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RESEARCH PAPER · Chemistry of Materials · 2016

Deep-Ultraviolet Transparent Cs 2 LiPO 4 Exhibits an Unprecedented Second Harmonic Generation

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Deep-Ultraviolet Transparent Cs 2 LiPO 4 Exhibits an Unprecedented Second Harmonic GenerationOriginalStrong Nonlinear-Optical Response in the Pyrophosphate CsLiCdP2O7 with a Short Cutoff Edge69LiRb 2 PO 4 : a new deep-ultraviolet nonlinear optical phosphate with a large SHG response95ChemInform Abstract: Deep‐Ultraviolet Transparent Cs2LiPO4 Exhibits an Unprecedented Second Harmonic Generation.0A new phase-matchable nonlinear optical silicate: Rb 2 ZnSi 3 O 825Enhancing optical anisotropy of crystals by optimizing bonding electron distribution in anionic groups236Structure comparison and optical properties of Na 7 Mg 4.5 (P 2 O 7 ) 4 : a sodium magnesium phosphate with isolated P 2 O 7 units16M4Mg4(P2O7)3 (M = K, Rb): Structural Engineering of Pyrophosphates for Nonlinear Optical Applications238Growth, Properties, and Theoretical Analysis of M2LiVO4 (M = Rb, Cs) Crystals: Two Potential Mid-Infrared Nonlinear Optical Materials36Second-harmonic generation in noncentrosymmetric phosphates47Li7(TeO3)3F: A Lithium Fluoride Tellurite with Large Second Harmonic Generation Responses and a Short Ultraviolet Cutoff Edge39K2[B3O3(OH)5]: A new deep-UV nonlinear optical crystal with isolated [B3O3(OH)5]2- anionic groups31A beryllium-free deep-UV nonlinear optical material CsNaMgP 2 O 7 with honeycomb-like topological layers53Cs 3 VO(O 2 ) 2 CO 3 : an exceptionally thermostable carbonatoperoxovanadate with an extremely large second-harmonic generation response129Li 8 NaRb 3 (SO 4 ) 6 ·2H 2 O as a new sulfate deep-ultraviolet nonlinear optical material93A Joint Strategy To Evaluate the Microscopic Origin of the Second-Harmonic-Generation Response in Nonpolar ABCO3F Compounds32Synthesis, crystal structure and characterizations of a new diphosphate Rb2CaP2O719The Large Second‐Harmonic Generation of LiCs2PO4 is caused by the Metal‐Cation‐Centered Groups107The Large Second‐Harmonic Generation of LiCs2PO4 is caused by the Metal‐Cation‐Centered Groups23Recent advances in ultraviolet and deep-ultraviolet second-order nonlinear optical crystals257Synergetic Influence of Alkali-Metal and Lone-Pair Cations on Frameworks of Tellurites15Expanding Frontiers of Ultraviolet Nonlinear Optical Materials with Fluorophosphates265Two noncentrosymmetric polyphosphates featuring infinite one-dimensional (PO3)∞ chain, LiMP2O6 (M = Rb, Cs): Synthesis, structure and optical properties8ALiZnP2O7 (A = Rb, Cs): Two Mixed Alkali Zinc Pyrophosphates Featuring a [Li2Zn2P4O20]14– Anionic Skeleton34A Langbeinite-Type Yttrium Phosphate LiCs2Y2(PO4)336Ba2NaClP2O7: Unprecedented Phase Matchability Induced by Symmetry Breaking and Its Unique Fresnoite-Type Structure245BaPO3Cl: a Metal Phosphate Chloride with Infinite [PO3]∞ Chains25Exploration of the deep-ultraviolet nonlinear optical materials in the derivatives of KBe2BO3F27Growth and theoretical study on the deep-ultraviolet transparent β-CsBa 2 (PO 3 ) 5 nonlinear optical crystal10Hybridization-activated new deep ultraviolet transparent nonlinear optical material Ba 11 [Al(PO 4 ) 4 ](P 2 O 7 )(PO 4 ) 3 with balanced overall performance and parsimony-forbidden structure23K 2 SrP 4 O 12 : a deep-UV transparent cyclophosphate as a nonlinear optical crystal79LiGeBO 4 : a nonlinear optical material with a balance between deep-ultraviolet cut-off edge and large SHG response induced by hand-in-hand tetrahedra21Three new phosphates, Cs8Pb4(P2O7)4, CsLi7(P2O7)2 and LiCa(PO3)3: structural comparison, characterization and theoretical calculation23Abrupt Structural Transformation in Asymmetric ABPO4F (A = K, Rb, Cs)21Lone‐Pair Enhanced Birefringence in an Alkaline‐Earth Metal Tin(II) Phosphate BaSn 2 (PO 4 ) 2130Two Non-π-Conjugated Deep-UV Nonlinear Optical Sulfates268Rational Design and Synthesis of a Deep-Ultraviolet Nonlinear Optical Fluorinated Orthophosphate: BaZn(PO4)F16Uniform Alignment of Non-π-Conjugated Species Enhances Deep Ultraviolet Optical Nonlinearity369Centrosymmetric Rb2Mg3(SO4)4 and non-centrosymmetric Cs2Mg3(SO4)4 with a phase-matching nonlinear optical response35Syntheses, crystal structures, and characterizations of three new pyrophosphates CsNaZnP2O7, RbNaZnP2O7, and RbLiMgP2O710[NH4]12[(MoO2)2O(HPO4)2]4[PO4]Cl·0.5H2O: A mixed phosphomolybdate with nonlinear optical properties4KMg(H 2 O)PO 4 : A Deep-Ultraviolet Transparent Nonlinear Optical Material Derived from KTiOPO 483Structural Origin of Thermally Induced Second Harmonic Generation Enhancement in RbNaMgP2O721β-Ba(PO3)2 with DUV cut-off edge and large birefringence5Na2Mg1−xZnxSiO4 (0 ≤ x ≤ 1): Noncentrosymmetric Sodium Metal Silicate Solid Solutions with Ultraviolet Nonlinear Optical Properties71Syntheses, characterization, and theoretical calculation of Rb2Mg3(P2O7)2 polymorphs with deep-ultraviolet cutoff edges18(NH 4 ) 3 [B(OH) 3 ] 2 (COOH) 3 : a graphite-like UV nonlinear optical material with a large birefringence via structural optimization31Na 3 Sc 2 (PO 4 ) 2 F 3 : rational design and synthesis of an alkali rare-earth phosphate fluoride as an ultraviolet nonlinear optical crystal with an enlarged birefringence49Optimal arrangement of π-conjugated anionic groups in hydro-isocyanurates leads to large optical anisotropy and second-harmonic generation effect42PbSrSiO 4 : a new ultraviolet nonlinear optical material with a strong second harmonic generation response and moderate birefringence37Second harmonic generation responses of KH 2 PO 4 : importance of K and breaking down of Kleinman symmetry49Syntheses, structures and characterization of non-centrosymmetric Rb 2 Zn 3 (P 2 O 7 ) 2 and centrosymmetric Cs 2 M 3 (P 2 O 7 ) 2 (M = Zn and Mg)26Three diphosphates, α-Li 2 Na 2 P 2 O 7 , Li 8 Pb 3 Ba(P 2 O 7 ) 4 and Li 7 Rb(P 2 O 7 ) 2 : influences of co-substitution on the crystal structure9Three non-centrosymmetric bismuth phosphates, Li 2 ABi(PO 4 ) 2 (A = K, Rb, and Cs): effects of cations on the crystal structure and SHG response23Ultraviolet nonlinear optical crystal: (NH4)ZnPO47Key Factors Controlling the Large Second Harmonic Generation in Nonlinear Optical Materials37Effects of P2O7 clusters arrangement on second harmonic generation responses of pyrophosphates14Synthesis, Crystal Structure, and Characterization of a Noncentrosymmetric Sulfate Cs2Ca2(SO4)320The first rare-earth lead phosphates Pb3AP3O12 (A=Sc, Gd) with remarkable SHG enhancement8Designing Silicates as Deep‐UV Nonlinear Optical (NLO) Materials using Edge‐Sharing Tetrahedra147Designing Silicates as Deep‐UV Nonlinear Optical (NLO) Materials using Edge‐Sharing Tetrahedra43Synthesis, characterizations and theoretical analysis of a noncentrosymmetric sulfate8Designing a Deep-UV Nonlinear Optical Fluorooxosilicophosphate127K4Sb(SO4)3Cl: The first apatite-type sulfate ultraviolet nonlinear optical material with sharply enlarged birefringence61Synthesis, crystal structures and optical properties of open-framework gallium phosphates: NaGa3F4(PO4)2(H2O)2 and AGa2P2O7(OH)3(H2O) (A = K, Rb)1K 2 Sb(P 2 O 7 )F: Cairo Pentagonal Layer with Bifunctional Genes Reveal Optical Performance297K2Sb(P2O7)F: Cairo Pentagonal Layer with Bifunctional Genes Reveal Optical Performance38A2BBi2(PO4)2(P2O7) (A = K, Rb, B = Pb, Cd): the Effect of Cation Sizes on Structural Evolution10A 3 BBi(P 2 O 7 ) 2 (A = Rb, Cs; B = Pb, Ba): Isovalent Cation Substitution to Sustain Large Second-Harmonic Generation Responses106Nonlinear Optical Oxythiophosphate Approaching the Good Balance with Wide Ultraviolet Transparency, Strong Second Harmonic Effect, and Large Birefringence92Nonlinear Optical Oxythiophosphate Approaching the Good Balance with Wide Ultraviolet Transparency, Strong Second Harmonic Effect, and Large Birefringence13K 3 B 4 PO 10 and K 2 MB 4 PO 10 (M = Rb/Cs): rare mixed-coordinated borophosphates with large birefringence33Centrosymmetric RbSnF 2 NO 3 vs. noncentrosymmetric Rb 2 SbF 3 (NO 3 ) 254Deep-ultraviolet transparent alkali metal–rare earth metal sulfate NaY(SO 4 ) 2 ·H 2 O as a nonlinear optical crystal: synthesis and characterization28In situ hydrothermal synthesis of polar second-order nonlinear optical selenate Na 5 (SeO 4 )(HSeO 4 ) 3 (H 2 O) 219K 2 ZnMoP 2 O 10 : a novel nonlinear optical molybdophosphate with a strong second harmonic generation response and moderate birefringence24A comprehensive survey on nonlinear optical phosphates: Role of multicoordinate groups106M(NH 2 SO 3 ) 2 (M=Sr, Ba): Two Deep‐Ultraviolet Transparent Sulfamates Exhibiting Strong Second Harmonic Generation Responses and Moderate Birefringence142M(NH 2 SO 3 ) 2 (M=Sr, Ba): Two Deep‐Ultraviolet Transparent Sulfamates Exhibiting Strong Second Harmonic Generation Responses and Moderate Birefringence27UV Solar‐Blind‐Region Phase‐Matchable Optical Nonlinearity and Anisotropy in a π‐Conjugated Cation‐Containing Phosphate196UV Solar‐Blind‐Region Phase‐Matchable Optical Nonlinearity and Anisotropy in a π‐Conjugated Cation‐Containing Phosphate28[Ag(NH 3 ) 2 ] 2 SO 4 : A Strategy for the Coordination of Cationic Moieties to Design Nonlinear Optical Materials**6[Ag(NH3)2]2SO4: A Strategy for the Coordination of Cationic Moieties to Design Nonlinear Optical Materials**85Non-π-Conjugated Deep-Ultraviolet Nonlinear Optical Crystal K2Zn3(SO4)(HSO4)2F437Face specific doping of Janus all-cis-1,2,3,4,5,6-hexafluorocyclohexane with superalkalis and alkaline earth metals leads to enhanced static and dynamic NLO responses41An Effective Strategy for Designing Nonlinear Optical Crystals by Combining the Structure‐Directing Property of Oxyfluorides with Chemical Substitution73An Effective Strategy for Designing Nonlinear Optical Crystals by Combining the Structure‐Directing Property of Oxyfluorides with Chemical Substitution10Ba 2 Bi 2 [Zn(PO 4 ) 4 ]: ionic-isolation-activated first barium bismuth zincophosphate with unprecedented ∞ [Zn(PO 4 ) 4 ] 10− chains and balanced overall performance4Pushing KTiOPO4-like Nonlinear Optical Sulfates into the Deep-Ultraviolet Spectral Region19Recent Development of Non-π-Conjugated Deep Ultraviolet Nonlinear Optical Materials106BaSc 2 (HPO 3 ) 4 (H 2 O) 2 : a new nonlinear optical phosphite exhibiting a 3D {[Sc 2 (HPO 3 ) 4 ] 2− } ∞ anionic framework and phase-matchable SHG effect32Mixed superalkalis are a better choice than pure superalkalis for B 12 N 12 nanocages to design high-performance nonlinear optical materials21Nain(C2o4)(Hpo4)(H2o)5: An Ultraviolet Transparent Nonlinear Optical Oxalate-Phosphate with Large Birefringence0Superalkali (Li2F, Li3F) doped Al12N12 electrides with enhanced static, dynamic nonlinear optical responses and refractive indices44Assessment of alkali and alkaline earth metals doped cubanes as high-performance nonlinear optical materials by first-principles study29Lone Pair-Driven Enhancement of Birefringence in Polar Alkali Metal Antimony Phosphates46Orbital projection technique to explore the materials genomes of optical susceptibilities5RbLiZn5(PO4)4 and BaLiZn3(PO4)3: two new zinc orthophosphates with all tetrahedra-based anion frameworks11Lanthanum doped corannulenes with enhanced static and dynamic nonlinear optical properties: A first principle study17Local Polarity-Induced Assembly of Second-Order Nonlinear Optical Materials128A series of novel phosphites/phosphates with deep-ultraviolet cut-off edges from 0D polar to 3D non-polar architectures13Deep-ultraviolet nonlinear-optical crystal BaNa2[PO3(OH)]2 with large birefringence and strong second-harmonic-generation response8Single crystal growth and phase transition mechanism of KCsMoP 2 O 9 with efficient second harmonic generation via the emerging additional periodic phase technology4Structure and optical property evolution in PbM(PO 4 )X (M = Zn, Sn; X = halogen): SHG effect and birefringence21Controlling the Nonlinear Optical Behavior and Structural Transformation with A‐Site Cation in α‐AZnPO4 (A = Li, K)20Recent advances of inorganic phosphates with UV/DUV cutoff edge and large second harmonic response7Recent advances in non-π-conjugated nonlinear optical sulfates with deep-UV absorption edge53Diamondoid as potential nonlinear optical material by superalkali doping: A first principles study28Li4AAl(SO4)2F4 (A = Cs, Rb): two deep-UV fluoroaluminosulfates with special motif [AlS2O8F4]1Designing a Strong Second-Harmonic Generation Polar Iodate by the Structure-Directing Properties of the “Tumbler-like” [Zn(IO3)(I2O5(OH))] Polyanions20Na2Mg2P2O7F2: A new diphosphate of the cuspidine family without disorder designed by targeted structural modulation1(NH4)3(H3O)Zn4(PO4)4: A nonlinear optical zinc orthophosphate crystal9SrCl2·6H2O: An Alkaline-Earth-Metal Chloride Hexahydrate as Deep-Ultraviolet Nonlinear-Optical Crystal with the {[Sr(H2O)6]2+}∞ Cationic Framework8Li2.9Cs1.1(SO4)2: An Ultraviolet Transparent Sulfate as a Nonlinear Optical Crystal16From Centrosymmetry to Noncentrosymmetry: Precise Structural Regulation and Characterization on ZnHPO3·2H2O Polymorphs13Li2RbSO4Cl with a Short Ultraviolet Absorption Edge and an Acentric Structure through Assembling Heteroleptic [LiO3Cl] Tetrahedra2Deep-ultraviolet (DUV) nonlinear optical (NLO) crystals: An application in photonic technologies29Strategy for a Rational Design of Deep-Ultraviolet Nonlinear Optical Materials from Zeolites2Sr(NO 3 )(NH 2 SO 3 )·H 2 O: First Nitrate Sulfamate Revealing Remarkable Second Harmonic Generation and Optimized Birefringence25Enlargement of Bandgap and Birefringence in Nonlinear Optical Alkali‐Metal Sulfate Crystals by the Substitution of Asymmetrical Non‐π‐Conjugated Cation8(SO3CF3)−: A Non‐π‐Conjugated Motif for Nonlinear Optical Crystals Transparent into the Deep‐Ultraviolet Region23Na 10 Zn(NO 3 ) 4 (SO 3 S) 4 : a nonlinear optical crystal combining inorganic π-conjugated and non-π-conjugated heteroanion groups8Syntheses, structures and characterization of noncentrosymmetric MZnPO 4 (M = K, NH 4 )4The enhanced bandgap and birefringence of rare-earth phosphates XPO 4 (X = Sc, Y, La, and Lu): a first-principles investigation7Unraveling the role of superalkalis in modulating the static and dynamic hyperpolarizabilities of emerging calix[4]arenes11LiASi2O5 (A = K, Rb): Effects of cations on crystal structure and optical properties1Unearthing Superior Inorganic UV Second‐Order Nonlinear Optical Materials: A Mineral‐Inspired Method Integrating First‐Principles High‐Throughput Screening and Crystal Engineering124Unearthing Superior Inorganic UV Second‐Order Nonlinear Optical Materials: A Mineral‐Inspired Method Integrating First‐Principles High‐Throughput Screening and Crystal Engineering4KPO2(NHCONH2)2: A Promising Deep-Ultraviolet Nonlinear Optical Phosphate Containing Polar [PO2(NHCONH2)2]− Tetrahedra15Enhanced Birefringence in Phosphates via “Two Steps in One”: d0 Transition Metal Regulation and Fluorination Synergistic Strategy7Enhanced UV Nonlinear Optical Properties in Layered Germanous Phosphites through Functional Group Sequential Construction11Enhanced UV Nonlinear Optical Properties in Layered Germanous Phosphites through Functional Group Sequential Construction116Impact of doping with organic dopants and mixed doping with alkali metals and organic dopants on the absorption, electronic, optoelectronic, thermodynamic and nonlinear optical properties of dibenzo[b,def]chrysene in gaseous media: DFT and TD-DFT studies3Screening Strategy Identifies an Overlooked Deep‐Ultraviolet Transparent Nonlinear Optical Crystal3Screening Strategy Identifies an Overlooked Deep‐Ultraviolet Transparent Nonlinear Optical Crystal45Promising Functional Structural Building Unit Trisulfimide (SO2N)33– and Its Contributions to Second Harmonic Generation and Birefringence1MgPO2F3: An Ultraviolet Nonlinear Optical System with an Extremely Short Phase-Matching Wavelength Achieved by Introducing Dual-Type Fluorine via Structure Prediction1A tri-alkali/alkaline-earth metal fluorophosphate deep-ultraviolet birefringent crystal with coexisting PO 3 F and PO 2 F 24An excellent ultraviolet nonlinear optical crystal derived from the polar methylphosphonate unit8Four noncentrosymmetric molybdophosphates discovered by a chemical substitution strategy4Pb9Si8O22Cl6 and Pb3.07Ca1.93Si3O11: Two Ultraviolet Nonlinear Optical Materials Exhibit a Moderate Second Harmonic Generation Response1SnHPO4: A Layered Tin(II) Phosphate with Enhanced Birefringence51Chiral-Unit-Oriented Design of Non-π-Conjugated Noncentrosymmetric Phosphates with Short Absorption Edges4Nonbonding 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 Properties26Three Deep-UV Phosphate Optical Materials with Interesting Structural Evolution0Design, Synthesis, and Improvement of Nonlinear Optical Properties from Aluminophosphite to Aluminophosphate1Tuning the Anionic Configuration in ASc2(P2O7)2 (A = Ba, Pb) through A-Site Cationic Coordination Engineering0KF·[SO 2 (NH 2 ) 2 ]: the First Deep‐Ultraviolet Transparent Sulfonamide Fluoride Nonlinear Optical Crystal with Novel Cairo Pentagonal Structure13KF·[SO 2 (NH 2 ) 2 ]: the First Deep‐Ultraviolet Transparent Sulfonamide Fluoride Nonlinear Optical Crystal with Novel Cairo Pentagonal Structure5Stepwise Substitution Strategy for Beryllium-Based Selenites with Enhanced SHG Response, Moderate Birefringence, and Short UV Cutoff Edges6

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