent-Melting Infrared Nonlinear-Optical Material with a Large Band Gap41Ternary Mixed-Metal Cd4GeS6: Remarkable Nonlinear-Optical Properties Based on a Tetrahedral-Stacking Framework41Modifying Disordered Sites with Rational Cations to Regulate Band-Gaps and Second Harmonic Generation Responses Markedly: Ba6Li2ZnSn4S16 vs Ba6Ag2ZnSn4S16 vs Ba6Li2.67Sn4.33S1625Zn 3 P 2 S 8 : A Promising Infrared Nonlinear-Optical Material with Excellent Overall Properties70A review on structure-performance relationship toward the optimal design of infrared nonlinear optical materials with balanced performances253Cu2EuMQ4 (M = Si, Ge; Q = S, Se): Syntheses, structure study and physical properties determination26BaB2S4: 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 halides223Pressure-Assisted Method for the Preparations of High-Quality AaGaS2 and AgGaGeS4 Crystals for Mid-Infrared Laser Applications11Noncentrosymmetric cubic RbBSi2O6 polymorph with deep ultraviolet cut-off edge4Experimental study on nonlinear−optical property of Ag4P2Se66A 2 SrM IV S 4 (A = Li, Na; M IV = Ge, Sn) concurrently exhibiting wide bandgaps and good nonlinear optical responses as new potential infrared nonlinear optical materials78ABaSbQ 3 (A = Li, Na; Q = S, Se): diverse arrangement modes of isolated SbQ 3 ligands regulating the magnitudes of birefringences50BaMnSnS 4 and BaCdGeS 4 : infrared nonlinear optical sulfides containing highly distorted motifs with centers of moderate electronegativity48Centric-to-acentric structure transformation induced by a stereochemically active lone pair: a new insight for design of IR nonlinear optical materials90From 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 threshold22Improved photo-dechlorination at polar photocatalysts K 3 B 6 O 10 X (X = Cl, Br) by halogen atoms-modulated polarization9Investigation 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 response43Mn-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 threshold19Planar graphitic ZnS, buckling ZnS monolayers and rolled-up nanotubes as nonlinear optical materials: first-principles simulation13Predicting viable isomers of [X,C,N] and [H,X,C,N] (X = Sn, Pb)2Rational design of a new chalcogenide with good infrared nonlinear optical performance: SrZnSnS 452Structural modulation induced by M IIIA metals in Ba 3 MQ 4 X (M = Al, Ga, In; Q = S, Se; X = Cl, Br): an experimental and computational analysis7Synthesis, crystal structures and nonlinear optical properties of β-RbCdI 3 ·H 2 O and CsCdI 3 ·H 2 O8BaV2O6·H2O: A nonlinear optical crystal with a large bandgap7Artificial Second-Order Nonlinear Optics in a Centrosymmetric Optical Material BiVO4: Breaking the Prerequisite for Nonlinear Optical Materials11Abrupt Structural Transformation in Asymmetric ABPO4F (A = K, Rb, Cs)21Hierarchy in nonlinear optical responses induced by metal cation tailoring effect in the In-containing chalcogenide compounds4[Ge2S5(S2)]4−, A NLO‐Active Unit Leading to an Asymmetric Structure Discovered in Li2Cs4Ge2S5(S2)Cl2: An Experimental and Theoretical study18Growth and physicochemical investigations on wide bandgap 2D polymeric amino acetic acid sulfato dilithium metal–organic framework1Large 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)19Mixed-Anion Inorganic Compounds: A Favorable Candidate for Infrared Nonlinear Optical Materials140Sn 2 Ga 2 S 5 : A Polar Semiconductor with Exceptional Infrared Nonlinear Optical Properties Originating from the Combined Effect of Mixed Asymmetric Building Motifs81LiBa2MIIIQ4 (MIII = Al, Ga, In; Q = S, Se): A Series of Metal Chalcogenides with a Structural Transition12Nontoxic KBBF Family Member Zn2BO3(OH): Balance between Beneficial Layered Structure and Layer Tendency81Partial Congener Substitution Induced Centrosymmetric to Noncentrosymmetric Transformation Witnessed by K3Ga3(Ge7–xMx)Se20 (M = Si, Sn) and Their Nonlinear Optical Properties51Li[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 Performance40BaGe 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 ) − groups53K5(W3O9F4)(IO3): An Efficient Mid-Infrared Nonlinear Optical Compound with High Laser Damage Threshold114A new family of quaternary thiosilicates SrA 2 SiS 4 (A = Li, Na, Cu) as promising infrared nonlinear optical crystals48Rational design of infrared nonlinear optical chalcogenides by chemical substitution287Alkali-earth metal lead( ii ) oxyhalide Ba 27 Pb 8 O 8 Cl 54 exhibiting interesting [Pb 4 Ba 4 O 4 ] 8+ species8A highly distorted HgS 4 tetrahedron-induced moderate second-harmonic generation response of EuHgGeS 462Ba 6 In 6 Zn 4 Se 19 : a high performance infrared nonlinear optical crystal with [InSe 3 ] 3− trigonal planar functional motifs22Mixed-metal thiophosphate CuCd 3 PS 6 : an infrared nonlinear optical material activated by its three-in-one tetrahedra-stacking architecture33Infrared Nonlinear Optical Polymorphs α- and β-SrCu 2 SnS 4 Exhibiting Large Second Harmonic Generation Responses with Requisite Phase-Matching Behavior44One-Dimensional Double Chains in Sodium-Based Quaternary Chalcogenides Displaying Intriguing Red Emission and Large Optical Anisotropy17AGaSnS4 (A = Rb, Cs): Three sulfides and their structure diversity8An assessment of the structural, electronic, optical and thermoelectric properties of the BaAg2GeS4 compound11Molecular Construction from AgGaS 2 to CuZnPS 4 : Defect-Induced Second Harmonic Generation Enhancement and Cosubstitution-Driven Band Gap Enlargement97Cd4SiQ6 (Q = S, Se): Ternary Infrared Nonlinear Optical Materials with Mixed Functional Building Motifs21LiBa4Ga5Q12 (Q = S, Se): Noncentrosymmetric Metal Chalcogenides with a Cesium Chloride Topological Structure Displaying a Remarkable Laser Damage Threshold32A2SnS5: 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 Structure146Inherent laws between tetrahedral arrangement pattern and optical performance in tetrahedron-based mid-infrared nonlinear optical materials131Na2MgSnS4 – a new member of the A 2 I B II C IV X 4 family of compounds6Na2MgSnS4 – a new member of the A(2)(I)B(II)C(IV)X(4) family of compounds0Salt-Inclusion Chalcogenide [Ba4Cl2][ZnGa4S10]: Rational Design of an IR Nonlinear Optical Material with Superior Comprehensive Performance Derived from AgGaS2134α‑Li2ZnGeS4: A Wide-Bandgap Diamond-like Semiconductor with Excellent Balance between Laser-Induced Damage Threshold and Second Harmonic Generation Response158Synthesis and study of structural, optical, and electrical properties of nontoxic and earth-abundant Na2ZnSnS4 material7Chalcophosphates: A Treasure House of Infrared Nonlinear Optical Materials75Sr6(Li2Cd)A4S16 (A = Ge, Sn): How to Go beyond the Band Gap Limitation via Site-Specific Modification40Investigation of the second-order nonlinear optical property of Sr6Sb6S173Recent 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 materials47Ba 2 Ge 2 Te 5 : a ternary NLO-active telluride with unusual one-dimensional helical chains and giant second harmonic-generation tensors31Breaking through the “3.0 eV wall” of energy band gap in mid-infrared nonlinear optical rare earth chalcogenides by charge-transfer engineering145From Ce(IO 3 ) 4 to CeF 2 (IO 3 ) 2 : fluorinated homovalent substitution simultaneously enhances SHG response and bandgap for mid-infrared nonlinear optics26Heterovalent cations substitution to design asymmetric chalcogenides with promising nonlinear optical performances44M 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 Variation and Switchable Nonlinear Optical Behavior of Metal–Organic Frameworks50Halonitrides Zn 2 NX (X=Cl,Br): Novel Mid-Infrared Nonlinear Optical Materials30LaSiP3 and LaSi2P6: Two Excellent Rare‐Earth Pnictides with Strong SHG Responses as Mid‐ and Far‐Infrared Nonlinear Optical Crystals36Introduction of Li into Ag-Based Noncentrosymmetric Sulfides for High-Performance Infrared Nonlinear Optical Materials40Two Lead Halides with Strong SHG Response Obtained by the Isovalent Substitutions of Alkali Metal Cation and Halogen Anion22Inorganic Chalcogenides: From Zero‐Dimensional Clusters to Three‐Dimensional Frameworks5AZn4Ga5Se12 (A = K, Rb, or Cs): Infrared Nonlinear Optical Materials with Simultaneous Large Second Harmonic Generation Responses and High Laser-Induced Damage Thresholds34BaCdGeSe4: Synthesis, structure and nonlinear optical properties13Li 4 MgGe 2 S 7 : The First Alkali and Alkaline‐Earth Diamond‐Like Infrared Nonlinear Optical Material with Exceptional Large Band Gap214Li4MgGe2S7: The First Alkali and Alkaline‐Earth Diamond‐Like Infrared Nonlinear Optical Material with Exceptional Large Band Gap16A Congruent‐Melting Mid‐Infrared Nonlinear Optical Vanadate Exhibiting Strong Second‐Harmonic Generation22A Congruent‐Melting Mid‐Infrared Nonlinear Optical Vanadate Exhibiting Strong Second‐Harmonic Generation64Transition-metal-based chalcogenides: A rich source of infrared nonlinear optical materials184Noncentrosymmetric Ba6In2Q10 (Q = S, Se): Structural Chemistry and Nonlinear-Optical Activity11Rational Crystal Structure Design and Nonlinear-Optical Properties of Noncentrosymmetric RbCu2NbS47Structural modification from centrosymmetric Rb 4 Hg 2 Ge 2 S 8 to noncentrosymmetric (Na 3 Rb)Hg 2 Ge 2 S 8 : mixed alkali metals strategy for infrared nonlinear optical material design28Building-block approach to the discovery of Na8Mn2(Ge2Se6)2: A polar chalcogenide exhibiting promising harmonic generation signals with a high laser-induced damage threshold9Phase Matchability Transformation in the Infrared Nonlinear Optical Materials with Diamond‐Like Frameworks63[ASr 4 Cl][Ge 3 S 10 ] (A = Na, K) and [KBa 4 Cl][Ge 3 S 10 ]: new salt-inclusion infrared nonlinear optical crystals with zero-dimensional [Ge 3 S 9 ] clusters32AAg 2 PS 4 (A = K, Na/K): the first-type of noncentrosymmetric alkali metal Ag-based thiophosphates exhibiting excellent second-order nonlinear optical performances21Alkali metal partial substitution-induced improved second-harmonic generation and enhanced laser-induced damage threshold for Ag-based sulfides21Chiral wheel anions of copper( ii )-early lanthanides( iii ) with high optical-limiting properties3Direct Synthesis of Catalytically Nifecomncu High Entropy Alloys for Highly Effective Overall Water-Splitting0Li-Free ternary sulphide Cs 5 Ga 9 S 16 with excellent nonlinear optical performance similar to classic LiGaS 213Rational design of a promising oxychalcogenide infrared nonlinear optical crystal60Rb2MGe3S8 (M=Zn, Cd): Non-Centrosymmetry Transformation Led by Structure Change of [MGe3S8]2- Unit※4The exploration of new infrared nonlinear optical crystals based on the polymorphism of BaGa 4 S 731

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  36. CsCu5Se3: A Copper-Rich Ternary Chalcogenide Semiconductor with Nearly Direct Band Gap for Photovoltaic Application

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  41. T3 supertetrahedral cluster [Mn4Sn6S20]8−: Solvothermal syntheses, crystal structures and photocatalytic properties of Mn(II) chalcogenidostannates

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  42. Strong SHG Response via High Orientation of Tetrahedral Functional Motifs in Polyselenide A2Ge4Se10 (A = Rb, Cs)

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  43. LiGa 2 PS 6 and LiCd 3 PS 6 : Molecular Designs of Two New Mid-Infrared Nonlinear Optical Materials

    Chemistry of Materials · 2018-05-17

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  44. Strong Infrared Nonlinear Optical Efficiency and High Laser Damage Threshold Realized in Quaternary Alkali Metal Sulfides Na2Ga2MS6 (M = Ge, Sn) Containing Mixed Nonlinear Optically Active Motifs

    Inorganic Chemistry · 2018-05-29

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  45. K2ZnGe3S8: A Congruent-Melting Infrared Nonlinear-Optical Material with a Large Band Gap

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  46. Ternary Mixed-Metal Cd4GeS6: Remarkable Nonlinear-Optical Properties Based on a Tetrahedral-Stacking Framework

    Inorganic Chemistry · 2018-07-13

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  47. Modifying Disordered Sites with Rational Cations to Regulate Band-Gaps and Second Harmonic Generation Responses Markedly: Ba6Li2ZnSn4S16 vs Ba6Ag2ZnSn4S16 vs Ba6Li2.67Sn4.33S16

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  50. Cu2EuMQ4 (M = Si, Ge; Q = S, Se): Syntheses, structure study and physical properties determination

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