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RESEARCH PAPER · Chemistry of Materials · 2018

Function of Tetrahedral ZnS3O Building Blocks in the Formation of SrZn2S2O: A Phase Matchable Polar Oxysulfide with a Large Second Harmonic Generation Response

Yoshihiro Tsujimoto, Christian A. Juillerat, Weiguo Zhang, Kotaro Fujii, Masatomo Yashima, P. Shiv Halasyamani, Hans‐Conrad zur Loye

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Function of Tetrahedral ZnS3O Building Blocks in the Formation of SrZn2S2O: A Phase Matchable Polar Oxysulfide with a Large Second Harmonic Generation ResponseOriginalMixed-Anion Compounds: A New Trend in Solid State Chemistry3A zinc-based oxysulfide photocatalyst SrZn 2 S 2 O capable of reducing and oxidizing water26Synthesis, crystal structures and optical properties of noncentrosymmetric oxysulfides AeGeS 2 O (Ae = Sr, Ba)45Sr 6 Cd 2 Sb 6 O 7 S 10 : Strong SHG Response Activated by Highly Polarizable Sb/O/S Groups124Sr6Cd2Sb6O7S10: Strong SHG Response Activated by Highly Polarizable Sb/O/S Groups22La2USe3S2: A Serendipitously Grown Lanthanide/Actinide Chalcogenide from a Eutectic Halide Flux3Molten Alkali Halide Flux Growth of an Extensive Family of Noncentrosymmetric Rare Earth Sulfides: Structure and Magnetic and Optical (SHG) Properties47One-Dimensional Quaternary and Penternary Alkali Rare Earth Thiophosphates Obtained via Alkali Halide Flux Crystal Growth12Synthesis, Crystal Structure, and Optical Characterization of the Sulfide Chloride Oxide CsBa6V4S12ClO4 with a Near-Infrared Fluorescence3Creating visible-to-near-infrared mechanoluminescence in mixed-anion compounds SrZn2S2O and SrZnSO145Nearly Identical but Not Isotypic: Influence of Lanthanide Contraction on Cs2NaLn(PS4)2 (Ln = La–Nd, Sm, and Gd–Ho)23Frustrated Magnetism in Triangular Lattice TlYbS2 Crystals Grown via Molten Flux14Metal Oxysulfides: From Bulk Compounds to Nanomaterials77Flux Crystal Growth, Structure, and Optical Properties of the New Germanium Oxysulfide La4(GeS2O2)35Oxysulfide Ba5(VO2S2)2(S2)2 Combining Disulfide Channels and Mixed-Anion Tetrahedra and Its Third-Harmonic-Generation Properties15Partial Isovalent Anion Substitution to Access Remarkable Second-Harmonic Generation Response: A Generic and Effective Strategy for Design of Infrared Nonlinear Optical Materials114Sr5Ga8O3S14: A Nonlinear Optical Oxysulfide with Melilite-Derived Structure and Wide Band Gap48Luminescence in Manganese (II)-Doped SrZn2S2O Crystals From Multiple Energy Conversion31Two Mixed-Anion Units of [GeOSe3] and [GeO3S] Originating from Partial Isovalent Anion Substitution and Inducing Moderate Second Harmonic Generation Response and Large Birefringence55From AgGaS 2 to AgHgPS 4 : vacancy defects and highly distorted HgS 4 tetrahedra double-induced remarkable second-harmonic generation response67Recent progress in oxychalcogenides as IR nonlinear optical materials79Noncentrosymmetric Tetrel Pnictides RuSi4P4 and IrSi3P3: Nonlinear Optical Materials with Outstanding Laser Damage Threshold47Expanding the Toolbox of Inorganic Mechanoluminescence Materials166AXHg3P2S8 (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]5−58Cs2ZnSn3S8: A Sulfide Compound Realizes a Large Birefringence by Modulating the Dimensional Structure24Structural Transformation and Second-Harmonic-Generation Activity in Rare-Earth and d0 Transition-Metal Oxysulfides RE3NbS3O4 (RE = Ce, Sm, Gd, Dy)38Ba4GeSb2Se11: An Infrared Nonlinear Optical Crystal with a V-Shaped Se32– Group Possessing a Large Contribution to the SHG Response8La 3 Ga 3 Ge 2 S 3 O 10 : An Ultraviolet Nonlinear Optical Oxysulfide Designed by Anion‐Directed Band Gap Engineering63La3Ga3Ge2S3O10: An Ultraviolet Nonlinear Optical Oxysulfide Designed by Anion‐Directed Band Gap Engineering18Highly polarized [GeOTe 3 ] motif-driven structural order promotion and an enhanced second harmonic generation response in the new nonlinear optical oxytelluride Ba 3 Ge 2 O 4 Te 334Complex coordinated functional groups: A great genes for nonlinear optical materials64[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 materials19Lanthanide thioborates, an emerging class of nonlinear optical materials, efficiently synthesized using the boron–chalcogen mixture method23Metal oxyhalides: an emerging family of nonlinear optical materials124Rational design of a promising oxychalcogenide infrared nonlinear optical crystal60Structural dimension modulation in a new oxysulfide system of Ae 2 Sb 2 O 2 S 3 (Ae = Ca and Ba)4Review of Heteroleptic Tetrahedra as Birefringent or Nonlinear Optical Motifs17Designing new polar materials1Sr3[SnOSe3][CO3]: A Heteroanionic Nonlinear Optical Material Containing Planar π‐conjugated [CO3] and Heteroleptic [SnOSe3] Anionic Groups78Sr3[SnOSe3][CO3]: A Heteroanionic Nonlinear Optical Material Containing Planar π‐conjugated [CO3] and Heteroleptic [SnOSe3] Anionic Groups7Multi anion-based materials: Synthesis and catalytic applications30Enhanced Second-Harmonic-Generation Efficiency and Birefringence in Melillite Oxychalcogenides Sr2MGe2OS6 (M = Mn, Zn, and Cd)97Heteroanionic Melilite Oxysulfide: A Promising Infrared Nonlinear Optical Candidate with a Strong Second-Harmonic Generation Response, Sufficient Birefringence, and Wide Bandgap65Mixed-Anion-Oriented Design of LnMGa3S6O (Ln = La, Pr, and Nd; M = Ca and Sr) Nonlinear Optical Oxysulfides with Targeted Property Balance56Oxychalcogenides as Promising Ultraviolet Nonlinear Optical Candidates: Experimental and Theoretical Studies of AEGeOS2(AE = Sr and Ba)24The 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 Groups35Heteroanion-introduction-driven birefringence enhancement in oxychalcogenide Ba 3 M II Ge 3 O 2 S 8 (M II = Mn, Cd)19Tunable Salt-Inclusion Chalcogenides for Ion Exchange, Photoluminescence, and Scintillation12Electron transport mechanisms in amorphous zinc oxysulfide thin films0Sr6Ge3OSe11: A Rationally Designed Noncentrosymmetric Oxyselenide with Polar [GeOSe3] Building Blocks16Comprehensive review on multiple mixed-anion ligands, physicochemical performances and application prospects in metal oxysulfides32Synthesis of uranium mixed anion compounds synthesized using the Boron-Chalcogen Mixture method: Ba6Co6U0·91S13·5O0.5 and Ba5·47K0·53Zn6US13·5O0.55The Crystal Structure of BaZn2Se2(OH)2 Featuring Brownmillerite‐Type Layers0Li2.9Cs1.1(SO4)2: An Ultraviolet Transparent Sulfate as a Nonlinear Optical Crystal16Synthesis of Non-centrosymmetric, Metastable Rare-Earth Oxysulfides by Anionic Redox Topochemistry8Towards the design of oxychalcogenide materials as candidates for solar water- splitting photocatalysis0Chiral and Polar Duality Design of Heteroanionic Compounds: Sr18Ge9O5S31 Based on [Sr3OGeS3]2+ and [Sr3SGeS3]2+ Groups20Synthesis of organic and inorganic mechanoluminescent compounds0Screening Large Birefringent Materials via Halogen Regulation in Ternary d0-Transition Metal Oxyhalides8Ba10In2Mn11Si3O12S18: First Hexanary Oxychalcogenide Containing an Infrequent Three-Dimensional Noncentrosysmmetric Framework8A Review of Mechanoluminescence Based on Quaternary Oxysulfides: Research Progress, Mechanism and Applications14Synthesis and Properties of La14TME6CuS24O4, Exhibiting Multivalent Spin Chains (TME = Cr, Fe)1Peierls-like distortion drives anion ordering in rutile TiOF0Synthesis and Properties of BaMTeS (M = Fe, Mn, Zn) and the Disordered Structural Analog BaGe0.5TeS0Exploring Mechanoluminescence of Zinc Alkaline Earth Metal Oxysulfides from Fundamentals to Advanced Applications26La 3 (Ga 3 S 3 O 3 )(Si 2 O 7 ): An Oxychalcogenide Demonstrating Ultrawide Optical Bandgap and Favorable Birefringence Propelled by Divergent Anionic Groups6Advances in oxychalcogenide materials for hydrogen evolution photocatalysis in aqueous media9Hetero‐Anionic Oxychalcogenides with Structures and Properties Tuned by the O:S Ratio14Layered Anion‐Mixed Oxycompounds: Synthesis, Properties, and Applications29Strong Second‐Harmonic Generation Responses in Salt‐Inclusion Oxychalcogenides Enabled by the Highly Distorted Polyhedra with Mixed‐Anions4Rate-Dependent Mechanoluminescence in SrZn2S2O:Mn2+ for Time-Characterized Optoelectronic Devices8Zero-Dimensional Oxyselenide Ba12[(Ga2OSe5)3(Si2O7)]: Enhanced Optical Anisotropy through Heteroanionic Engineering4Unravelling the impact of octahedral distortion and non-covalent interactions on the hyperpolarizabilities of Co(II) and Ni(II) coordination complexes with uridine nucleotide11Eu(II) 4 Eu(III) 2 Ge 3 S 11 O 2 : a Single‐Element Mixed‐Valence Engineering Breakthrough for Strongly Enhanced Nonlinearity and Anisotropy in Rare‐Earth Oxysulfides8Luminescent Materials for Emerging Sensing Technologies7Smart Semiconductors: An Overview of AZnOS (A= Ca, Sr, Ba) Based Phosphors, Multi‐Stimuli Responsive Luminescence, and Potential Application Prospects12Mechanoluminescent Janus architecture for stimulus-responsive photodynamic therapy3Computational Investigation of the Thermoelectric Performance of Environmentally Friendly and Earth-Abundant SrZn 2 S 2 O0Hydrostatic pressure effects on structural stability, elastic properties and band-gap modulation in SrZn2S2O: A first-principles study0Activator co-doped SrZnOS/SrZn2S2O heterojunctions: Constructing dual mapping of stress to luminescence intensity and color variation0

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  1. Mixed-Anion Compounds: A New Trend in Solid State Chemistry

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  3. Synthesis, crystal structures and optical properties of noncentrosymmetric oxysulfides AeGeS 2 O (Ae = Sr, Ba)

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  4. Sr 6 Cd 2 Sb 6 O 7 S 10 : Strong SHG Response Activated by Highly Polarizable Sb/O/S Groups

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  5. Sr6Cd2Sb6O7S10: Strong SHG Response Activated by Highly Polarizable Sb/O/S Groups

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  6. La2USe3S2: A Serendipitously Grown Lanthanide/Actinide Chalcogenide from a Eutectic Halide Flux

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  49. Oxychalcogenides: A Promising Class of Materials for Nonlinear Optical Crystals with Mixed‐Anion Groups

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  50. Heteroanion-introduction-driven birefringence enhancement in oxychalcogenide Ba 3 M II Ge 3 O 2 S 8 (M II = Mn, Cd)

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