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RESEARCH PAPER · Chemistry of Materials · 2020

Salt-Inclusion Chalcogenide [Ba4Cl2][ZnGa4S10]: Rational Design of an IR Nonlinear Optical Material with Superior Comprehensive Performance Derived from AgGaS2

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Salt-Inclusion Chalcogenide [Ba4Cl2][ZnGa4S10]: Rational Design of an IR Nonlinear Optical Material with Superior Comprehensive Performance Derived from AgGaS2OriginalA new type of novel salt-inclusion chalcogenide with ultralow thermal conductivity14Salt-inclusion chalcogenides: an emerging class of IR nonlinear optical materials54Sr6(Li2Cd)A4S16 (A = Ge, Sn): How to Go beyond the Band Gap Limitation via Site-Specific Modification40Ultralow thermal conductivity in the quaternary semiconducting chalcogenide Cs 4 [Ho 26 Cd 7 Se 48 ] with an unprecedented closed cavity architecture7Hydrogen-Bond-Assisted Alignment of [MCu(SeO 3 ) 4 Cl(H 2 O)] 4– (M = Fe, Ga) Anionic Layers to Form Two Polar Oxychlorides: Pb 2 MCu(SeO 3 ) 4 Cl(H 2 O)10A 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 frameworks53Aliovalent-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 tensors31M 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 anions70A Series of Pentanary Salt-Inclusion Chalcogenoborates Containing a B12Q12 (Q = S, Se) Cluster Exhibiting a Kleinman-Forbidden Frequency-Doubling Effect25Quaternary Chalcohalides CdSnSX2 (X = Cl or Br) with Neutral Layers: Syntheses, Structures, and Photocatalytic Properties18Structural Modulation from Cu 3 PS 4 to Cu 5 Zn 0.5 P 2 S 8 : Single-Site Aliovalent-Substitution-Driven Second-Harmonic-Generation Enhancement28AXHg3P2S8 (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]5−58From K[ZnBP2O8] to K[(Zn0.5Al0.5)2P2O8]: Substitution-Induced Microporous Zincoaluminophosphate with a Congruent-Melting Behavior5Solvothermal Syntheses of Three-Dimensional Open-Framework Thioantimonates Displaying Nonlinear Optical Responses5Transition-metal-based chalcogenides: A rich source of infrared nonlinear optical materials184The Rise of Infrared Nonlinear Optical Pnictides: Advances and Outlooks36H{[Na(H2O)3]6F}(PO4)2 ⋅ 2(H2O): A New Polycation‐Type Phosphate with Deep Ultraviolet Transparency0Superior 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 threshold17Designing A New Infrared Nonlinear Optical Material, β‐BaGa 2 Se 4 Inspired by the Phase Transition of the BaB 2 O 4 (BBO) Crystal75Designing A New Infrared Nonlinear Optical Material, β‐BaGa2Se4 Inspired by the Phase Transition of the BaB2O4 (BBO) Crystal13Hg-based chalcogenides: An intriguing class of infrared nonlinear optical materials128Partial congener substitution induced centrosymmetric to noncentrosymmetric structural transformation and nonlinear optical properties of PbSnSiS413Phase 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 ] clusters32Achieving a strong second harmonic generation response and a wide band gap in a Hg-based material41CsAB 8 O 12 F 2 ·CsI (A = K + , NH 4 + ): design of two fluorooxoborates with benign layered structures via a salt-inclusion strategy28First polar quaternary sulphide CsLiGa 6 S 10 with mixed ordered alkali cations displaying excellent infrared nonlinear optical properties16Phase matching achieved by isomorphous substitution in IR nonlinear optical material Ba 2 SnSSi 2 O 7 with an undiscovered [SnO 4 S] functional motif47Rational design of a promising oxychalcogenide infrared nonlinear optical crystal60Rational design via dual-site aliovalent substitution leads to an outstanding IR nonlinear optical material with well-balanced comprehensive properties68The synthesis and structure–property relation analysis of metal chalcohalide crystals Cs 2 InPS 4 X 2 (X = Cl, Br) with mixed anions6From Cc to P 6 3 mc : Structural Variation in La 3 S 2 Cl 2 [SbS 3 ] and La 3 OSCl 2 [SbS 3 ] Induced by the Isovalent Anion Substitution22NaGa3Se5: An Infrared Nonlinear Optical Material with Balanced Performance Contributed by Complex {[Ga3Se5]−}∞ Anionic Network14Enhanced Second-Harmonic-Generation Efficiency and Birefringence in Melillite Oxychalcogenides Sr2MGe2OS6 (M = Mn, Zn, and Cd)97BaSi7P10 and SrSi7P10: Two Infrared Nonlinear Optical Phosphides with T2 Supertetrahedra Exhibiting Strong Second‐Harmonic Generation Effects22Novel pull–push organic switches with D–π–A structural designs: computational design of star shape organic materials38Design of Infrared Nonlinear Optical Compounds with Diamond-like Structures and Balanced Optical Performance9A comprehensive review on metal chalcogenides with three-dimensional frameworks for infrared nonlinear optical applications114Efficient Strategy for Investigating the Third-Order Nonlinear Optical (NLO) Properties of Solid-State Coordination Polymers34Oxychalcogenides as Promising Ultraviolet Nonlinear Optical Candidates: Experimental and Theoretical Studies of AEGeOS2(AE = Sr and Ba)24Simple yet extraordinary: Super-polyhedra-built 3D chalcogenide framework of Cs5Ga9S16 with excellent infrared nonlinear optical performance29Ternary AGa5S8 (A = K, Rb, Cs): Promising infrared nonlinear optical materials rationally realized by “one-for-multiple substitution” strategy37Chalcohalides: A Rising Type of Second‐Order Nonlinear Optical Materials28AeMg6Ga6S16 (Ae = Ca, Sr, Ba): The First Double Alkaline‐Earth Metal Chalcogenides with Excellent Performances29Rb 2 CdSi 4 S 10 : novel [Si 4 S 10 ] T2-supertetrahedra-contained infrared nonlinear optical material with large band gap79The Antiperovskite‐Type Oxychalcogenides Ae3Q[GeOQ3] (Ae = Ba, Sr; Q = S, Se) with Large Second Harmonic Generation Responses and Wide Band Gaps68Ba5Ga2SiO4S6: a Phase-Matching Nonlinear Optical Oxychalcogenide Design via Structural Regulation Originated from Heteroanion Introduction25Oxychalcogenides: A Promising Class of Materials for Nonlinear Optical Crystals with Mixed‐Anion Groups35[Ba 4 X][In 19 S 32 ] (X = Cl, Br): two quaternary metal chalcohalides exhibiting remarkable photocurrent responses1[Sr 4 Cl 2 ][Si 3 S 9 ]: Ultrawide-bandgap salt-inclusion thiosilicate nonlinear optical material with unprecedented tri-polymerized [Si 3 S 9 ] clusters21A non-centrosymmetric chalcohalide synthesized through the combination of chemical tailoring with aliovalent substitution12An overview of Mg-based IR nonlinear optical materials22Breaking the bottleneck of simultaneously wide band gap and large nonlinear optical coefficient by a “pore reconstruction” strategy in a salt-inclusion chalcogenide26LaAeAl 3 S 7 (Ae = Ca, Sr): Cairo pentagonal layered thioaluminates achieving a good balance between a strong second harmonic generation response and a wide bandgap23Melilite oxychalcogenide Sr 2 FeGe 2 OS 6 : a phase-matching IR nonlinear optical material realized by isomorphous substitution30Recent progress on sulfide infrared nonlinear optical materials with large SHG response and wide band gap26Tunable Salt-Inclusion Chalcogenides for Ion Exchange, Photoluminescence, and Scintillation12Salt-inclusion chalcogenides: Double functional moieties design strategy toward excellent nonlinear optical materials12Recent progress in the design of IR nonlinear optical materials by partial chemical substitution: Structural evolution and performance optimization133Rational Design of a Rare‐Earth Oxychalcogenide Nd3[Ga3O3S3][Ge2O7] with Superior Infrared Nonlinear Optical Performance64Partial substitution induced structural transformation and enhanced nonlinear optical properties of Na2GaxIn6-xSe10 (x = 3, 3.76)23[K2PbX][Ga7S12] (X = Cl, Br, I): The First Lead‐Containing Cationic Moieties with Ultrahigh Second‐Harmonic Generation and Band Gaps Exceeding the Criterion of 2.33 eV46Na3SiS3F: A Wide Bandgap Fluorothiosilicate with Unique [SiS3F] Unit and High Laser‐Induced Damage Threshold39Recent advances in IR nonlinear optical chalcogenides with well-balanced comprehensive performance56[Ba4(S2)][ZnGa4S10]: Design of an Unprecedented Infrared Nonlinear Salt‐Inclusion Chalcogenide with Disulfide‐Bonds36Advances in Chalcogenide Crystal Growth: Flux and Solution Syntheses, and Approaches for Postsynthetic Modifications13Halide-Induced Band Gap Enhancement from Ba2SnSe4 to KBa2SnSe4Cl2Three-in-One Tetrahedral Functional Units Constructing Diamondlike Ag2In2SiS3.06Se2.94 with High-Performance Nonlinear-Optical Activity4Mixed Anionic Tetrahedra Guided Design of New Infrared Nonlinear Optical Material Cs 3 Ga 8 S 13 Cl with High Laser‐Induced Damage Threshold26Excellent Nonlinear Optical M[M4Cl][Ga11S20] (M = A/Ba, A = K, Rb) Achieved by Unusual Cationic Substitution Strategy20Adduct‐Type Compounds for Nonlinear Optical Crystals0Breaking Through the Trade‐Off Between Wide Band Gap and Large SHG Coefficient in Mercury‐Based Chalcogenides for IR Nonlinear Optical Application49Advances in Solid-State Nonlinear Optical Materials: From Fundamentals to Applications61K4ZnV5O15Cl: A Congruent‐Melting Mid‐Infrared Nonlinear Optical Crystal Combined with Strong Second‐Harmonic Generation and High Laser‐Induced Damage Threshold14Regulating the key performance parameters for Hg-based IR NLO chalcogenides via bandgap engineering strategy26Ga-based IR nonlinear optical materials: Synthesis, structures, and properties65Ba 2 GeF 2 Q 3 (Q = S, Se) and Ba 3 GeF 2 Se 4 : new F-based chalcohalides with enhanced birefringence9Pb 3.5 GeS 4 Br 3 : the first phase-matching thiogermanate halide infrared nonlinear optical material12Pb 6 Ba 3 Si 2 S 8 I 10 : a new thiohalide with a quasi-two-dimensional structure and wide band gap2Rare-earth-based chalcogenides and their derivatives: an encouraging IR nonlinear optical material candidate70RbPbPS 4 : a promising IR nonlinear optical material achieved by lone-pair-cation-substitution-induced structure transformation23Salt-inclusion chalcogenides with d-orbital components: unveiling remarkable nonlinear optical properties and dual-band photoluminescence10Salt-inclusion sulfides [K 4 Cl][M II 11 In 9 S 26 ] (M II = Zn, Cd) displaying robust nonlinear optical activity4Cs 3 In(In 4 Se 7 )(P 2 Se 6 ): A Multi‐Chromophore Chalcogenide with Excellent Nonlinear Optical Property Designed by Group Grafting55Cs3In(In4Se7)(P2Se6): A Multi‐Chromophore Chalcogenide with Excellent Nonlinear Optical Property Designed by Group Grafting2KREP 2 S 6 (RE = Sm, Gd, Tb, Dy): A Series of Polar Rare-Earth Thiophosphates with High Laser-Induced Damage Thresholds and Moderate Nonlinear-Optical Responses Synergistically Contributed by Isolated P 2 S 6 Units and {[RE 2 S 15 ] 24– } ∞ Layers8Ba10In2Mn11Si3O12S18: First Hexanary Oxychalcogenide Containing an Infrequent Three-Dimensional Noncentrosysmmetric Framework8[Na2PbI][Ga7S12]: Combining Diamond-Like Anionic Framework with Polycationic Chain toward Achieving Remarkable Nonlinear Optical Response21[Rb3BaCl][In8Se14]: Compressed chalcopyrite-type selenide achieved by polycationic substitution strategy toward excellent nonlinear optical property18EuSi7P10: An Inorganic Supramolecular Nonlinear Optical Crystal Exhibiting Strong Second-Harmonic Generation Response4Recent advances and future perspectives on rare-earth-based nonlinear optical materials with π-conjugated [XO3] (X = B, C, N) units66Ag 2 GeS 3 : A Diamond‐Like Chalcogenide as an IR Nonlinear Optical Material with Outstanding Second‐Harmonic Generation Response28AAg2MS4 (A = Na, K, Rb; M = P, As) Nonlinear Optical Series with Unique Cation‐Regulated Highly Anisotropic [AgS4] Hypertetrahedral Layered Framework10[Cs14Cl][Tm71Se110]: An unusual salt-inclusion chalcogenide containing different valent Tm centers and ultralow thermal conductivity10Realizing Excellent Infrared Nonlinear Optical Performance in Eu-Based Chalcogenides via Rational Cross Substitution Strategy26ACuGa 6 S 10 (A = Rb, Cs): Design and Synthesis of Two New Cavity‐Chalcopyrite Chalcogenides Based on “Iterative Substitution” Strategy4Balanced IR Nonlinear Optical Performance Achieved by Cation–Anion Module Cosubstitution in V-Based Salt-Inclusion Oxychalcogenides22Emergent Mid‐Infrared Nonlinear Optical Candidates With Targeted Balance Performances17A wide band gap selenohalide Cs 9 Si 8 Se 20 Cl with unprecedented [CsSe 7 Cl] mixed anionic units2Isovalent cation substitution drives structural transformation and infrared nonlinear optical activity in Eu-based chalcogenides11AgGaS2 and Derivatives: Design, Synthesis, and Optical Properties8Assembly between diverse polycations and diamond-like anionic frameworks in salt-inclusion phosphides enables excellent nonlinear optical properties4Two-in-one: assembling hybrid supertetrahedra chromophores and achieving high-performance “hexagonal warriors” in nonlinear optical crystals6Expanding the Spectral Range in T2‐Supertetrahedral Nonlinear Optical Chalcogenides via Incorporating Inorganic Polycations4Expanding the Spectral Range in T2‐Supertetrahedral Nonlinear Optical Chalcogenides via Incorporating Inorganic Polycations29Discovering Pseudo-Supertetrahedral Functional Units in Salt-Inclusion Nonlinear Optical Material [Ba22(SO4)5][Zn14Ga18S58]14Nonbonding Electron Inversion‐Driven Structural Engineering: Synergistic Enhancement of Linear and Nonlinear Optical Properties3Nonbonding Electron Inversion‐Driven Structural Engineering: Synergistic Enhancement of Linear and Nonlinear Optical Properties26KYSiSe 4 : A Rare-Earth Selenide Infrared Nonlinear Optical Crystal with Wide Infrared Transparency and Well-Balanced E g and SHG Response9Achieving excellent nonlinear optical performance via “dimensionality elevation”-driven transformation from centrosymmetric to non-centrosymmetric structures1From Centrosymmetric Eu 2 Ga 2 S 5 to Noncentrosymmetric EuMg 6 Ga 6 S 16 via Introduction of Distorted MgS 6 Octahedron: Featuring Wide Bandgap and Nonlinear Optical Activity3Synergistic Enhancement of Band Gap and Optical Anisotropy via Functional-Site Cosubstitution in Antiperovskite-Type Chalcohalides [Ba2K][X][MS4] (M = Ge, Si; X = Cl, Br)2Structure-property relationships in IR nonlinear optical chalcogenides with stereochemically active lone pairs29Ba 10 Zn 7 Ga 6 S 26 : Promising Infrared Nonlinear Optical Crystal Exhibiting a High Laser Damage Threshold0A high-performance IR nonlinear optical material Sr 3 MnGe 2 S 8 achieved via partial cation substitution-induced structural transformation2Maximizing the second-harmonic generation response via coordination-induced localization of nonbonding electrons12Ba-based IR nonlinear optical materials: synthesis, growth, structures, and properties6[Rb 4 Cl][Cd 11 In 9 Se 26 ]: a salt inclusion chalcogenide with a diamond-like framework for infrared nonlinear optics0Strain-engineered indirect-to-direct band gap transition, photocatalytic water splitting activity, and optical responses in ACuGa 6 S 10 (A = Rb and Cs)0[Ba2K][Br][SiS4]: An antiperovskite-type chalcohalide with simultaneously enhanced birefringence and band gap via cation-anion co-substitution0K 3 Mg 2 [K 6 MgCl 3 ][Ga 20 S 36 ]: A Diamond-like Framework Based on Mixed-Type Supertetrahedra for Excellent Nonlinear Optical Property1Heterovalent Coexistence‐Driven Symmetry Breaking and Dimensional Evolution: Designing Polar Heart‐Shaped Channels for Exceptional MFIR Nonlinear Optics5Defect Diamond‐Like d 10 Metal Indium Selenium With Strong Second‐Harmonic Generation and Enhanced Laser‐Induced Damage Threshold2A Rigid‐Flexible Cooperative Bond‐Engineering Strategy for the Rational Design of Advanced Infrared Nonlinear Optical Crystals2Breaking Layered Limitations via Electrostatic-to-Covalent Conversion toward Three-Dimensional T2-Cluster-Based Chalcogenides7From KBa 4 Ge 3 S 10 Cl to ABa 3 EuGe 3 S 11 (A = Na, K) Synthesized by Reactive Flux Assisted Metal Oxide-Boron-Chalcogen (MOBQ) Method: Effect of Cation/Anion Cosubstitution on Crystal Structure and Nonlinear Optical Properties0Achieving Excellent Nonlinear Optics in α ‑Ba 2 Ge 4 S 10 via Flux‑Induced Symmetry Breaking1First‐Principles Investigation of the Structural, Electronic, Optical, Elastic, and Thermal Properties of Defect Diamond‐Like Hg 3 P 2 S 80A new phase and transformation mechanism in BaGa4Se7 infrared nonlinear optical crystal0Eu5ZnGa6S15, Eu5Zn3Ga2Sn2S15, and Pb5HgGa6S15: Crystal Chemistry and Nonlinear Optical Properties0From AgGaSe2 to MIIGa2Se4 (MII = Zn, Cd): Heterovalent Substitution Creates Ordered Vacancies for Balanced IR-NLO Performance0[La3Br][GeS4]2: Cationic-Moiety-Guided Strategy Enables Record Birefringence and Broad Optical Window0

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