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RESEARCH PAPER · Chemistry of Materials · 2017

Ba 6 Zn 7 Ga 2 S 16 : A Wide Band Gap Sulfide with Phase-Matchable Infrared NLO Properties

Yanyan Li, Pengfei Liu, Li‐Ming Wu

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Ba 6 Zn 7 Ga 2 S 16 : A Wide Band Gap Sulfide with Phase-Matchable Infrared NLO PropertiesOriginalHg-Based Infrared Nonlinear Optical Material KHg4Ga5Se12 Exhibits Good Phase-Matchability and Exceptional Second Harmonic Generation Response101Experimental and theoretical studies on the NLO properties of two quaternary non-centrosymmetric chalcogenides: BaAg 2 GeS 4 and BaAg 2 SnS 468A 3D neutral chalcogenide framework built from a supertetrahedral T3 cluster and a metal complex for the electrocatalytic oxygen reduction reaction12A facile synthesis of two new IR optical perovskites based on 1,4-diazabicyclo[2,2,2]octane with a high laser damage threshold7Design and synthesis of a nonlinear optical material BaAl 4 S 7 with a wide band gap inspired from SrB 4 O 764Na 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 performances31Sr 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)13Cs2Ge3In6Se14: A Structure Transformation Driven by the Size Preference and Its Properties8Strong SHG Response via High Orientation of Tetrahedral Functional Motifs in Polyselenide A2Ge4Se10 (A = Rb, Cs)31Nonbonding Electrons Driven Strong SHG Effect in Hg2GeSe4: Experimental and Theoretical Investigations61Ternary Mixed-Metal Cd4GeS6: Remarkable Nonlinear-Optical Properties Based on a Tetrahedral-Stacking Framework41Elucidating linear and nonlinear optical properties of defect chalcopyrite compounds ZnX2Te4 (X=Al, Ga, In) from electronic transitions13Adduct-Type IR Nonlinear-Optical Crystal SbI 3 ·(S 8 ) 3 with a Large Second-Harmonic Generation and a High Laser-Induced Damage Threshold59A review on structure-performance relationship toward the optimal design of infrared nonlinear optical materials with balanced performances253Transition metals doped fullerenes: structures – NLO property relationships26Pressure-Assisted Method for the Preparations of High-Quality AaGaS2 and AgGaGeS4 Crystals for Mid-Infrared Laser Applications11Ba10Zn7M6Q26: Two New Mid-infrared Nonlinear Optical Crystals with T2 Supertetrahedron 3D Framework11A 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 birefringences50Monoclinic gallium selenide: an AgGaS 2 -type structure variant with balanced infrared nonlinear optical performance43Pb 7 F 12 Cl 2 : a promising infrared nonlinear optical material with high laser damage threshold19Quaternary 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, crystal structures and nonlinear optical properties of β-RbCdI 3 ·H 2 O and CsCdI 3 ·H 2 O8Syntheses, structures, optical properties, and electronic structures of Ba6Cu2GSn4S16 (G = Fe, Ni) and Sr6D2FeSn4S16 (D = Cu, Ag)9Theoretical Design of Layered AlGaS3 as a New Nonlinear Optical Material with a Strong Second Harmonic Generation Response5Balanced Second-Order Nonlinear Optical Properties of Adducts CHI3·(S8)3 and AsI3·(S8)3: A Systematic Survey48Mixed-Anion Inorganic Compounds: A Favorable Candidate for Infrared Nonlinear Optical Materials140LiBa2MIIIQ4 (MIII = Al, Ga, In; Q = S, Se): A Series of Metal Chalcogenides with a Structural Transition12Rb10Zn4Sn4S17: A Chalcogenide with Large Laser Damage Threshold Improved from the Mn-Based Analogue28Li[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 Effects54Ba 13 In 12 Zn 7 S 38 and Ba 12 In 12 Zn 8 Se 38 : infrared nonlinear optical chalcogenides designed by zinc-induced non-centrosymmetry transformation22One-Dimensional Double Chains in Sodium-Based Quaternary Chalcogenides Displaying Intriguing Red Emission and Large Optical Anisotropy17Molecular 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 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 Materials55LiBa4Ga5Q12 (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)86[ABa2Cl][Ga4S8] (A = Rb, Cs): Wide-Spectrum Nonlinear Optical Materials Obtained by Polycation-Substitution-Induced Nonlinear Optical (NLO)-Functional Motif Ordering270Inherent laws between tetrahedral arrangement pattern and optical performance in tetrahedron-based mid-infrared nonlinear optical materials131Salt-Inclusion Chalcogenide [Ba4Cl2][ZnGa4S10]: Rational Design of an IR Nonlinear Optical Material with Superior Comprehensive Performance Derived from AgGaS2134Pb 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 μm38Phase Matching, Strong Frequency Doubling, and Outstanding Laser-Induced Damage Threshold in the Biaxial, Quaternary Diamond-like Semiconductor Li 4 CdSn 2 S 779A 3 Mn 2 Sb 3 S 8 (A = K and Rb): a new type of multifunctional infrared nonlinear optical material based on unique three-dimensional open frameworks53Synthesis, crystal structure, photocatalysis, photocurrent response: one-dimensional K 2 HgSnSe 4 and three-dimensional Na 6 Cu 8 Sn 3 Se 1323High Pressure Synthesis of the Spin Chain Sulfide Ba9V3S11(S2)29Inorganic Chalcogenides: From Zero‐Dimensional Clusters to Three‐Dimensional Frameworks5α-Ca2CdP2 and β-Ca2CdP2: Two Polymorphic Phosphide-Based Infrared Nonlinear Crystals with Distorted NLO-Active Tetrahedral Motifs Realizing Large Second Harmonic Generation Effects and Suitable Band Gaps30AZn4Ga5Se12 (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 properties13Solvothermal synthesis and properties of three antimony chalcogenides containing transition metal zinc13Li 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 Gap16Transition-metal-based chalcogenides: A rich source of infrared nonlinear optical materials184Ba4GeSb2Se11: An Infrared Nonlinear Optical Crystal with a V-Shaped Se32– Group Possessing a Large Contribution to the SHG Response8Solvothermal syntheses and characterization of three quaternary selenidoarsenates containing mercury [TM(en)3][HgAs2Se4](TM Mn, Ni, Zn)5Superior Infrared Nonlinear Optical Performance Achieved by Synergetic Functional Motif and Vacancy Site Modulations48Noncentrosymmetric chalcohalide K2Ba3Ge3S9Cl2: A new nonlinear optical material with remarkable laser-induced damage threshold17β-BaGa 4 Se 7 : a promising IR nonlinear optical crystal designed by predictable structural rearrangement46First-principles study of opto-electronic and thermoelectric properties of SrCdSnX4 (X=S, Se, Te) alkali metal chalcogenides35Phase Matchability Transformation in the Infrared Nonlinear Optical Materials with Diamond‐Like Frameworks63Alkali metal partial substitution-induced improved second-harmonic generation and enhanced laser-induced damage threshold for Ag-based sulfides21Li-Free ternary sulphide Cs 5 Ga 9 S 16 with excellent nonlinear optical performance similar to classic LiGaS 213Metal oxyhalides: an emerging family of nonlinear optical materials124A new salt-inclusion chalcogenide exhibiting distinctive [Cd11In9S26]3− host framework and decent nonlinear optical performances16AgGaSe2-Inspired Nonlinear Optical Materials: Tetrel Selenides of Alkali Metals and Mercury34A comprehensive review on metal chalcogenides with three-dimensional frameworks for infrared nonlinear optical applications115Transuranium Sulfide via the Boron Chalcogen Mixture Method and Reversible Water Uptake in the NaCuTS3 Family21Remarkable Infrared Nonlinear Optical, Dielectric, and Strong Diamagnetic Characteristics of Semiconducting K3[BiS3]5(Na0.74Ag1.26)BaSnS4: A New AgGaS2‐Type Nonlinear Optical Sulfide with a Wide Band Gap and High Laser Induced Damage Threshold14Ba 3 HgGa 2 S 7 : A Zero-Dimensional Quaternary Sulfide Featuring a Unique [Hg 2 Ga 4 S 14 ] 12– String and Exhibiting a High Photocurrent Response27Ternary AGa5S8 (A = K, Rb, Cs): Promising infrared nonlinear optical materials rationally realized by “one-for-multiple substitution” strategy37AeMg6Ga6S16 (Ae = Ca, Sr, Ba): The First Double Alkaline‐Earth Metal Chalcogenides with Excellent Performances29Oxychalcogenides: A Promising Class of Materials for Nonlinear Optical Crystals with Mixed‐Anion Groups35Na 2 Ba[Na 2 Sn 2 S 7 ]: Structural Tolerance Factor‐Guided NLO Performance Improvement50Na2Ba[Na2Sn2S7]: Structural Tolerance Factor‐Guided NLO Performance Improvement0Rational Design of a Rare‐Earth Oxychalcogenide Nd3[Ga3O3S3][Ge2O7] with Superior Infrared Nonlinear Optical Performance64Theoretical Prediction‐Assisted Synthesis and Characterization of Infrared Nonlinear Optical Material NaSrBS324Three‐in‐One Strategy Constructing the First High‐Performance Nonlinear Optical Sulfide Crystallizing with the P43 Space Group27[Ba4(S2)][ZnGa4S10]: Design of an Unprecedented Infrared Nonlinear Salt‐Inclusion Chalcogenide with Disulfide‐Bonds36Solvothermal syntheses and characterization of one-dimensional (1,4-dabH2)Cu1.72Ag0.28SnSe4 (1) and (1,4-dabH2)Cu2SnSe4 (2)0NaMn3Ga3S8: Noncentrosymmetric inorganic metal chalcogenide with nonlinear optical response, antiferromagnetic, and photoluminescence performances13Flexible Anionic Groups‐Activated Structure Dissymmetry for Strong Nonlinearity in Ln 2 Ae 3 M IV 3 S 12 Family16Torch-like high-performance NLO and electrochromic bifunctional molecular switch exhibiting superalkalide and superalkali metal salt characteristics7ZnGa 2 S 4 : an infrared nonlinear optical material with large second‐harmonic generation response and wide band gap29Ga-based IR nonlinear optical materials: Synthesis, structures, and properties65Polysulfide Anions [S x ] 2− ( x = 2, 3, 4, 5): Promising Functional Building Units for Infrared Nonlinear Optical Materials22DFT‐Based Investigation of Electronic, Optical, and Thermoelectric Properties of TaCu 3 X 4 (X = S, Se, Te) Chalcogenides for Optoelectronic and Energy Applications5From NaSc 3 Ga 2 Q 8 (Q = S, Se) to KGa 2 In 3 S 8 : substitution of Sc 3+ with In 3+ to achieve doubled birefringence17Isovalent cation substitution drives structural transformation and infrared nonlinear optical activity in Eu-based chalcogenides11AgGaS2 and Derivatives: Design, Synthesis, and Optical Properties10AI2Mg3Ga12S22 (AI = K, Rb): T2-type supertetrahedra coupled with [MgS6] octahedra for designing wide-band gap infrared nonlinear optical materials with well-balanced properties16Alkali Metal-adsorbed Graphyne and Graphdiyne (M@GY, M&GDY, M=Li or Na) as high-performance SP3T or 3P3T Near- and Mid-Far-infrared NLO molecular switches: A theoretical study0BaPb2Ga6Q12 (Q = S, Se): The first two compounds in the Ba–Pb-Ga-Q (Q = S, Se) systems0Discovering Pseudo-Supertetrahedral Functional Units in Salt-Inclusion Nonlinear Optical Material [Ba22(SO4)5][Zn14Ga18S58]14Cation Equivalent Multisubstitution Realizing Structure Transformation and Balanced Nonlinear Optical Performance of Quaternary Eu-Based Chalcogenides8Ba 10 Zn 7 Ga 6 S 26 : Promising Infrared Nonlinear Optical Crystal Exhibiting a High Laser Damage Threshold0SrZnGeSe4: An Infrared Nonlinear Optical Crystal Material with Wide Transmission Range and Large SHG Response7LnMg 6 Ga 6 S 16 (Ln = Nd, Sm), two bifunctional optical materials exhibiting both nonlinear optical and photoluminescent properties0高性能硫属化物红外非线性光学材料构效关系（特邀）0High‐Performance Infrared Nonlinear Optical Crystals Discovery Guided by High‐Throughput Computation, Machine Learning, and Experimental Verification6High‐Performance Infrared Nonlinear Optical Crystals Discovery Guided by High‐Throughput Computation, Machine Learning, and Experimental Verification3Interior-to-Exterior Transition of an Alkaline Earth Metal in B36 Nanocage: Excellent Full-infrared Single-Pole Triple-Throw (SP3T) NLO Molecular Switchable Effect–Theoretical Insight0A Composition-Matched Intermediate Reveals Site-Specific Symmetry Evolution with Retained Second-Harmonic Generation in Supertetrahedral Sulfides0

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