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RESEARCH PAPER · Coordination Chemistry Reviews · 2020

Inherent laws between tetrahedral arrangement pattern and optical performance in tetrahedron-based mid-infrared nonlinear optical materials

Weikang Wang, Dajiang Mei, Fei Liang, Jun Zhao, Yuandong Wu, Zheshuai Lin

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Inherent laws between tetrahedral arrangement pattern and optical performance in tetrahedron-based mid-infrared nonlinear optical materialsOriginalChalcophosphates: A Treasure House of Infrared Nonlinear Optical Materials75A novel promising infrared nonlinear optical selenide KAg 3 Ga 8 Se 14 designed from benchmark AgGaQ 2 (Q = S, Se)55Recent Achievements in Lone-Pair Cation-Based Infrared Second-Order Nonlinear Optical Materials95[GaF(H 2 O)][IO 3 F]: a promising NLO material obtained by anisotropic polycation substitution42A 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 tensors31Breaking through the “3.0 eV wall” of energy band gap in mid-infrared nonlinear optical rare earth chalcogenides by charge-transfer engineering145Recent progress in oxychalcogenides as IR nonlinear optical materials79A comprehensive survey on nonlinear optical phosphates: Role of multicoordinate groups106Introduction 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 Anion22Synthesis, structure, melting and optical properties of three complex orthorhombic sulfides BaDyCuS3, BaHoCuS3 and BaYbCuS318Cyanurates consisting of intrinsic planar π-conjugated 6-membered rings: An emerging source of optical functional materials112Structure-performance relationship in tri-coordinated nonlinear optical materials toward optimal second harmonic generation and phase matching31Cs2ZnSn3S8: A Sulfide Compound Realizes a Large Birefringence by Modulating the Dimensional Structure25AZn4Ga5Se12 (A = K, Rb, or Cs): Infrared Nonlinear Optical Materials with Simultaneous Large Second Harmonic Generation Responses and High Laser-Induced Damage Thresholds34Recent advances in nonlinear optical rare earth structures63Stepwise Li Substitution Induced Structure Evolution and Improved Nonlinear Optical Performance for Diamond-like Sulfides28Transition-metal-based chalcogenides: A rich source of infrared nonlinear optical materials184The Rise of Infrared Nonlinear Optical Pnictides: Advances and Outlooks36Synthesis, structure, and nonlinear optical property of Bi0.33Sb0.67SI1Signature Of stiffness transition in electrical behaviour of Se-Te-Sn-Ge glassy alloys1Machine Learning with Multilevel Descriptors for Screening of Inorganic Nonlinear Optical Crystals35Noncentrosymmetric chalcohalide K2Ba3Ge3S9Cl2: A new nonlinear optical material with remarkable laser-induced damage threshold17Halogen-Ion-Induced Structural Phase Transition Giving a Polymorph of HgBr2 with Balanced Nonlinear Optical Properties8Complex coordinated functional groups: A great genes for nonlinear optical materials65Hg-based chalcogenides: An intriguing class of infrared nonlinear optical materials129Structural Chemistry and Excellent Nonlinear Optical Properties of a Series of Ternary Selenides GaxIn2–xSe322Partial congener substitution induced centrosymmetric to noncentrosymmetric structural transformation and nonlinear optical properties of PbSnSiS413AAg 2 PS 4 (A = K, Na/K): the first-type of noncentrosymmetric alkali metal Ag-based thiophosphates exhibiting excellent second-order nonlinear optical performances21Bridging oxygen atoms in trigonal prism units driven strong second-harmonic-generation efficiency in Sr 3 Ge 2 O 4 Te 318Phase 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 via dual-site aliovalent substitution leads to an outstanding IR nonlinear optical material with well-balanced comprehensive properties69The exploration of new infrared nonlinear optical crystals based on the polymorphism of BaGa 4 S 731Two-step nonlinear optical switch in a hydrogen-bonded perovskite-type crystal15A new salt-inclusion chalcogenide exhibiting distinctive [Cd11In9S26]3− host framework and decent nonlinear optical performances16Quaternary Noncentrosymmetric Rare-Earth Sulfides Ba4RE2Cd3S10 (RE = Sm, Gd, or Tb): A Joint Experimental and Theoretical Investigation17Optimizing the Nonlinear Optical Performance of an A-N-M-Q (A: Alkali Metal; N: d10 Metal; M: Main Group Metal; Q: Chalcogen) System44From 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 Substitution22Design of a diamond-like infrared nonlinear optical material LiBS2 with ultra-wide band gap11SrZnSnSe4: A quaternary selenide with large second harmonic generation and birefringence40Targeted ginkgo kernel biomass precursor using eco-friendly synthesis of efficient carbon quantum dots for detection of trace nitrite ions and cell imaging44Enhanced Second-Harmonic-Generation Efficiency and Birefringence in Melillite Oxychalcogenides Sr2MGe2OS6 (M = Mn, Zn, and Cd)97Crystal Growth, Characterization, and Thermal Annealing of Nonlinear Optical Crystals AgGaGenSe2(n+1) (n = 1.5, 1.75, 2, 3, 4, 5, and 9) for Mid-infrared Applications12Heteroanionic Melilite Oxysulfide: A Promising Infrared Nonlinear Optical Candidate with a Strong Second-Harmonic Generation Response, Sufficient Birefringence, and Wide Bandgap65Li2Mg2Si2S6 and Li2Mg2Ge2S6: Two nonlinear optical sulfides featuring a unique, polar trigonal structure incorporating ethane‐like anions5AgGaGeSe4: An Infrared Nonlinear Quaternary Selenide with Good Performance6A comprehensive review on metal chalcogenides with three-dimensional frameworks for infrared nonlinear optical applications115(Na0.74Ag1.26)BaSnS4: A New AgGaS2‐Type Nonlinear Optical Sulfide with a Wide Band Gap and High Laser Induced Damage Threshold14Ag4SnGe2S7: A Noncentrosymmetric Chalcogenide in I4–II–IV2–VI7 System with Non-Diamond-Like Structure Featuring 1D ∞[SnGe2S8]6– Infinite Chain2Simple yet extraordinary: Super-polyhedra-built 3D chalcogenide framework of Cs5Ga9S16 with excellent infrared nonlinear optical performance29Characterizations and Nonlinear-Optical Properties of Pentanary Transition-Metal Oxysulfide Sr2CoGe2OS626AIB3IIC3IIIQ8VI: A New Family for the Design of Infrared Nonlinear Optical Materials by Coupling Octahedra and Tetrahedra Units152AeMg6Ga6S16 (Ae = Ca, Sr, Ba): The First Double Alkaline‐Earth Metal Chalcogenides with Excellent Performances29Ag-based chalcogenides and derivatives as promising infrared nonlinear optical materials90Growth and characterization of IR nonlinear optical PbIn6Te10 crystal3[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 new infrared nonlinear optical material BaZnGeS 4 with a wide band gap and large nonlinear optical response34Honeycomb layered topology construction for exceptional long-wave infrared nonlinear optical crystals29LaAeAl 3 S 7 (Ae = Ca, Sr): Cairo pentagonal layered thioaluminates achieving a good balance between a strong second harmonic generation response and a wide bandgap23Na 6 Sn 3 P 4 S 16 : Sn( ii )-chelated PS 4 groups inspired an ultra-strong SHG response22Recent progress on sulfide infrared nonlinear optical materials with large SHG response and wide band gap26The first quaternary rare-earth oxythiogermanate with second-harmonic generation and ferromagnetic behavior26Organic Nonlinear Optical Crystals for Highly Efficient Terahertz-Wave Generation36Phase Competition and Strong SHG Responses of the Li2MIIMIVSe4 Family: Atom Response Theory Predictions versus Experimental Results24Recent 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)23Optimal Design of Mid-Infrared Nonlinear-Optical Crystals: From SrZnSnSe 4 to SrZnSiSe 423Structure and Optical Properties of LixAg1–xGaSe2 and LixAg1–xInSe27Theoretical Prediction‐Assisted Synthesis and Characterization of Infrared Nonlinear Optical Material NaSrBS324Crystal Growth, Thermal Treatment, and Characterization of Nonlinear Optical Crystal LiGa0.5In0.5Se2 for Mid-infrared Applications8Synthesis, Structure, and optical properties of Y3GaGe0.5S7: A new member in the polar R3MTQ7 family4Inherent law of SHG and phase-matching in 0D NLO materials: Permutation tetra-coordinated groups2Three‐in‐One Strategy Constructing the First High‐Performance Nonlinear Optical Sulfide Crystallizing with the P43 Space Group27Recent advances in IR nonlinear optical chalcogenides with well-balanced comprehensive performance57[Ba4(S2)][ZnGa4S10]: Design of an Unprecedented Infrared Nonlinear Salt‐Inclusion Chalcogenide with Disulfide‐Bonds36Zn 2 HgP 2 S 8 : A Wide Bandgap Hg‐Based Infrared Nonlinear Optical Material with Large Second‐Harmonic Generation Response75Three-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 Threshold26Evolution of Structures and Optical Properties in a Series of Infrared Nonlinear Optical Crystals LixAg1–xInSe2 (0 ≤ x ≤ 1)12Double 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 system18Adduct‐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 Application49Regulating the key performance parameters for Hg-based IR NLO chalcogenides via bandgap engineering strategy26Ga-based IR nonlinear optical materials: Synthesis, structures, and properties65Nonlinear Optical Phosphide CuInSi2P4: The Inaugural Member of Diamond-Like Family I–III–IV2–V4 Inspired by ZnGeP216Multi-step cation substitution facilitating the exploration of potential infrared nonlinear optical materials6RbPbPS 4 : a promising IR nonlinear optical material achieved by lone-pair-cation-substitution-induced structure transformation23Structural strategy for advancing nonlinear optical effects in 1D-[MX 2 ] ∞ chains: internal distortion and atomic types2Wide band gap selenide infrared nonlinear optical materials A II Mg 6 Ga 6 Se 16 with strong SHG responses and high laser-induced damage thresholds31Cs 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 Grafting2Design of Pentanary Mixed-Chalcogenides Ag2In2SiS6–xSex (x = 1, 2) Based on the Bucket Effect: Local Structural Difference and High-Performance Nonlinear-Optical Properties Realized by Partial Congener Substitution5The first Hg-based oxychalcogenide Sr2HgGe2OS6: Achieving balanced IR nonlinear optical properties through synergistic cation and anion substitution28Phase Matching of Infrared Nonlinear Optical Salt-Inclusion Chalcogenides Achieved by the Modulation of the Fractal Dimension of Anionic Motifs18A Rare Earth Chalcogenide Nonlinear Optical Crystal KLaGeS4: Achieving Good Balance among Band Gap, Second Harmonic Generation Effect, and Birefringence13Effects of different groups on phase-matching and SHG in “3+4” Pn materials0β-Pb3P2S8: A new optical crystal with exceptional birefringence effect12A Congruent-Melt Infrared Nonlinear Optical Crystal Na4SrAs2S83Phase-Matching Second-Harmonic Generation and Enhanced Laser-Induced Damage Threshold Induced by Cs Substitution: Cu 3 PSe 4 vs Cs 2 CuP 3 S 94A 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 applications1Isovalent cation substitution drives structural transformation and infrared nonlinear optical activity in Eu-based chalcogenides11The sensitization effects of Ni 2+ on Ho 3+ 3.9 μm luminescence in PbF 2 single crystal6新型非线性光学晶体和双折射晶体的研究进展（特邀）4磷属红外非线性光学晶体带隙调控的可能策略（特邀）5Assembly 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 crystals6Nonlinear Optical Effects Modulated by Distinctive Monovalent Cations with Lone Electron Pairs in AGaI 4 (A = Ga + , In + )4Second-Harmonic Generation Response in Nitridophosphates MP2N4 (M = Ge, Sn, Pb) and the Role of Stereochemically Active Lone Pairs6A Series of Pentanary Rare-Earth Oxysulfides Obtained by Heterovalent Cation and Anion Cosubstitution Exhibiting Nonlinear Optical Activity and Ultrawide Band Gaps1First-principles study of ABSe₃ (A = Li, Na) Perselenoborates: A Promising Family of Nonlinear Optical Materials1Patterning and Dynamics of Structured Surfaces in Metal/Covalent Organic Frameworks and Polymer Chemistry5Structure-property relationships in IR nonlinear optical chalcogenides with stereochemically active lone pairs29SrZnSiS4: Shattering the 4.0 eV Threshold toward Dual-Optimized Bandgap and Second-Harmonic Generation7Maximizing the second-harmonic generation response via coordination-induced localization of nonbonding electrons12Ba 4 Al 4 SnS 12 : balancing bandgap and nonlinear optical performance in thioaluminate via multifunctional group engineering0KHg 4 Ga 5 S 12 : A Diamond-like Tetrahedral Chalcogenide Exhibiting Giant Phase-Matching Second Harmonic Generation6Origin of Large Second-Harmonic Generation in Nonpolar Molybdenum Tellurite Compounds0Crystal chemical aspects of solid solutions – natural resources, applications and basic research1Mg Substitution in BaGa 4 Se 7 : Synthesis, Structure, and Property Modulation2Achieving phase matching in infrared nonlinear optical crystal Cd3ZnSiS6 via isovalent substitution from Cd4SiS60K 3 Mg 2 [K 6 MgCl 3 ][Ga 20 S 36 ]: A Diamond-like Framework Based on Mixed-Type Supertetrahedra for Excellent Nonlinear Optical Property1Circumventing the Eg–SHG trade-off in selenides: Salt-inclusion [X4Br2][MGa4Se10] with concurrent large band gap and strong nonlinear optical response1From 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 Properties0Beyond the bandgap bottleneck: structure–property design principles for infrared nonlinear optical phosphides0A Composition-Matched Intermediate Reveals Site-Specific Symmetry Evolution with Retained Second-Harmonic Generation in Supertetrahedral Sulfides0

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