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RESEARCH PAPER · Chemistry of Materials · 2015

Oxychalcogenide BaGeOSe2: Highly Distorted Mixed-Anion Building Units Leading to a Large Second-Harmonic Generation Response

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Oxychalcogenide BaGeOSe2: Highly Distorted Mixed-Anion Building Units Leading to a Large Second-Harmonic Generation ResponseOriginalChemInform Abstract: Oxychalcogenide BaGeOSe2: Highly Distorted Mixed‐Anion Building Units Leading to a Large Second‐Harmonic Generation Response.0The structure and band gap design of high Si doping level Ag1−xGa1−xSixSe2 (x=1/2)15Face‐Shared Octahedral Dimer In2O7S2 in the Non‐Centrosymmetric Barium Indiumsilicate Oxysulfide Ba2In2Si3O10S9Anion Ordering in Bichalcogenides25Syntheses, crystal and electronic structure of a series of quaternary rare-earth sulfides MgRE6Si2S14 (RE = Y, Ce, Pr, Nd and Sm)7Synthesis and characterization of sulfide oxide SrZnSO with strongly polar crystal structure34Recent 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 intensity44Li 2 CdGeSe 4 and Li 2 CdSnSe 4 : biaxial nonlinear optical materials with strong infrared second-order responses and laser-induced damage thresholds influenced by photoluminescence54Spin-polarized Second Harmonic Generation from the Antiferromagnetic CaCoSO Single Crystal148Large Second-Harmonic Generation Responses Achieved by the Dimeric [Ge2Se4(μ-Se2)]4– Functional Motif in Polar Polyselenides A4Ge4Se12 (A = Rb, Cs)49Sulfide oxide XZnSO (X = Ca or Sr) as novel active photocatalytic water splitting solar-to-hydrogen energy conversion40Influence of A-site cations on germanium iodates as mid-IR nonlinear optical materials: A 2 Ge(IO 3 ) 6 (A = Li, K, Rb and Cs) and BaGe(IO 3 ) 6 ·H 2 O43Second-order nonlinear optical crystals with mixed anions250Function of Tetrahedral ZnS3O Building Blocks in the Formation of SrZn2S2O: A Phase Matchable Polar Oxysulfide with a Large Second Harmonic Generation Response83Synthesis, crystal structures and optical properties of noncentrosymmetric oxysulfides AeGeS 2 O (Ae = Sr, Ba)45The Ba10S(VO3S)6 Oxysulfide: One-Dimensional Structure and Mixed Anion Chemical Bonding11Balanced Second-Order Nonlinear Optical Properties of Adducts CHI3·(S8)3 and AsI3·(S8)3: A Systematic Survey48Sr 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 Groups22[(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 Materials140Creating visible-to-near-infrared mechanoluminescence in mixed-anion compounds SrZn2S2O and SrZnSO145Oxysulfide Ba5(VO2S2)2(S2)2 Combining Disulfide Channels and Mixed-Anion Tetrahedra and Its Third-Harmonic-Generation Properties15Second-Order Nonlinear-Optical-Active Selenide Borate YSeBO2: Featuring a [YSeBO2]n Planar Belt39Partial Isovalent Anion Substitution to Access Remarkable Second-Harmonic Generation Response: A Generic and Effective Strategy for Design of Infrared Nonlinear Optical Materials114“Soft” Alkali Bromide and Iodide Fluxes for Crystal Growth36Sr5Ga8O3S14: A Nonlinear Optical Oxysulfide with Melilite-Derived Structure and Wide Band Gap48Two Mixed-Anion Units of [GeOSe3] and [GeO3S] Originating from Partial Isovalent Anion Substitution and Inducing Moderate Second Harmonic Generation Response and Large Birefringence55Crystal growth, characterization and theoretical studies of the noncentrosymmetric compound Al3(IO3)9·(HIO3)6·18H2O4From AgGaS 2 to AgHgPS 4 : vacancy defects and highly distorted HgS 4 tetrahedra double-induced remarkable second-harmonic generation response67Applying band gap engineering to tune the linear optical and nonlinear optical properties of noncentrosymmetric chalcogenides La 4 Ge 3 Se x S 12− x ( x = 0, 2, 4, 6, 8, 10)21Recent progress in oxychalcogenides as IR nonlinear optical materials79Inorganic Chalcogenides: From Zero‐Dimensional Clusters to Three‐Dimensional Frameworks5AXHg3P2S8 (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]5−58Structural Transformation and Second-Harmonic-Generation Activity in Rare-Earth and d0 Transition-Metal Oxysulfides RE3NbS3O4 (RE = Ce, Sm, Gd, Dy)38La 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 ] clusters32Bridging oxygen atoms in trigonal prism units driven strong second-harmonic-generation efficiency in Sr 3 Ge 2 O 4 Te 318Metal 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)4Synthesis, structural evolution and optical properties of a new family of oxychalcogenides [Sr 3 VO 4 ][MQ 3 ] (M = Ga, In, Q = S, Se)10Pb 4 SeBr 6 : A Congruently Melting Mid‐Infrared Nonlinear Optical Material with Excellent Comprehensive Performance39Sr3[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 Groups7Enhanced Second-Harmonic-Generation Efficiency and Birefringence in Melillite Oxychalcogenides Sr2MGe2OS6 (M = Mn, Zn, and Cd)97Negative Second Harmonic Response of Sn4+in the Fresnoite Oxysulfide Ba2SnSSi2O720Heteroanionic Melilite Oxysulfide: A Promising Infrared Nonlinear Optical Candidate with a Strong Second-Harmonic Generation Response, Sufficient Birefringence, and Wide Bandgap65First Investigation of Nonlinear Optical Oxychalcogenide with Three‐Dimensional Anionic Framework and Special Windmill‐Like Functional Motifs †28[Ba2F2][Ge2O3S2]: An Unprecedented Heteroanionic Infrared Nonlinear Optical Material Containing Three Typical Anions47Oxychalcogenides 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 Gaps68Enhanced Second-Harmonic-Generation Response in a KH2PO4-Type Calcium Nitrate Carboxylate with Unusual Three-Dimensional Inorganic and Organic Connections3Ba5Ga2SiO4S6: 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 Groups35Anisotropic structure building unit involving diverse chemical bonds: a new opportunity for high-performance second-order NLO materials181Heteroanion-introduction-driven birefringence enhancement in oxychalcogenide Ba 3 M II Ge 3 O 2 S 8 (M II = Mn, Cd)19Linear optical afterglow and nonlinear optical harmonic generation from chiral tin( iv ) halides: the role of lattice distortions37The first quaternary rare-earth oxythiogermanate with second-harmonic generation and ferromagnetic behavior26Ultralow thermal conductivity in the mixed-anion solid solution Sn 2 SbS 2− x Se x I 319Rational Design of a Rare‐Earth Oxychalcogenide Nd3[Ga3O3S3][Ge2O7] with Superior Infrared Nonlinear Optical Performance64Sr6Ge3OSe11: A Rationally Designed Noncentrosymmetric Oxyselenide with Polar [GeOSe3] Building Blocks16Comprehensive review on multiple mixed-anion ligands, physicochemical performances and application prospects in metal oxysulfides32Recent advances in IR nonlinear optical chalcogenides with well-balanced comprehensive performance56The Crystal Structure of BaZn2Se2(OH)2 Featuring Brownmillerite‐Type Layers0Hole and Electron Doping Outcomes in Bi2YO4Cl9Synthesis 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+ Groups20Cation and anion co-partial substitution induced centrosymmetric to noncentrosymmetric structural transformation to construct nonlinear-optical rare-earth oxythiogermanates13Heteroanionic [VO x S 4− x ] groups: tetrahedral units with large birefringence for mid-infrared nonlinear optical crystals9Partial substitution with a significant effect: coexistence of a wide band gap and large birefringence in the oxychalcogenide AEGe 2 O 4 Se (AE = Sr and Ba)17Ba10In2Mn11Si3O12S18: First Hexanary Oxychalcogenide Containing an Infrequent Three-Dimensional Noncentrosysmmetric Framework8Infrared nonlinear optical materials with multiple strongly ionic cations5Pentanary Oxythiogermanates Ba3MGe3O2S8 (M = Ca, Zn) Featuring [Ge3O2S8]8– Trimers and {[MGe3O2S8]6–}∞ Chains: Structural Chemistry and Physical Properties4Synthesis and Properties of La14TME6CuS24O4, Exhibiting Multivalent Spin Chains (TME = Cr, Fe)1[Rb3BaCl][In8Se14]: Compressed chalcopyrite-type selenide achieved by polycationic substitution strategy toward excellent nonlinear optical property18From CaBaM2F12 to K2BaM2F12 (M = Zr, Hf): Heterovalent Cation-Substitution-Induced Symmetry Break and Nonlinear-Optical Activity11Wide-Gap p-Type Layered Oxychalcogenides AE2CuInO3Ch (AE: Alkaline Earth; Ch: Chalcogen): Unusually Low Residual Carrier Concentration and Green-to-Red Emission7From [Ba3S][GeS4] to [Ba3CO3][MS4] (M = Ge, Sn): Enhancing optical anisotropy in IR birefringent crystals via functional group implantation11Balanced IR Nonlinear Optical Performance Achieved by Cation–Anion Module Cosubstitution in V-Based Salt-Inclusion Oxychalcogenides22La 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 media9Designing infrared nonlinear optical crystals, Sr 2 MgSn 2 OS 6 and Sr 2 SnGa 2 OS 6 , with hybrid anionic frameworks via a double substitution strategy4Hetero‐Anionic Oxychalcogenides with Structures and Properties Tuned by the O:S Ratio14Strong Second‐Harmonic Generation Responses in Salt‐Inclusion Oxychalcogenides Enabled by the Highly Distorted Polyhedra with Mixed‐Anions4Recent progress in structural design strategies of high-birefringence optical crystals54Unravelling the impact of octahedral distortion and non-covalent interactions on the hyperpolarizabilities of Co(II) and Ni(II) coordination complexes with uridine nucleotide11Enhancement of optical anisotropy from [BF4] units by ligand substitution0From Centrosymmetric Ca3Ge2O3S4 to Noncentrosymmetric Ca3Ge2O4Se3: A Nonlinear Optical Ca-Based Oxyselenide5Crystal structures and electronic structures of SrSiSe 3 and BaGeSe 30Heterometallic Ge–O–Sn-Bridged Oxychalcogenides Sr3GeSnO4Q3 (Q = S, Se) with Wide Band Gaps and Moderate Infrared Nonlinear Optical Responses0

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  2. The structure and band gap design of high Si doping level Ag1−xGa1−xSixSe2 (x=1/2)

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  3. Face‐Shared Octahedral Dimer In2O7S2 in the Non‐Centrosymmetric Barium Indiumsilicate Oxysulfide Ba2In2Si3O10S

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  4. Anion Ordering in Bichalcogenides

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  5. Syntheses, crystal and electronic structure of a series of quaternary rare-earth sulfides MgRE6Si2S14 (RE = Y, Ce, Pr, Nd and Sm)

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  6. Synthesis and characterization of sulfide oxide SrZnSO with strongly polar crystal structure

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

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  10. Spin-polarized Second Harmonic Generation from the Antiferromagnetic CaCoSO Single Crystal

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  11. 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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  13. Influence of A-site cations on germanium iodates as mid-IR nonlinear optical materials: A 2 Ge(IO 3 ) 6 (A = Li, K, Rb and Cs) and BaGe(IO 3 ) 6 ·H 2 O

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  31. From AgGaS 2 to AgHgPS 4 : vacancy defects and highly distorted HgS 4 tetrahedra double-induced remarkable second-harmonic generation response

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  32. Applying band gap engineering to tune the linear optical and nonlinear optical properties of noncentrosymmetric chalcogenides La 4 Ge 3 Se x S 12− x ( x = 0, 2, 4, 6, 8, 10)

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  33. Recent progress in oxychalcogenides as IR nonlinear optical materials

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  34. Inorganic Chalcogenides: From Zero‐Dimensional Clusters to Three‐Dimensional Frameworks

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  39. Highly 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 3

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  40. Complex coordinated functional groups: A great genes for nonlinear optical materials

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  41. [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 ] clusters

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  45. Structural dimension modulation in a new oxysulfide system of Ae 2 Sb 2 O 2 S 3 (Ae = Ca and Ba)

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  46. Synthesis, structural evolution and optical properties of a new family of oxychalcogenides [Sr 3 VO 4 ][MQ 3 ] (M = Ga, In, Q = S, Se)

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  50. Enhanced Second-Harmonic-Generation Efficiency and Birefringence in Melillite Oxychalcogenides Sr2MGe2OS6 (M = Mn, Zn, and Cd)

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    Mao‐Yin Ran, Shenghua Zhou, Bingxuan Li, Wenbo Wei, Xintao Wu, Hua Lin, Qi‐Long Zhu

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