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RESEARCH PAPER · Chemistry of Materials · 2018

LiGa 2 PS 6 and LiCd 3 PS 6 : Molecular Designs of Two New Mid-Infrared Nonlinear Optical Materials

Jianghe Feng, Chun‐Li Hu, Bingxuan Li, Jiang‐Gao Mao

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LiGa 2 PS 6 and LiCd 3 PS 6 : Molecular Designs of Two New Mid-Infrared Nonlinear Optical MaterialsOriginalAdduct-Type IR Nonlinear-Optical Crystal SbI 3 ·(S 8 ) 3 with a Large Second-Harmonic Generation and a High Laser-Induced Damage Threshold59A review on structure-performance relationship toward the optimal design of infrared nonlinear optical materials with balanced performances253Cu2EuMQ4 (M = Si, Ge; Q = S, Se): Syntheses, structure study and physical properties determination26Pressure-Assisted Method for the Preparations of High-Quality AaGaS2 and AgGaGeS4 Crystals for Mid-Infrared Laser Applications11Experimental study on nonlinear−optical property of Ag4P2Se66Recent progress on new infrared nonlinear optical materials with application prospect133Ba 4 (BS 3 S) 2 S 4 : a new thioborate with unprecedented [BS 3 -S] and [S 4 ] fundamental building blocks19SnGa 2 GeSe 6 , a benign addition to the AMIII2M IV Q 6 family: synthesis, crystal structure and nonlinear optical performance20Synthesis and nonlinear optical properties of new gallium thiophosphate Rb 2 Ga 2 P 2 S 913Theoretical investigation on the promotion of second harmonic generation from chalcopyrite family A I GaS 2 to A II Ga 2 S 47Broadening Frontiers of Infrared Nonlinear Optical Materials with π-Conjugated Trigonal-Planar Groups67Balanced Second-Order Nonlinear Optical Properties of Adducts CHI3·(S8)3 and AsI3·(S8)3: A Systematic Survey48BaHgGeSe 4 and SrHgGeSe 4 : Two New Hg-Based Infrared Nonlinear Optical Materials142Synthesis, Structure, and Characterization of Two Mixed-Cation Quaternary Chalcogenides K2BaSnQ4 (Q = S, Se)19AHgSnQ4 (A = Sr, Ba; Q = S, Se): A Series of Hg-Based Infrared Nonlinear-Optical Materials with Strong Second-Harmonic-Generation Response and Good Phase Matchability76Ba 8 SrPb 24 O 24 Cl 18 : the first alkali-earth metal lead( ii ) oxyhalide with an intriguing multimember-ring layer9BaGe 2 Pn 2 (Pn = P, As): Two Congruent-Melting Non-chalcopyrite Pnictides as Mid- and Far-Infrared Nonlinear Optical Materials Exhibiting Large Second Harmonic Generation Effects54K5(W3O9F4)(IO3): An Efficient Mid-Infrared Nonlinear Optical Compound with High Laser Damage Threshold114Rational design of infrared nonlinear optical chalcogenides by chemical substitution287A review of the AI2B II C IV DVI4 family as infrared nonlinear optical materials: the effect of each site on the structure and optical properties59Experimental and theoretical studies of the ternary thiophosphate PbPS 3 featuring ethane-like [P 2 S 6 ] 4− units15Li 2 CdSiS 4 , a promising IR NLO material with a balanced E g and SHG response originating from the effect of Cd with d 10 configuration36Mixed-metal thiophosphate CuCd 3 PS 6 : an infrared nonlinear optical material activated by its three-in-one tetrahedra-stacking architecture33Non-centrosymmetric sulfides A 2 Ba 6 MnSn 4 S 16 (A = Li, Ag): syntheses, structures and properties21One-Dimensional Double Chains in Sodium-Based Quaternary Chalcogenides Displaying Intriguing Red Emission and Large Optical Anisotropy17Quaternary rare-earth sulfide LaSnGa3S7: Synthesis, structure, thermal and optical properties5Molecular Construction from AgGaS 2 to CuZnPS 4 : Defect-Induced Second Harmonic Generation Enhancement and Cosubstitution-Driven Band Gap Enlargement97Cd4SiQ6 (Q = S, Se): Ternary Infrared Nonlinear Optical Materials with Mixed Functional Building Motifs21Crystal chemistry, second-order nonlinear optical, and magnetic properties of Eu8Sn4Se2014Inherent laws between tetrahedral arrangement pattern and optical performance in tetrahedron-based mid-infrared nonlinear optical materials131First principles study of the electronic, elastic, infrared and electrical properties of LiZnPS42Pb 18 O 8 Cl 15 I 5 : A Polar Lead Mixed Oxyhalide with Unprecedented Architecture and Excellent Infrared Nonlinear Optical Properties166Pb18O8Cl15I5: A Polar Lead Mixed Oxyhalide with Unprecedented Architecture and Excellent Infrared Nonlinear Optical Properties29Chalcophosphates: A Treasure House of Infrared Nonlinear Optical Materials75Revisiting thiophosphate Pb 3 P 2 S 8 : a multifunctional material combining a nonlinear optical response and photocurrent response23α-Ca2CdP2 and β-Ca2CdP2: Two Polymorphic Phosphide-Based Infrared Nonlinear Crystals with Distorted NLO-Active Tetrahedral Motifs Realizing Large Second Harmonic Generation Effects and Suitable Band Gaps30A review of the structural diversity of [P x S y ] n − motifs and their potential application prospects in metal thiophosphates21Transition-metal-based chalcogenides: A rich source of infrared nonlinear optical materials184SnPQ3 (Q = S, Se, S/Se): A Series of Lone-Pair Cationic Chalcogenophosphates Exhibiting Balanced NLO Activity Originating from SnQ8 Units49Polymorphic Pb14O8I12 and Pb7O4I6 oxyhalides featuring unprecedented [O8Pb14] clusters with broad IR transparency20Cd7SiAs6, a Nonchalcopyrite Arsenide with a Strong Nonlinear-Optical Response9Na+/Ag+ substitution induced birefringence enhancement from AgGaS2 to NaGaS218Partial 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 performances21New Quaternary Sulfide LiGaSiS 4: Synthesis, Structure and Optical Properties0Wide band gap thiophosphates ASrPS 4 (A = Li, Na, K, Rb, Cs): cation size effect induced successive structural transformation13Two Nonlinear Optical Thiophosphates Cu 5 Hg 0.5 P 2 S 8 and AgHg 3 PS 6 Activated by Their Tetrahedra-Stacking Architecture12Phosphogermanate Crystal: A New Ultraviolet–Infrared Nonlinear Optical Crystal with Excellent Optical Performances16α- and β-Ag4P2S7: Two Semiconductors with Promising Photocatalytic Hydrogen Production Based on a Density Functional Theory Study6Hg2P2S6: A layered mercury hexathiodiphosphate (IV) with large birefringence11Fluorotrithiophosphate Abstraction from the Difluoropentathiodiphosphate Dianion: d8 and d6 Complexes of [η2-S3PF]2–6Ternary AGa5S8 (A = K, Rb, Cs): Promising infrared nonlinear optical materials rationally realized by “one-for-multiple substitution” strategy37Novel structural transformation in K3ReP2S8 thiophosphates originating from the rare-earth (Re) cation sizes induced local coordination asymmetry25Ag[SC(NH2)2]2F: A Laser Damage-Tolerant Infrared Nonlinear Optical Material9Synthesis, Crystal and Electronic Structures, Nonlinear Optical Properties, and Magnetic Properties of Two Thiophosphates: KInP2S7 and KCrP2S79AIB3IIC3IIIQ8VI: A New Family for the Design of Infrared Nonlinear Optical Materials by Coupling Octahedra and Tetrahedra Units152KREP2Se6 (RE = Sm, Gd, Tb): The First Rare‐Earth Selenophosphates with Remarkable Nonlinear Optical Activities Realized by Synergistic Effect of RE‐ and P‐Based Motifs39γ-P 4 S 3 I 2 : a new metal-free infrared second-order nonlinear optical crystal designed by polymorphism strategy17From BPS 4 to AB 3 P 2 S 10 (A = Na, K): cations inducing dimension reduction and bandgap enlargement7Na 6 Sn 3 P 4 S 16 : Sn( ii )-chelated PS 4 groups inspired an ultra-strong SHG response22Quaternary alkaline-earth metal thiophosphate SrAgPS 4 : syntheses, structures, and optical properties9Revisiting two thiophosphate compounds constituting d 0 transition metal HfP 2 S 6 and d 10 transition metal α-Ag 4 P 2 S 6 as multifunctional materials for combining second harmonic generation response and photocurrent response12The induced polarization enhanced birefringence in AlPS4 family: A first-principles investigation6Data driven enhancement of mid-infrared non-linear optical properties of quaternary and ternary chalcogenides6Enhancing second harmonic generation response in infrared nonlinear optical material through Pb substitution: A study of LiPbSiS compound2Na 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 ] octahedra4Noncentrosymmetric Na6Pb3P4S16 and Centrosymmetric K2MIIP2S6 (MII = Mg and Zn) Displaying Multiple Membered-Ring Configurations and Strong Optical Anisotropy10Ga-based IR nonlinear optical materials: Synthesis, structures, and properties65Polysulfide Anions [S x ] 2− ( x = 2, 3, 4, 5): Promising Functional Building Units for Infrared Nonlinear Optical Materials22Infrared nonlinear optical materials with multiple strongly ionic cations5Homoatomic Polychalcogenide Nonlinear Optical Anionic Groups with Ultra-Large Optical Anisotropy31Structure‐Prediction‐Oriented Synthesis of Thiophosphates as Promising Infrared Nonlinear Optical Materials24Structure‐Prediction‐Oriented Synthesis of Thiophosphates as Promising Infrared Nonlinear Optical Materials1Emergent Mid‐Infrared Nonlinear Optical Candidates With Targeted Balance Performances18Aliovalent Al 3+ substituted ultra-wide bandgap CuAlX 4 (X = Cl, Br) for infrared nonlinear optics6Pb 4 O 3 I 2 : A Lead Oxyhalide IR Optical Crystal with an Unprecedented 1 ∞ [O 3 Pb 4 ] Chain Featuring a Wide Transmittance Range and Large Birefringence3Nonbonding Electron Inversion‐Driven Structural Engineering: Synergistic Enhancement of Linear and Nonlinear Optical Properties3Nonbonding Electron Inversion‐Driven Structural Engineering: Synergistic Enhancement of Linear and Nonlinear Optical Properties26Alkali Metal Substitution-Induced Structural Transformation for RbREP2Se6 (RE = Gd, Tb, Dy) with Second-Harmonic Generation Responses6SrZnSiS4: Shattering the 4.0 eV Threshold toward Dual-Optimized Bandgap and Second-Harmonic Generation7SrZnGeSe4: An Infrared Nonlinear Optical Crystal Material with Wide Transmission Range and Large SHG Response7高性能硫属化物红外非线性光学材料构效关系（特邀）0Rare-Earth Selenophosphates Cs 2 YP 2 Se 7 and KYP 2 Se 6 Synthesized by the RFMOBQ Routine: Structural Evolution and Nonlinear Optical Activity2K 3 Mg 2 [K 6 MgCl 3 ][Ga 20 S 36 ]: A Diamond-like Framework Based on Mixed-Type Supertetrahedra for Excellent Nonlinear Optical Property1Nonlinear Optical-Active NaAlP 2 S 6 Synthesized by the MOBQ Method: Synthesis, Structure, and Optical Properties0AVP2S7 (A = K, Rb): Dual-Optimized Infrared Nonlinear Optical Thiophosphates via Heterovalent-Substitution-Driven Symmetry Breaking and Reinforced Interlayer Interactions0Laporte Selection Rule Induced the Suppression of d ‐ d Transitions and Vacancies Enhanced the Second Harmonic Generation in I 4¯‐MnGa 2 S 40NaGa2PS6: A Noncentrosymmetric Thiophosphate with Wide Band Gap and High Laser-Induced Damage Threshold0

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  2. A review on structure-performance relationship toward the optimal design of infrared nonlinear optical materials with balanced performances

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  3. Cu2EuMQ4 (M = Si, Ge; Q = S, Se): Syntheses, structure study and physical properties determination

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  4. Pressure-Assisted Method for the Preparations of High-Quality AaGaS2 and AgGaGeS4 Crystals for Mid-Infrared Laser Applications

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  5. Experimental study on nonlinear−optical property of Ag4P2Se6

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  6. Recent progress on new infrared nonlinear optical materials with application prospect

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  7. Ba 4 (BS 3 S) 2 S 4 : a new thioborate with unprecedented [BS 3 -S] and [S 4 ] fundamental building blocks

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  8. SnGa 2 GeSe 6 , a benign addition to the AMIII2M IV Q 6 family: synthesis, crystal structure and nonlinear optical performance

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

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  10. Theoretical investigation on the promotion of second harmonic generation from chalcopyrite family A I GaS 2 to A II Ga 2 S 4

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  11. Broadening Frontiers of Infrared Nonlinear Optical Materials with π-Conjugated Trigonal-Planar Groups

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

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  13. BaHgGeSe 4 and SrHgGeSe 4 : Two New Hg-Based Infrared Nonlinear Optical Materials

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  14. Synthesis, Structure, and Characterization of Two Mixed-Cation Quaternary Chalcogenides K2BaSnQ4 (Q = S, Se)

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  15. AHgSnQ4 (A = Sr, Ba; Q = S, Se): A Series of Hg-Based Infrared Nonlinear-Optical Materials with Strong Second-Harmonic-Generation Response and Good Phase Matchability

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  16. Ba 8 SrPb 24 O 24 Cl 18 : the first alkali-earth metal lead( ii ) oxyhalide with an intriguing multimember-ring layer

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  17. BaGe 2 Pn 2 (Pn = P, As): Two Congruent-Melting Non-chalcopyrite Pnictides as Mid- and Far-Infrared Nonlinear Optical Materials Exhibiting Large Second Harmonic Generation Effects

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  18. K5(W3O9F4)(IO3): An Efficient Mid-Infrared Nonlinear Optical Compound with High Laser Damage Threshold

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  19. Rational design of infrared nonlinear optical chalcogenides by chemical substitution

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  20. A review of the AI2B II C IV DVI4 family as infrared nonlinear optical materials: the effect of each site on the structure and optical properties

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  21. Experimental and theoretical studies of the ternary thiophosphate PbPS 3 featuring ethane-like [P 2 S 6 ] 4− units

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  22. Li 2 CdSiS 4 , a promising IR NLO material with a balanced E g and SHG response originating from the effect of Cd with d 10 configuration

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  23. Mixed-metal thiophosphate CuCd 3 PS 6 : an infrared nonlinear optical material activated by its three-in-one tetrahedra-stacking architecture

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  34. Chalcophosphates: A Treasure House of Infrared Nonlinear Optical Materials

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  35. Revisiting thiophosphate Pb 3 P 2 S 8 : a multifunctional material combining a nonlinear optical response and photocurrent response

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  36. α-Ca2CdP2 and β-Ca2CdP2: Two Polymorphic Phosphide-Based Infrared Nonlinear Crystals with Distorted NLO-Active Tetrahedral Motifs Realizing Large Second Harmonic Generation Effects and Suitable Band Gaps

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  37. A review of the structural diversity of [P x S y ] n − motifs and their potential application prospects in metal thiophosphates

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  40. Polymorphic Pb14O8I12 and Pb7O4I6 oxyhalides featuring unprecedented [O8Pb14] clusters with broad IR transparency

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  43. Partial congener substitution induced centrosymmetric to noncentrosymmetric structural transformation and nonlinear optical properties of PbSnSiS4

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  44. 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

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  46. Wide band gap thiophosphates ASrPS 4 (A = Li, Na, K, Rb, Cs): cation size effect induced successive structural transformation

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  47. Two Nonlinear Optical Thiophosphates Cu 5 Hg 0.5 P 2 S 8 and AgHg 3 PS 6 Activated by Their Tetrahedra-Stacking Architecture

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  48. Phosphogermanate Crystal: A New Ultraviolet–Infrared Nonlinear Optical Crystal with Excellent Optical Performances

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  49. α- and β-Ag4P2S7: Two Semiconductors with Promising Photocatalytic Hydrogen Production Based on a Density Functional Theory Study

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

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