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RESEARCH PAPER · Coordination Chemistry Reviews · 2021

Hg-based chalcogenides: An intriguing class of infrared nonlinear optical materials

Chunxiao Li, Xianghe Meng, Zhuang Li, Jiyong Yao

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Hg-based chalcogenides: An intriguing class of infrared nonlinear optical materialsOriginalAAg 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 sulfides21Ba 2 HgTe 5 : a Hg-based telluride with giant birefringence induced by linear [HgTe 2 ] units17From oxides to oxysulfides: the mixed-anion GeS 3 O unit induces huge improvement in the nonlinear optical effect and optical anisotropy for potential nonlinear optical materials19Homovalent Cation Substitutions Leading to New Lithium-Containing La3cusis7 Family Members Having Chiral, Uniaxial Structures and Exhibiting Second- and Third-Harmonic Generation7The Combination of Structure Prediction and Experiment for the Exploration of Alkali‐Earth Metal‐Contained Chalcopyrite‐Like IR Nonlinear Optical Material104AgGaSe2-Inspired Nonlinear Optical Materials: Tetrel Selenides of Alkali Metals and Mercury34Hg2P2S6: A layered mercury hexathiodiphosphate (IV) with large birefringence11(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 Response27Mixed-Anion-Oriented Design of LnMGa3S6O (Ln = La, Pr, and Nd; M = Ca and Sr) Nonlinear Optical Oxysulfides with Targeted Property Balance56Chalcohalides: A Rising Type of Second‐Order Nonlinear Optical Materials28Ag-based chalcogenides and derivatives as promising infrared nonlinear optical materials90[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 response34An overview of Mg-based IR nonlinear optical materials22From BPS 4 to AB 3 P 2 S 10 (A = Na, K): cations inducing dimension reduction and bandgap enlargement7Honeycomb layered topology construction for exceptional long-wave infrared nonlinear optical crystals29Lone-pair, electron-dominated, nonlinear optical responses in sulfur clusters and electric tunability properties11Na 6 Sn 3 P 4 S 16 : Sn( ii )-chelated PS 4 groups inspired an ultra-strong SHG response22Open honeycomb frameworks of sulphides AHg 4 Ga 5 S 12 (A = Rb, Cs) exhibiting infrared nonlinear optical properties12Recent progress on sulfide infrared nonlinear optical materials with large SHG response and wide band gap26The Kurtz–Perry Powder Technique Revisited: A Study of the Effect of Reference Selection on Powder Second-Harmonic Generation Response20Recent progress in the design of IR nonlinear optical materials by partial chemical substitution: Structural evolution and performance optimization133[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 eV46{[In2S7]8–}∞ Chain and Isolated HgS4 Planar Unit Constructed One-Dimensional Pentanary Sulfide K2Ba7HgIn4S16 Exhibiting Nonlinear-Optical Activity10HgB2S4: A d10 Metal Thioborate with Giant Birefringence and Wide Band Gap31Recent advances in IR nonlinear optical chalcogenides with well-balanced comprehensive performance56Improved Birefringence Activated by Tetrahedra Decorated with a Single Linear Unit38Improved Birefringence Activated by Tetrahedra Decorated with a Single Linear Unit1Synthesis, Crystal Structure, and Nonlinear-Optical Properties of a Diamond-Like Chalcogenide Cu 2 GeS 313Defect diamond-like tellurides as infrared nonlinear optical materials with giant second-harmonic generation tensor13Zn 2 HgP 2 S 8 : A Wide Bandgap Hg‐Based Infrared Nonlinear Optical Material with Large Second‐Harmonic Generation Response75Wide band gaps in nonlinear optical materials AMgAgGa6S11 (A = K, Rb) achieved by the incorporation of dual s-block elements in Ag-based sulfide11Structure–Property Relationships of ITIC-Based Acceptor–Donor–Acceptor Type Molecules as Novel Organic Nonlinear Optical Materials11Mixed 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 generation29Breaking Through the Trade‐Off Between Wide Band Gap and Large SHG Coefficient in Mercury‐Based Chalcogenides for IR Nonlinear Optical Application49A Machine Learning Study on High Thermal Conductivity Assisted to Discover Chalcogenides with Balanced Infrared Nonlinear Optical Performance58Na 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 ] octahedra4A2Hgx(SeO3)y (A = K, Rb, Cs): Three Alkali Metal Mercury Selenites Featuring Unique 1D [HgOm(SeO3)n]∞ Chains13Regulating the key performance parameters for Hg-based IR NLO chalcogenides via bandgap engineering strategy26Ga-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 Effect80Ba4Cd2Ge2Te9: A promising infrared functional crystal with large birefringent and photoluminescence properties2Computer-aided screening of bismuth molybdates nonlinear optical crystals γ -Bi 2 MoO 63Enhanced near-infrared optical transmission in zinc germanium phosphide crystals via precise magnesium doping3Hg 3 AsS 4 X (X = Cl and Br): two Hg-based chalcogenides as long-wave infrared nonlinear optical crystals with superior comprehensive performances33Quality Improvement of Baga 4 Se 7 Crystal by Annealing in Base Vapor Atmosphere2Rare-earth oxychalcogenide Eu 2 ZnGe 2 OS 6 : a phase-matching infrared nonlinear optical material with [GeOS 3 ] units7Rare-earth-based chalcogenides and their derivatives: an encouraging IR nonlinear optical material candidate70Salt-inclusion chalcogenides with d-orbital components: unveiling remarkable nonlinear optical properties and dual-band photoluminescence10Syntheses, crystal structures and photocurrent responses of Cs 2 Ag 2 Sb 2 S 5 and CsAgSb 4 S 7 with thiourea as a mineralizer4β -CsHg 2 I 5 , a compound with rare [Hg 2 I 5 ] dimers and large optical anisotropy2基于光参量振荡及放大技术的长波固体激光研究进展8Molecular 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 Crystals34UV-Transparent SHG Material Explored in an Alkali Metal Sulfate Selenite System16Evaluation and prospect of Mid-Infrared nonlinear optical materials in f0 rare earth (RE = Sc, Y, La) chalcogenides44Infrared nonlinear optical materials with multiple strongly ionic cations5The first Hg-based oxychalcogenide Sr2HgGe2OS6: Achieving balanced IR nonlinear optical properties through synergistic cation and anion substitution28Sr2HgGe2OS6: A Hg-Based Oxychalcogenide Infrared Nonlinear Optical Material Exhibiting Favorable Balance between a Large Band Gap and Strong Second Harmonic Generation Response10EuSi7P10: An Inorganic Supramolecular Nonlinear Optical Crystal Exhibiting Strong Second-Harmonic Generation Response4Old tree blossoms anew: Research progress on the structures and optical properties of ultraviolet selenites56Quality improvement of BaGa4Se7 crystal by annealing in BaSe vapor atmosphere8Ag 2 GeS 3 : A Diamond‐Like Chalcogenide as an IR Nonlinear Optical Material with Outstanding Second‐Harmonic Generation Response28Sulfate Derivatives with Heteroleptic Tetrahedra: New Deep‐Ultraviolet Birefringent Materials in which Weak Interactions Modulate Functional Module Ordering61Sulfate Derivatives with Heteroleptic Tetrahedra: New Deep‐Ultraviolet Birefringent Materials in which Weak Interactions Modulate Functional Module Ordering4K2HgGe3Se8: A Quaternary Hg-Based Selenide with Nonlinear Optical Properties6Achieving 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 Materials14Hg4InS2Cl5: Achieving Giant Optical Anisotropy by Introducing Well‐Aligned Linear [Hg2S2] Units14Emergent Mid‐Infrared Nonlinear Optical Candidates With Targeted Balance Performances17(C 6 H 5 N 2 )HgCl 3 : Discovery of a Polar Hg‐Based Hybrid Halide as Preeminent Nonlinear Optical and Birefringent Material Activated by π‐Conjugated Organic Cation Substitution38(CN 4 H 7 ) 2 SO 4 ·H 2 O: high-performance metal-free ultraviolet birefringent crystal with KBBF-like configuration5A wide band gap selenohalide Cs 9 Si 8 Se 20 Cl with unprecedented [CsSe 7 Cl] mixed anionic units2A π-conjugated organic molecule-modified strategy to achieve high-performance metal nitrate birefringent crystals9Alkali metal/mercury dual-metal sulfides as infrared nonlinear optical materials with high laser-induced damage thresholds5AgGaS2 and Derivatives: Design, Synthesis, and Optical Properties8Prediction and Evaluation of Li 2 ZnS 2 Crystals as Mid‐Infrared Nonlinear Optical Material with High Thermal Conductivity7Chalcophosphates: A plentiful source of infrared nonlinear optical materials42Synergically Assembling Advantageous Groups toward High‐Performance Infrared Nonlinear Optical Materials A II CdSiSe 4 (A II = Sr, Ba)40From Orthorhombic Cu8GeS6 to Cubic Cu6HgGeS6: Second-Harmonic Generation and Photocurrent Responses7Mild solvothermal syntheses, crystal structures, characterizations and properties of four ternary alkaline earth metal sulfides1From AgHgI(SO4) to AgHg3I3.2Cl1.8(SO4): Symmetry Breaking of the Belousovite‐Type Topology by Mixed Halides to Achieve Strong Nonlinear Optical Effect14Polyaniline-modified cathode interface for enhanced mercury electroreduction recovery0Pressure optimized 2D-IV monochalcogenide for enhanced photovoltaic performance in skyscraper-integrated solar cell: A computational insight2Recent progress in structural design strategies of high-birefringence optical crystals54Cation Equivalent Multisubstitution Realizing Structure Transformation and Balanced Nonlinear Optical Performance of Quaternary Eu-Based Chalcogenides8Planar [HgCl 3 ] and V‑Shaped [HgCl 2 ] Units Synergistically Creating a Prominent Halide Birefringent Crystal β ‐CsHg 2 Cl 5 with Wide‐Spectrum7Cd 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 Crystals9Diamond-Like HgIn2Q4 (Q = Se, Te) Synthesized by Flux-Assisted Boron-Chalcogen Method Exhibit Noteworthy Nonlinear Optical Properties Contributed by Three Types of Tetrahedral Motifs8From Centrosymmetric Ca3Ge2O3S4 to Noncentrosymmetric Ca3Ge2O4Se3: A Nonlinear Optical Ca-Based Oxyselenide5Chiral BN-Heteroacenes Embedded with B←N Coordination: Acid-Triggered Reversible Bond Switching and Optical Limiting Behavior5AlGaSe3: Tuning Stability via Partial Cation Substitution and Achieving a Nonlinear Optical Property Leap6Syntheses, Structures, and Characterizations of Two Superatom-Based Cubic Perovskites0LiPb 3 GeS 4 Cl 3 : Quasi‐T 2 ‐Supertetrahedral 3D Framework Enabling Superior Optical Performance14LiPb 3 GeS 4 Cl 3 : Quasi‐T 2 ‐Supertetrahedral 3D Framework Enabling Superior Optical Performance3NaAg3Ga8S14: A new diamond-like framework infrared nonlinear optical material derived from AgGaS26Reactive flux assisted metal oxide–boron–sulfur routine for syntheses of CsRESiS 4 (RE = Sm, Gd–Ho): featuring nonlinear optical activity and wide band gaps5Ba-based IR nonlinear optical materials: synthesis, growth, structures, and properties6Structural Symmetry and Mixed‐anion Engineering in Halopnictides for Extraordinary Second‐Harmonic Generation6Structural Symmetry and Mixed‐anion Engineering in Halopnictides for Extraordinary Second‐Harmonic Generation3A mercury-based selenite with wide bandgap and moderate birefringence via cation substitution and partial fluorination1van der Waals layered CuInP 2 S 6 as infrared nonlinear optical material1高性能硫属化物红外非线性光学材料构效关系（特邀）0Selenium-Based Molecular Cage Crystal β-P 4 Se 3 Br 2 : A Promising Candidate for Infrared Nonlinear Optical Applications1Solvothermal Syntheses, Characterization, and Properties of Five Quaternary Thioarsenates and Thioantimonates0Harnessing tetrahedral diversity: The path to superior diamond-like IR NLO crystals13Origin of Large Second-Harmonic Generation in Nonpolar Molybdenum Tellurite Compounds0{[Ge 2 S 7 ] 6– } ∞ Chains-Mediated Framework Reorganization Triggers Dimensional Upgrade and Infrared Nonlinear Optical Response3CdY 2 Si 2 S 8 : A Wide Bandgap IR NLO Material with d 10 Metal-Induced Structure Transformation from CS to NCS1Recent Progress in Hg-Based Oxysalt Crystals for Nonlinear Optics and Birefringence Applications5The Power of Pnictogen Bond: As─As Linkages Drive Wide Bandgap, Strong NLO Response and Large Birefringence in SrGa 3 Si 4 As 115The Power of Pnictogen Bond: As─As Linkages Drive Wide Bandgap, Strong NLO Response and Large Birefringence in SrGa 3 Si 4 As 110Circumventing the Eg–SHG trade-off in selenides: Salt-inclusion [X4Br2][MGa4Se10] with concurrent large band gap and strong nonlinear optical response1Steric hindrance and hydrogen-bond networks synergistically directing molecular alignment for high-performance ultraviolet birefringent1Structure–Property Correlation for Third‐Order Nonlinear Optical Performance of Achiral Tetradentate Aminophosphine Metal Complexes: Role of Metal and Conjugation Pathways0Rb 2 ZnGe 3 Se 8 : A Large-Birefringence Layered Chalcogenide Enabled by Anisotropic Electrons in Tetrahedral Units0Salt-Inclusion Rare-Earth Chalcogenides: Exploring Infrared Nonlinear Optical Crystals via a Guest-Framework Modulation Strategy0Mid‐ to Far‐Infrared Nonlinear Optical Crystals: Design Strategies, Structure–Property Relationships and Engineering Prospects0First‐Principles Investigation of the Structural, Electronic, Optical, Elastic, and Thermal Properties of Defect Diamond‐Like Hg 3 P 2 S 80Chalcogenide glasses for nonlinear photonics: Structure-nonlinearity relationship and fundamental tradeoff1Cation-substitution-driven electronic, nonlinear optical, elastic, and thermal transport properties of layered AeHgGeSe4 (Ae = Ba, Sr): A first-principles study0d-f synergistic effect contributing record-high second-harmonic generation response in phase-matchable Mn-based chalcogenides0AlGaS3: a wide band gap ternary diamond-like infrared nonlinear optical material with high laser-induced damage threshold1

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  1. AAg 2 PS 4 (A = K, Na/K): the first-type of noncentrosymmetric alkali metal Ag-based thiophosphates exhibiting excellent second-order nonlinear optical performances

    Inorganic Chemistry Frontiers · 2022-01-01

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  2. Alkali metal partial substitution-induced improved second-harmonic generation and enhanced laser-induced damage threshold for Ag-based sulfides

    Inorganic Chemistry Frontiers · 2022-01-01

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  3. Ba 2 HgTe 5 : a Hg-based telluride with giant birefringence induced by linear [HgTe 2 ] units

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  4. From oxides to oxysulfides: the mixed-anion GeS 3 O unit induces huge improvement in the nonlinear optical effect and optical anisotropy for potential nonlinear optical materials

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  5. Homovalent Cation Substitutions Leading to New Lithium-Containing La3cusis7 Family Members Having Chiral, Uniaxial Structures and Exhibiting Second- and Third-Harmonic Generation

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  6. The Combination of Structure Prediction and Experiment for the Exploration of Alkali‐Earth Metal‐Contained Chalcopyrite‐Like IR Nonlinear Optical Material

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  7. AgGaSe2-Inspired Nonlinear Optical Materials: Tetrel Selenides of Alkali Metals and Mercury

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  8. Hg2P2S6: A layered mercury hexathiodiphosphate (IV) with large birefringence

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  9. (Na0.74Ag1.26)BaSnS4: A New AgGaS2‐Type Nonlinear Optical Sulfide with a Wide Band Gap and High Laser Induced Damage Threshold

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  10. Ba 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 Response

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  11. Mixed-Anion-Oriented Design of LnMGa3S6O (Ln = La, Pr, and Nd; M = Ca and Sr) Nonlinear Optical Oxysulfides with Targeted Property Balance

    ACS Applied Materials & Interfaces · 2022-08-11

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  12. Chalcohalides: A Rising Type of Second‐Order Nonlinear Optical Materials

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  13. Ag-based chalcogenides and derivatives as promising infrared nonlinear optical materials

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  14. [Sr 4 Cl 2 ][Si 3 S 9 ]: Ultrawide-bandgap salt-inclusion thiosilicate nonlinear optical material with unprecedented tri-polymerized [Si 3 S 9 ] clusters

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  15. A new infrared nonlinear optical material BaZnGeS 4 with a wide band gap and large nonlinear optical response

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  16. An overview of Mg-based IR nonlinear optical materials

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  17. From BPS 4 to AB 3 P 2 S 10 (A = Na, K): cations inducing dimension reduction and bandgap enlargement

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  18. Honeycomb layered topology construction for exceptional long-wave infrared nonlinear optical crystals

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  19. Lone-pair, electron-dominated, nonlinear optical responses in sulfur clusters and electric tunability properties

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  20. Na 6 Sn 3 P 4 S 16 : Sn( ii )-chelated PS 4 groups inspired an ultra-strong SHG response

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  21. Open honeycomb frameworks of sulphides AHg 4 Ga 5 S 12 (A = Rb, Cs) exhibiting infrared nonlinear optical properties

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  22. Recent progress on sulfide infrared nonlinear optical materials with large SHG response and wide band gap

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  23. The Kurtz–Perry Powder Technique Revisited: A Study of the Effect of Reference Selection on Powder Second-Harmonic Generation Response

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  24. Recent progress in the design of IR nonlinear optical materials by partial chemical substitution: Structural evolution and performance optimization

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  28. Recent advances in IR nonlinear optical chalcogenides with well-balanced comprehensive performance

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  29. Improved Birefringence Activated by Tetrahedra Decorated with a Single Linear Unit

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  31. Synthesis, Crystal Structure, and Nonlinear-Optical Properties of a Diamond-Like Chalcogenide Cu 2 GeS 3

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  32. Defect diamond-like tellurides as infrared nonlinear optical materials with giant second-harmonic generation tensor

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  33. Zn 2 HgP 2 S 8 : A Wide Bandgap Hg‐Based Infrared Nonlinear Optical Material with Large Second‐Harmonic Generation Response

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  34. Wide band gaps in nonlinear optical materials AMgAgGa6S11 (A = K, Rb) achieved by the incorporation of dual s-block elements in Ag-based sulfide

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  35. Structure–Property Relationships of ITIC-Based Acceptor–Donor–Acceptor Type Molecules as Novel Organic Nonlinear Optical Materials

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  36. Mixed Anionic Tetrahedra Guided Design of New Infrared Nonlinear Optical Material Cs 3 Ga 8 S 13 Cl with High Laser‐Induced Damage Threshold

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  37. A 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 Gaps

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  38. Double alkaline earth metals sulfide SrMgGeS4 with high laser-induced damage threshold and strong second-harmonic generation

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  39. Breaking Through the Trade‐Off Between Wide Band Gap and Large SHG Coefficient in Mercury‐Based Chalcogenides for IR Nonlinear Optical Application

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  40. A Machine Learning Study on High Thermal Conductivity Assisted to Discover Chalcogenides with Balanced Infrared Nonlinear Optical Performance

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  41. Na 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 ] octahedra

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    Yi Chu Huang, Dongdong Chu, Xueling Hou, Guangmao Li, Yong an Zhang

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  42. A2Hgx(SeO3)y (A = K, Rb, Cs): Three Alkali Metal Mercury Selenites Featuring Unique 1D [HgOm(SeO3)n]∞ Chains

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    Jinxuan Ren, Hui Cui, Linhong Cheng, Yuqiao Zhou, Xuehua Dong, Daojiang Gao, Ling Huang, Liling Cao, Ning Ye

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  43. Regulating the key performance parameters for Hg-based IR NLO chalcogenides via bandgap engineering strategy

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  44. Ga-based IR nonlinear optical materials: Synthesis, structures, and properties

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    Jiaxiang Zhang, Ping Feng, Mao‐Yin Ran, Xintao Wu, Hua Lin, Qi‐Long Zhu

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  45. “Three‐in‐One”: A New Hg‐Based Selenide Hg 7 P 2 Se 12 Exhibiting Wide Infrared Transparency Range and Strong Nonlinear Optical Effect

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