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RESEARCH PAPER · Journal of Materials Chemistry C · 2014

Noncentrosymmetric chalcohalide NaBa 4 Ge 3 S 10 Cl with large band gap and IR NLO response

Kai Feng, Lei Kang, Zheshuai Lin, Jiyong Yao, Yicheng Wu

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Noncentrosymmetric chalcohalide NaBa 4 Ge 3 S 10 Cl with large band gap and IR NLO responseOriginalDevelopment of nonlinear optical materials promoted by density functional theory simulations32Ba 4 AgGa 5 Pn 8 (Pn = P, As): new pnictide-based compounds with nonlinear optical potential30BaGa 2 SnSe 6 : a new phase-matchable IR nonlinear optical material with strong second harmonic generation response58Expanding the structural versatility of thiostannate( iv ) complexes15Strong IR NLO Material Ba4MGa4Se10Cl2: Highly Improved Laser Damage Threshold via Dual Ion Substitution Synergy97Four new chalcohalides, NaBa2SnS4Cl, KBa2SnS4Cl, KBa2SnS4Br and CsBa2SnS4Cl: Syntheses, crystal structures and optical properties18Supercubooctahedron (Cs6Cl)2Cs5[Ga15Ge9Se48] Exhibiting Both Cation and Anion Exchange13Pb17O8Cl18: A Promising IR Nonlinear Optical Material with Large Laser Damage Threshold Synthesized in an Open System223Synthesis, crystal and electronic structure, and optical property of the pentanary chalcohalide Ba3KSb4S9Cl17Metal Thiophosphates with Good Mid-infrared Nonlinear Optical Performances: A First-Principles Prediction and Analysis441Synthesis, crystal structure, and optical property of the quaternary chalcohalide Ba4Sb3S8Cl14BaCdSnS 4 and Ba 3 CdSn 2 S 8 : syntheses, structures, and non-linear optical and photoluminescence properties97Pb 5 Ga 6 ZnS 15 : a noncentrosymmetric framework with chains of T2-supertetrahedra41Synthesis, crystal structure and second-order nonlinear optical property of a novel pentanary selenide (K 3 I)[InB 12 (InSe 4 ) 3 ]48The effect of indium substitution on the structure and NLO properties of Ba 6 Cs 2 Ga 10 Se 20 Cl 446Ba 3 FeS 4 Br: A 0D Iron‐Based Chalcohalide with Unusual Magnetic Properties9Na 2 Hg 3 M 2 S 8 (M = Si, Ge, and Sn): New Infrared Nonlinear Optical Materials with Strong Second Harmonic Generation Effects and High Laser-Damage Thresholds186Trigonal Planar [HgSe3]4– Unit: A New Kind of Basic Functional Group in IR Nonlinear Optical Materials with Large Susceptibility and Physicochemical Stability196Experimental and theoretical second harmonic generation and photoluminescence from the pseudo-centrosymmetric dihydrochloride salt dihydrate of trans-1,2-bis(4-pyridyl)ethene5Non‐centrosymmetric Selenides AZn4In5Se12 (A=Rb, Cs): Synthesis, Characterization and Nonlinear Optical Properties47Recent achievements on middle and far-infrared second-order nonlinear optical materials433Ba 6 Li 2 CdSn 4 S 16 : lithium substitution simultaneously enhances band gap and SHG intensity44Syntheses and characterization of three new sulfides with large band gaps: acentric Ba 4 Ga 4 SnS 12 , centric Ba 12 Sn 4 S 23 and Ba 7 Sn 3 S 1327Tailored synthesis of nonlinear optical quaternary chalcohalides: Ba 4 Ge 3 S 9 Cl 2 , Ba 4 Si 3 Se 9 Cl 2 and Ba 4 Ge 3 Se 9 Cl 252Two excellent phase-matchable infrared nonlinear optical materials based on 3D diamond-like frameworks: RbGaSn 2 Se 6 and RbInSn 2 Se 639Superpolyhedron-Built Second Harmonic Generation Materials Exhibit Large Mid-Infrared Conversion Efficiencies and High Laser-Induced Damage Thresholds101Mid-Infrared Nonlinear Optical Materials Based on Metal Chalcogenides: Structure–Property Relationship338Li3VO4: A Promising Mid-Infrared Nonlinear Optical Material with Large Laser Damage Threshold51A review of the structural chemistry and physical properties of metal chalcogenide halides147Large Second-Harmonic Generation Responses Achieved by the Dimeric [Ge2Se4(μ-Se2)]4– Functional Motif in Polar Polyselenides A4Ge4Se12 (A = Rb, Cs)49Oxyhalides: prospecting ore for optical functional materials with large laser damage thresholds76Crystal Structure and Optical Property of Quaternary Sulfide Ba2.77SnSb2.16S80Second-order nonlinear optical crystals with mixed anions250Modifying Disordered Sites with Rational Cations to Regulate Band-Gaps and Second Harmonic Generation Responses Markedly: Ba6Li2ZnSn4S16 vs Ba6Ag2ZnSn4S16 vs Ba6Li2.67Sn4.33S1625Intriguing Structural Transition Inducing Variable Birefringences in ABa2MS4Cl (A = Rb, Cs; M = Ge, Sn)32Combined experimental and theoretical investigations of Ba 3 GaS 4 I: interesting structural transformation originated from halogen substitution16Synthesis and nonlinear optical properties of new gallium thiophosphate Rb 2 Ga 2 P 2 S 913BaV2O6·H2O: A nonlinear optical crystal with a large bandgap7The first barium lead oxychloride Ba27Pb8O8Cl54 with new isolated [Pb4O4] clusters3Balanced Second-Order Nonlinear Optical Properties of Adducts CHI3·(S8)3 and AsI3·(S8)3: A Systematic Survey48[(Ba19Cl4)(Ga6Si12O42S8)]: a Two-Dimensional Wide-Band-Gap Layered Oxysulfide with Mixed-Anion Chemical Bonding and Photocurrent Response20Mixed-Anion Inorganic Compounds: A Favorable Candidate for Infrared Nonlinear Optical Materials140Li[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 Performance40A new type of novel salt-inclusion chalcogenide with ultralow thermal conductivity14Salt-inclusion chalcogenides: an emerging class of IR nonlinear optical materials54LiBa4Ga5Q12 (Q = S, Se): Noncentrosymmetric Metal Chalcogenides with a Cesium Chloride Topological Structure Displaying a Remarkable Laser Damage Threshold32[ABa2Cl][Ga4S8] (A = Rb, Cs): Wide-Spectrum Nonlinear Optical Materials Obtained by Polycation-Substitution-Induced Nonlinear Optical (NLO)-Functional Motif Ordering270Partial Isovalent Anion Substitution to Access Remarkable Second-Harmonic Generation Response: A Generic and Effective Strategy for Design of Infrared Nonlinear Optical Materials114First non-centrosymmetric antimony chalcogenides containing mixed cations of alkali and alkaline-Earth: Ba14Na4Sb11S31Cl3 featuring unique disorded 43 helical chains of [Sb5S18]21–5Structure-property survey and computer-assisted screening of mid-infrared nonlinear optical chalcohalides114Evaluation of nonlinear optical properties of quaternary chalcogenide halides Ba4Si3Se9Br2 and Ba4Ge3Se9Br222Salt-Inclusion Chalcogenide [Ba4Cl2][ZnGa4S10]: Rational Design of an IR Nonlinear Optical Material with Superior Comprehensive Performance Derived from AgGaS2134Two Mixed-Anion Units of [GeOSe3] and [GeO3S] Originating from Partial Isovalent Anion Substitution and Inducing Moderate Second Harmonic Generation Response and Large Birefringence55Ba3[LiSbS2(S2)2Cl2]: The first zero-dimensional (0D) lithium metal thioantimonate featuring molecular anions of [LiSbS2(S2)2Cl2]6–3From AgGaS 2 to AgHgPS 4 : vacancy defects and highly distorted HgS 4 tetrahedra double-induced remarkable second-harmonic generation response68Intriguing Dimensional Transition Inducing Variable Birefringence in K2Na2Sn3S8 and Rb3NaSn3Se828From thiophosphate to chalcohalide: mixed-anion AgS x Cl y ligands concurrently enhancing nonlinear optical effects and laser-damage threshold10M 6 PS 5 X (M = Ag, Cu; X = Cl, Br) chalcohalides exhibiting strong nonlinear optical responses and high laser damage resistances9Na 2 GaS 2 Cl: a new sodium-rich chalcohalide with two-dimensional [GaS 2 ] ∞ layers and wide interlayer space15RbPb 8 O 4 Cl 9 : the first alkali metal lead oxyhalide with distorted [PbO 3 Cl 3 ] and [PbOCl 5 ] mixed-anion groups6Structural diversities in centrosymmetric La 8 S 4 Cl 8 La 12 S 8 Cl 4 [SbS 3 ] 8 and non-centrosymmetric Ln 12 S 8 Cl 8 [SbS 3 ] 4 (Ln = La and Ce): syntheses, crystal and electronic structures, and optical properties10Synthesis, characterization and theoretical investigation of a new chalcohalide, Ba 4 GaS 4 F 311Quaternary Chalcohalides CdSnSX2 (X = Cl or Br) with Neutral Layers: Syntheses, Structures, and Photocatalytic Properties18AXHg3P2S8 (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]5−58Li 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 Gap16Noncentrosymmetric 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 materials129[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 ] clusters32From 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 materials19The synthesis and structure–property relation analysis of metal chalcohalide crystals Cs 2 InPS 4 X 2 (X = Cl, Br) with mixed anions6Cs2Bi2OSi2O7: A Promising Bismuth Silicate Nonlinear Optical Crystal with Face-Sharing BiO5 Polyhedra Exhibiting Strengthened Second Harmonic Generation Response and Birefringence43NaBaBS3: A Promising Infrared Functional Material with Large Birefringence Induced by π-Conjugated [BS3] Units32[Ba2F2][Ge2O3S2]: An Unprecedented Heteroanionic Infrared Nonlinear Optical Material Containing Three Typical Anions47Ag4SnGe2S7: A Noncentrosymmetric Chalcogenide in I4–II–IV2–VI7 System with Non-Diamond-Like Structure Featuring 1D ∞[SnGe2S8]6– Infinite Chain2Chalcohalides: A Rising Type of Second‐Order Nonlinear Optical Materials28AIB3IIC3IIIQ8VI: A New Family for the Design of Infrared Nonlinear Optical Materials by Coupling Octahedra and Tetrahedra Units152Recent Advances in Infrared Nonlinear Optical Crystal7[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 substitution12K2CdGe3S8: A New Infrared Nonlinear Optical Sulfide6Polar Phosphorus Chalcogenide Cage Molecules: Enhancement of Nonlinear Optical Properties in Adducts39Polar Phosphorus Chalcogenide Cage Molecules: Enhancement of Nonlinear Optical Properties in Adducts1Tunable 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 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 eV46Shooting mid-infrared nonlinear optical materials with targeted balance performances in ternary d0-transition metal oxides through first-principles14Cs4Zn5P6S18I2: the Largest Birefringence in Chalcohalide Achieved by Highly Polarizable Nonlinear Optical Functional Motifs22Exploring the Optoelectronic Potential of M2SnX3F2 (M = Sr, Ba; X = S, Se) Compounds Through First-Principles Analysis of Structural, Electronic, and Optical Properties15[RbSr 3 X][(BS 3 ) 2 ] (X = Cl, Br): two salt-inclusion thioborates with large birefringence and structure transformation from centrosymmetric to asymmetric8Pb 3.5 GeS 4 Br 3 : the first phase-matching thiogermanate halide infrared nonlinear optical material12Mixed-anion square-pyramid [SbS3I2] units causing strong second-harmonic generation intensity and large birefringence9Infrared nonlinear optical materials with multiple strongly ionic cations5Phase Matching of Infrared Nonlinear Optical Salt-Inclusion Chalcogenides Achieved by the Modulation of the Fractal Dimension of Anionic Motifs18[Cs14Cl][Tm71Se110]: An unusual salt-inclusion chalcogenide containing different valent Tm centers and ultralow thermal conductivity10Tin chalcohalide Sn 11 (PS 4 ) 4 I 10 obtained from structural-template-oriented synthesis: exhibiting balanced infrared nonlinear optical performance6A wide band gap selenohalide Cs 9 Si 8 Se 20 Cl with unprecedented [CsSe 7 Cl] mixed anionic units2Selenoborates: a latent structure resource for infrared functional crystal materials1Strain-engineered indirect-to-direct band gap transition, photocatalytic water splitting activity, and optical responses in ACuGa 6 S 10 (A = Rb and Cs)0Salt-Inclusion Rare-Earth Chalcogenides: Exploring Infrared Nonlinear Optical Crystals via a Guest-Framework Modulation Strategy0

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  1. Development of nonlinear optical materials promoted by density functional theory simulations

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  2. Ba 4 AgGa 5 Pn 8 (Pn = P, As): new pnictide-based compounds with nonlinear optical potential

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  3. BaGa 2 SnSe 6 : a new phase-matchable IR nonlinear optical material with strong second harmonic generation response

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  4. Expanding the structural versatility of thiostannate( iv ) complexes

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  5. Strong IR NLO Material Ba4MGa4Se10Cl2: Highly Improved Laser Damage Threshold via Dual Ion Substitution Synergy

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  6. Four new chalcohalides, NaBa2SnS4Cl, KBa2SnS4Cl, KBa2SnS4Br and CsBa2SnS4Cl: Syntheses, crystal structures and optical properties

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  7. Supercubooctahedron (Cs6Cl)2Cs5[Ga15Ge9Se48] Exhibiting Both Cation and Anion Exchange

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  8. Pb17O8Cl18: A Promising IR Nonlinear Optical Material with Large Laser Damage Threshold Synthesized in an Open System

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  9. Synthesis, crystal and electronic structure, and optical property of the pentanary chalcohalide Ba3KSb4S9Cl

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  10. Metal Thiophosphates with Good Mid-infrared Nonlinear Optical Performances: A First-Principles Prediction and Analysis

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  11. Synthesis, crystal structure, and optical property of the quaternary chalcohalide Ba4Sb3S8Cl

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  12. BaCdSnS 4 and Ba 3 CdSn 2 S 8 : syntheses, structures, and non-linear optical and photoluminescence properties

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  13. Pb 5 Ga 6 ZnS 15 : a noncentrosymmetric framework with chains of T2-supertetrahedra

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  14. Synthesis, crystal structure and second-order nonlinear optical property of a novel pentanary selenide (K 3 I)[InB 12 (InSe 4 ) 3 ]

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  15. The effect of indium substitution on the structure and NLO properties of Ba 6 Cs 2 Ga 10 Se 20 Cl 4

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  16. Ba 3 FeS 4 Br: A 0D Iron‐Based Chalcohalide with Unusual Magnetic Properties

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  17. Na 2 Hg 3 M 2 S 8 (M = Si, Ge, and Sn): New Infrared Nonlinear Optical Materials with Strong Second Harmonic Generation Effects and High Laser-Damage Thresholds

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  18. Trigonal Planar [HgSe3]4– Unit: A New Kind of Basic Functional Group in IR Nonlinear Optical Materials with Large Susceptibility and Physicochemical Stability

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  19. Experimental and theoretical second harmonic generation and photoluminescence from the pseudo-centrosymmetric dihydrochloride salt dihydrate of trans-1,2-bis(4-pyridyl)ethene

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  20. Non‐centrosymmetric Selenides AZn4In5Se12 (A=Rb, Cs): Synthesis, Characterization and Nonlinear Optical Properties

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  21. Recent achievements on middle and far-infrared second-order nonlinear optical materials

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  22. Ba 6 Li 2 CdSn 4 S 16 : lithium substitution simultaneously enhances band gap and SHG intensity

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  23. Syntheses and characterization of three new sulfides with large band gaps: acentric Ba 4 Ga 4 SnS 12 , centric Ba 12 Sn 4 S 23 and Ba 7 Sn 3 S 13

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  24. Tailored synthesis of nonlinear optical quaternary chalcohalides: Ba 4 Ge 3 S 9 Cl 2 , Ba 4 Si 3 Se 9 Cl 2 and Ba 4 Ge 3 Se 9 Cl 2

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  25. Two excellent phase-matchable infrared nonlinear optical materials based on 3D diamond-like frameworks: RbGaSn 2 Se 6 and RbInSn 2 Se 6

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  29. A review of the structural chemistry and physical properties of metal chalcogenide halides

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  30. Large Second-Harmonic Generation Responses Achieved by the Dimeric [Ge2Se4(μ-Se2)]4– Functional Motif in Polar Polyselenides A4Ge4Se12 (A = Rb, Cs)

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  31. Oxyhalides: prospecting ore for optical functional materials with large laser damage thresholds

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  32. Crystal Structure and Optical Property of Quaternary Sulfide Ba2.77SnSb2.16S8

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  33. Second-order nonlinear optical crystals with mixed anions

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  34. Modifying Disordered Sites with Rational Cations to Regulate Band-Gaps and Second Harmonic Generation Responses Markedly: Ba6Li2ZnSn4S16 vs Ba6Ag2ZnSn4S16 vs Ba6Li2.67Sn4.33S16

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  35. Intriguing Structural Transition Inducing Variable Birefringences in ABa2MS4Cl (A = Rb, Cs; M = Ge, Sn)

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  36. Combined experimental and theoretical investigations of Ba 3 GaS 4 I: interesting structural transformation originated from halogen substitution

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  37. Synthesis and nonlinear optical properties of new gallium thiophosphate Rb 2 Ga 2 P 2 S 9

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  38. BaV2O6·H2O: A nonlinear optical crystal with a large bandgap

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  39. The first barium lead oxychloride Ba27Pb8O8Cl54 with new isolated [Pb4O4] clusters

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  40. Balanced Second-Order Nonlinear Optical Properties of Adducts CHI3·(S8)3 and AsI3·(S8)3: A Systematic Survey

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  41. [(Ba19Cl4)(Ga6Si12O42S8)]: a Two-Dimensional Wide-Band-Gap Layered Oxysulfide with Mixed-Anion Chemical Bonding and Photocurrent Response

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  42. Mixed-Anion Inorganic Compounds: A Favorable Candidate for Infrared Nonlinear Optical Materials

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  43. Li[LiCs2Cl][Ga3S6]: A Nanoporous Framework of GaS4 Tetrahedra with Excellent Nonlinear Optical Performance

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  44. Li[LiCs2Cl][Ga3S6]: A Nanoporous Framework of GaS4 Tetrahedra with Excellent Nonlinear Optical Performance

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  45. A new type of novel salt-inclusion chalcogenide with ultralow thermal conductivity

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  46. Salt-inclusion chalcogenides: an emerging class of IR nonlinear optical materials

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  47. LiBa4Ga5Q12 (Q = S, Se): Noncentrosymmetric Metal Chalcogenides with a Cesium Chloride Topological Structure Displaying a Remarkable Laser Damage Threshold

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  48. [ABa2Cl][Ga4S8] (A = Rb, Cs): Wide-Spectrum Nonlinear Optical Materials Obtained by Polycation-Substitution-Induced Nonlinear Optical (NLO)-Functional Motif Ordering

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  49. Partial Isovalent Anion Substitution to Access Remarkable Second-Harmonic Generation Response: A Generic and Effective Strategy for Design of Infrared Nonlinear Optical Materials

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