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RESEARCH PAPER · Journal of the American Chemical Society · 2022

AIB3IIC3IIIQ8VI: A New Family for the Design of Infrared Nonlinear Optical Materials by Coupling Octahedra and Tetrahedra Units

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AIB3IIC3IIIQ8VI: A New Family for the Design of Infrared Nonlinear Optical Materials by Coupling Octahedra and Tetrahedra UnitsOriginalRb 2 CdSi 4 S 10 : novel [Si 4 S 10 ] T2-supertetrahedra-contained infrared nonlinear optical material with large band gap79Na 2 Ba[Na 2 Sn 2 S 7 ]: Structural Tolerance Factor‐Guided NLO Performance Improvement50Na2Ba[Na2Sn2S7]: Structural Tolerance Factor‐Guided NLO Performance Improvement0A new infrared nonlinear optical material BaZnGeS 4 with a wide band gap and large nonlinear optical response34An overview of Mg-based IR nonlinear optical materials22Ba 3 (BS 3 )(PS 4 ): the first alkaline-earth metal thioborate–thiophosphate with strong optical anisotropy originating from planar [BS 3 ] units8Cs[B 3 O 3 F 2 (OH) 2 ]: discovery of a hydroxyfluorooxoborate guided by selective organic–inorganic transformation13From BPS 4 to AB 3 P 2 S 10 (A = Na, K): cations inducing dimension reduction and bandgap enlargement7From CdPb 8 (SeO 3 ) 4 Br 10 to Pb 3 (TeO 3 )Br 4 : the first tellurite bromide exhibiting an SHG response and mid-IR transparency21Honeycomb layered topology construction for exceptional long-wave infrared nonlinear optical crystals29Hydroxyfluorooxoborate (NH 4 )[C(NH 2 ) 3 ][B 3 O 3 F 4 (OH)] for exploring the effects of cation substitution on structure and optical properties26KRb 2 (NO 3 ) 2 Cl: a new birefringent crystal exhibiting a perovskite-related framework and a short cutoff edge6MB 3 P 2 S 10 (M = Rb, Cs): two new alkali metal thioboratephosphates with [B 6 P 4 S 20 ] T3-supertetrahedra2Recent progress on sulfide infrared nonlinear optical materials with large SHG response and wide band gap26Synthesis, structure and characterization of Cd 2 TeO 3 Cl 2 with unprecedented [Cd 2 O 6 Cl 4 ] octahedral dimers5The first polyanion-substitution-driven centrosymmetric-to-noncentrosymmetric structural transformation realizing an excellent nonlinear optical supramolecule [Cd 4 P 2 ][CdBr 4 ]17Recent advances of inorganic phosphates with UV/DUV cutoff edge and large second harmonic response7Unbiased Screening of Novel Infrared Nonlinear Optical Materials with High Thermal Conductivity: Long‐neglected Nitrides and Popular Chalcogenides12Unbiased Screening of Novel Infrared Nonlinear Optical Materials with High Thermal Conductivity: Long‐neglected Nitrides and Popular Chalcogenides48Enhancing Third-Order Nonlinear Optical Property by Regulating Interaction between Zr4(embonate)6 Cage and N, N-Chelated Transition-Metal Cation6Target‐Driven Design of Deep‐UV Nonlinear Optical Materials via Interpretable Machine Learning125Optimal Design of Mid-Infrared Nonlinear-Optical Crystals: From SrZnSnSe 4 to SrZnSiSe 422Theoretical Prediction‐Assisted Synthesis and Characterization of Infrared Nonlinear Optical Material NaSrBS324Na3SiS3F: A Wide Bandgap Fluorothiosilicate with Unique [SiS3F] Unit and High Laser‐Induced Damage Threshold39Cd2Nb2Te4O15: A Novel Pseudo‐Aurivillius‐Type Tellurite with Unprecedented Nonlinear Optical Properties and Excellent Stability40BaMo3O10 Polymorphs with Tunable Symmetries and Properties3Improved Birefringence Activated by Tetrahedra Decorated with a Single Linear Unit38Improved Birefringence Activated by Tetrahedra Decorated with a Single Linear Unit1Zn 2 HgP 2 S 8 : A Wide Bandgap Hg‐Based Infrared Nonlinear Optical Material with Large Second‐Harmonic Generation Response75Realization of flexible in-memory computing in a van der Waals ferroelectric heterostructure tri-gate transistor34Wide band gaps in nonlinear optical materials AMgAgGa6S11 (A = K, Rb) achieved by the incorporation of dual s-block elements in Ag-based sulfide11Heterologous Isomorphic Substitution Induces Optical Property Enhancement for Deep-UV Crystals: a Case in Rb[B3O3F2(OH)2]10Mixed Anionic Tetrahedra Guided Design of New Infrared Nonlinear Optical Material Cs 3 Ga 8 S 13 Cl with High Laser‐Induced Damage Threshold26A ll HgM IV S 4 (A ll = Sr, Ba, M IV = Si, Ge): A Series of Materials with Large Second Harmonic Generation Response and Wide Band Gaps27Double alkaline earth metals sulfide SrMgGeS4 with high laser-induced damage threshold and strong second-harmonic generation29Theoretical investigations on ternary defective diamond-like infrared nonlinear optical materials in Be-Ga-Se system18A prediction-driven database to enable rapid discovery of nonlinear optical materials46Flexible Anionic Groups‐Activated Structure Dissymmetry for Strong Nonlinearity in Ln 2 Ae 3 M IV 3 S 12 Family15A I B 3 II C 2 III Q 6 VI X VII : A Thioborate Halide Family for Developing Wide Bandgap Infrared Nonlinear Materials by Coupling Planar [BS 3 ] and Polycations25Na 6 Mg 3 P 4 S 16 and RbMg 2 PS 4 Cl 2 : two Mg-based thiophosphates with ultrawide bandgaps resulting from [MgS 6 ] and [MgS x Cl 6− x ] octahedra4Noncentrosymmetric Na6Pb3P4S16 and Centrosymmetric K2MIIP2S6 (MII = Mg and Zn) Displaying Multiple Membered-Ring Configurations and Strong Optical Anisotropy10K4ZnV5O15Cl: A Congruent‐Melting Mid‐Infrared Nonlinear Optical Crystal Combined with Strong Second‐Harmonic Generation and High Laser‐Induced Damage Threshold14Multifunctional Chiral d 10 ‐Metal Coordination Polymers: Tunable Photoluminescence and Efficient Second‐Harmonic Generation with Circular Dichroic Response18Fluorination strategy toward chemical and functional modification65Ga-based IR nonlinear optical materials: Synthesis, structures, and properties65“Three‐in‐One”: A New Hg‐Based Selenide Hg 7 P 2 Se 12 Exhibiting Wide Infrared Transparency Range and Strong Nonlinear Optical Effect80Chemical modulation of A I RE III C IV QVI4 family compounds for band gap and optical anisotropy enhancement16Discovery of a new bimetallic borate with strong optical anisotropy activated by π-conjugated [B 2 O 5 ] units3Effectively designing infrared nonlinear optical materials with magnetism, MMn 6 Ga 6 S 16 (M = Ca, Sr, Ba, and Pb), aided by stable open frameworks13Hg 3 AsS 4 X (X = Cl and Br): two Hg-based chalcogenides as long-wave infrared nonlinear optical crystals with superior comprehensive performances33Pb 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 gap2RbPbPS 4 : a promising IR nonlinear optical material achieved by lone-pair-cation-substitution-induced structure transformation23Reconstructing nearly isotropic microstructures to construct a one-dimensional framework causing record birefringence in thiophosphates13Salt-inclusion chalcogenides with d-orbital components: unveiling remarkable nonlinear optical properties and dual-band photoluminescence10Structural strategy for advancing nonlinear optical effects in 1D-[MX 2 ] ∞ chains: internal distortion and atomic types2Syntheses, crystal structures and photocurrent responses of Cs 2 Ag 2 Sb 2 S 5 and CsAgSb 4 S 7 with thiourea as a mineralizer4Theoretical prediction on the stability, elastic, electronic and optical properties of MAB-phase M 4 AlB 4 compounds (M = Cr, Mo, W)7Wide band gap selenide infrared nonlinear optical materials A II Mg 6 Ga 6 Se 16 with strong SHG responses and high laser-induced damage thresholds31β -CsHg 2 I 5 , a compound with rare [Hg 2 I 5 ] dimers and large optical anisotropy2Molecular Crystals Constructed by Polar Molecular Cages: A Promising System for Exploring High‐performance Infrared Nonlinear Optical Crystals6Molecular Crystals Constructed by Polar Molecular Cages: A Promising System for Exploring High‐performance Infrared Nonlinear Optical Crystals34Rational Design of Novel Promising Infrared Nonlinear Optical Materials: Structural Chemistry and Balanced Performances156Where do the Fluorine Atoms Go in Inorganic‐Oxide Fluorinations? A Fluorooxoborate Illustration under Terahertz Light1Where do the Fluorine Atoms Go in Inorganic‐Oxide Fluorinations? A Fluorooxoborate Illustration under Terahertz Light33Hg4(Te2O5)(SO4): A Giant Birefringent Sulfate Crystal Triggered by a Highly Selective Cation153Infrared nonlinear optical materials with multiple strongly ionic cations5LaMg6Ga6S16: a chemical stable divalent lanthanide chalcogenide70Na3K6(CO3)3(NO3)2X·6H2O (X = NO3, Cl, Br): Exploring High-Performance UV Birefringent Crystals Induced by Coplanar π-Conjugated CO3 and NO3 Groups15Tunable Optical Anisotropy in Rare‐Earth Borates with Flexible [BO3] Clusters7Homoatomic Polychalcogenide Nonlinear Optical Anionic Groups with Ultra-Large Optical Anisotropy31A Rare Earth Chalcogenide Nonlinear Optical Crystal KLaGeS4: Achieving Good Balance among Band Gap, Second Harmonic Generation Effect, and Birefringence12Ag 2 GeS 3 : A Diamond‐Like Chalcogenide as an IR Nonlinear Optical Material with Outstanding Second‐Harmonic Generation Response28[B3O3F4(OH)]2–: A Versatile Hydroxyfluorooxoborate Heteroanion Producing Compounds with Highly Tunable Optical Anisotropy19The centrosymmetric to non-centrosymmetric transformation induced by alkaline-earth cations producing infrared nonlinear optical AeMn6Ga6S16 (Ae = Ca, Sr)13β-Pb3P2S8: A new optical crystal with exceptional birefringence effect11FeSi4P4 and CoSi3P3: Hidden Gems of Ternary Tetrel Pnictides with Outstanding Nonlinear Optical Properties11Constructing Ultraviolet Nonlinear Optical Crystals with Superior Thermal Stability Based on Organic π-Conjugated [HCOO] Groups6Achieving strong optical nonlinearity and wide bandgap of pnictides via ionic motif–driven directed assembly of covalent groups39Achieving Phase‐Matching in Nonlinear Optical Materials CsM 2 In 2 S 6 (M = Cd/In, Hg/In) by the Incorporation of Unprecedented Trigonal Planar MS 3 Motifs6Computer‐Aided Development of New Nonlinear Optical Materials38Computer‐Aided Development of New Nonlinear Optical Materials14Design of High‐Performance Infrared Nonlinear Optical PAs 3 S 3 with Perfectly Aligned Polar Molecular Cage via a Bipolar‐Axis‐Symmetry Coupling Strategy16Design of High‐Performance Infrared Nonlinear Optical PAs 3 S 3 with Perfectly Aligned Polar Molecular Cage via a Bipolar‐Axis‐Symmetry Coupling Strategy8K6NaCaRe2(B5O10)3 (Re = Y, Lu): Two NLO Compounds Exhibiting a Short Absorption Edge in the A7–xA’xAeRe2(B5O10)3 (x = 0, 1) Family4Breaking Performance Barriers in KBe 2 BO 3 F 2 (KBBF) Analogs by Functional Group Self‐Polymerization5Breaking Performance Barriers in KBe 2 BO 3 F 2 (KBBF) Analogs by Functional Group Self‐Polymerization48Rare‐Earth Substitution Induced Symmetry Breaking for The First Sc‐Based Nonlinear Optical Chalcogenide with High‐Performance30A new ultraviolet-transparent molybdate featuring a layered structure and moderate birefringence0A wide band gap selenohalide Cs 9 Si 8 Se 20 Cl with unprecedented [CsSe 7 Cl] mixed anionic units2Ca 2 La(MS 4 )(BS 3 ) (M = Ge/Si and Sn/Si): high-performance infrared nonlinear optical materials designed using an atomic site co-occupancy strategy9Cationic substitution engineering induces a new quaternary chalcogenide in the A–M IIIA –M IVA –Q system for optical crystal applications1Cd 5 Te 4 O 12 X 2 (X = Cl, Br, I): a new oxyhalide family with [CdO 4 X] mixed anionic units and adjustable optical properties4Exploring the first and second hyperpolarizabilities of l -glutamine-based Schiff base ligands and their Cu( ii ) coordination complexes17From 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 birefringence17NaCaGa 3 S 6 : a mixed alkali metal and alkaline earth metal sulfide with a distinctive [Ga 5 S 10 ] ∞ layered framework0Non-centrosymmetric structures designed rationally via a “dimensionality addition” strategy toward the promising nonlinear optical family [A–X][In–Se] (A = K/Ba and Rb/Ba; X = Cl and Br)13Phase transition engineering to break the symmetry of diamond-like chalcogenide for second-order nonlinear optics2Prismatic crystal field stabilized divalent rare-earth chalcogenide REIIBII6CIII6QVI16 with bifunctionality30磷属红外非线性光学晶体带隙调控的可能策略(特邀)5Pb9Si8O22Cl6 and Pb3.07Ca1.93Si3O11: Two Ultraviolet Nonlinear Optical Materials Exhibit a Moderate Second Harmonic Generation Response1Experimental and theoretical investigation of nonlinear optical properties in novel anthracene-based chalcone compounds9AI2Mg3Ga12S22 (AI = K, Rb): T2-type supertetrahedra coupled with [MgS6] octahedra for designing wide-band gap infrared nonlinear optical materials with well-balanced properties16Nonlinear Optical Effects Modulated by Distinctive Monovalent Cations with Lone Electron Pairs in AGaI 4 (A = Ga + , In + )4Chalcophosphates: A plentiful source of infrared nonlinear optical materials42Expanding 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 Polycations29A new selenide semiconductor NaMn3Ga3Se8 with strong second-harmonic generation and significant luminescence property5Synergically Assembling Advantageous Groups toward High‐Performance Infrared Nonlinear Optical Materials A II CdSiSe 4 (A II = Sr, Ba)40SrZnGeSe 4 : a promising infrared nonlinear optical material with strong second harmonic generation and high laser-induced damage threshold4First-Principles High-Throughput Screening Combined with Experimental Synthesis to Find Vanadate Nonlinear Optical Material BiCa2VO64Synergistic Machine Learning Guided Discovery of ABa 3 (BSe 3 ) 2 X (A = Rb, Cs; X = Cl, Br, I): A Promising Family as Property‐Balanced IR Functional Materials10Cation Equivalent Multisubstitution Realizing Structure Transformation and Balanced Nonlinear Optical Performance of Quaternary Eu-Based Chalcogenides8Cd 7 I 12 Q·As 4 Q n (Q = S, Se; n = 3, 4): In Situ Alteration of Functional Molecules in Polar Metal Inorganic Framework Tailoring High‐Performance Infrared Nonlinear Optical Crystals9Research progress and future prospect of chalcogenides with large optical anisotropy46Achieving the birefringence-bandgap trade-off: Hydrogen-bond engineered biuret-cyanurate14From 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 Activity3SrZnSiS4: Shattering the 4.0 eV Threshold toward Dual-Optimized Bandgap and Second-Harmonic Generation5[HgX 2 ] Linear Group Enabled Ultraviolet Birefringent Crystal RbHg 5 Br 11 with Strong Optical Anisotropy and Wide Bandgap12LnEuGa3OS6 (Ln = La, Pr, Nd): three dual rare earth metal-based oxychalcogenides with good IR nonlinear optical performances1SrZnGeSe4: An Infrared Nonlinear Optical Crystal Material with Wide Transmission Range and Large SHG Response6NaAg3Ga8S14: A new diamond-like framework infrared nonlinear optical material derived from AgGaS26pH‐Regulated Ring‐Opening/Closing Transformation in Polyoxometalates Enables High‐Performance Nonlinear Optical Crystals1pH‐Regulated Ring‐Opening/Closing Transformation in Polyoxometalates Enables High‐Performance Nonlinear Optical Crystals13Stepwise Substitution Strategy for Beryllium-Based Selenites with Enhanced SHG Response, Moderate Birefringence, and Short UV Cutoff Edges6Tuning birefringence in alkaline-earth metal oxyhalides through diverse mixed-cation coordination architectures1A series of langasite-type compounds: size effect regulation for cation occupation and enhanced SHG response1Ba 4 Al 4 SnS 12 : balancing bandgap and nonlinear optical performance in thioaluminate via multifunctional group engineering0Broadband infrared-transparent crystals enabled by heterologous isomorphic substitution0KGdSiSe 4 and KGdGeSe 4 : two rare earth-based selenides with wide bandgaps and large nonlinear optical responses0KGdSiSe4 and KGdGeSe4: Two Rare Earth Metal-Based Selenides with Wide Bandgaps and Large Nonlinear Optical Responses0LnMg 6 Ga 6 S 16 (Ln = Nd, Sm), two bifunctional optical materials exhibiting both nonlinear optical and photoluminescent properties0Te–Se replacement induced structural transition and enhanced band gaps in Cd 5 Se 4 O 12 Cl 2 and Cd 5 Se 4 O 12 Br 21Confinement-assembled ultraviolet nonlinear optical crystal from pyridine-expanded π-systems with exhibiting strong SHG and birefringence18Realizing Phase‐Matching of Nonlinear Optical [ABa 3 Br 2 ][Ga 5 Se 10 ] (A = Cs, Rb, K, Na) Through Large Anisotropic Lattice Distortion6Realizing Phase‐Matching of Nonlinear Optical [ABa 3 Br 2 ][Ga 5 Se 10 ] (A = Cs, Rb, K, Na) Through Large Anisotropic Lattice Distortion11Harnessing tetrahedral diversity: The path to superior diamond-like IR NLO crystals13Topology-Guided Discovery of BaIn 2 Si 7 P 12 : A Quaternary Diamond-like Framework Phosphide with Giant Second-Harmonic Generation and High Laser-Induced Damage Threshold22CdY 2 Si 2 S 8 : A Wide Bandgap IR NLO Material with d 10 Metal-Induced Structure Transformation from CS to NCS1Polar Antiperovskite Oxides: Promising Mid-Infrared Nonlinear Optical Materials with Strong Second-Harmonic Generation2From Centrosymmetric Mg 2 GeS 4 to Noncentrosymmetric CdMg 3 Ge 2 S 8 : Cation-Mixing-Driven Symmetry Reduction4Achieving High‐Birefringence Thiophosphates From Low Polarizability Anisotropy Units by an Axial Linear Matching Strategy1Linear [ICl 2 ] Units Induced Giant Optical Anisotropy in AICl 2 (A = NH 4 , Rb): A Pathway to Advanced Birefringent Materials4First‐Principles Investigation of the Structural, Electronic, Optical, Elastic, and Thermal Properties of Defect Diamond‐Like Hg 3 P 2 S 80CaM 3 Si 4 P 11 (M = Al, Ga): [P 2 ] Motifs‐Modified Quasi‐T 3 Supertetrahedra Drive Superior Infrared Nonlinear Optical Performances1Mineral‐Inspired and Computation‐Assisted Rational Design of Polar Gittinsite‐Type Thiophosphates With Exceptional Nonlinear Optical Performance3AgEuPS4: Unlocking the Centrosymmetric Shackle of Rare-Earth Thiophosphates via Microscopic Distortion Cascading for Enhanced Second-Harmonic Generation Response0AlGaS3: a wide band gap ternary diamond-like infrared nonlinear optical material with high laser-induced damage threshold1Short-UV Metal Halide Nitrates: Moderate SHG in K3Sb(NO3)3F3 and Enhanced Optical Anisotropy in K3Zn(NO3)X4 (X = Cl, Br)0Homologous lattice coupling drives the formation of tetrahedra-ordered phase exhibiting enhanced optical nonlinearity and band gap0

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