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RESEARCH PAPER · Journal of the American Chemical Society · 2014

Deep-Ultraviolet Transparent Phosphates RbBa 2 (PO 3 ) 5 and Rb 2 Ba 3 (P 2 O 7 ) 2 Show Nonlinear Optical Activity from Condensation of [PO 4 ] 3– Units

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Deep-Ultraviolet Transparent Phosphates RbBa 2 (PO 3 ) 5 and Rb 2 Ba 3 (P 2 O 7 ) 2 Show Nonlinear Optical Activity from Condensation of [PO 4 ] 3– UnitsOriginalGrowth and properties of a noncentrosymmetric polyphosphate CsLa(PO 3 ) 4 crystal with deep-ultraviolet transparency100Anomalous second-harmonic generation response in SrBPO 5 and BaBPO 541Assembly of noncentrosymmetric coordination polymers by the integration of acentric Ba( ii )/Sr( ii ) and Li( i ) coordination polyhedra8Synthesis, characterization and theoretical studies of nonlinear optical crystal Sr 2 B 5 O 9 (OH)·H 2 O29Recent advances on second-order NLO materials based on metal iodates328Tailored Synthesis of a Nonlinear Optical Phosphate with a Short Absorption Edge241Tailored Synthesis of a Nonlinear Optical Phosphate with a Short Absorption Edge60Three Alkali Metal Lead Orthophosphates – Syntheses, Crystal Structures and Properties of APbPO4 (A = K, Rb, Cs)20Highly Efficient Red-Light Emission in An Organic–Inorganic Hybrid Ferroelectric: (Pyrrolidinium)MnCl 3378(3+1)-Dimensional incommensurately modulated structure and photoluminescence property of polyphosphate Ho(PO3)310Crystal structure, spectroscopic studies and non‐linear optical properties of 2‐amino‐3‐nitropyridinium trichloroacetate15Synthesis, crystal structures and properties of lead phosphite compounds27Design and Synthesis of the Beryllium‐Free Deep‐Ultraviolet Nonlinear Optical Material Ba3(ZnB5O10)PO4300The mechanism for the nonlinear optical properties in La9Na3B8O27, La2Na3B3O9and La2CaB10O19:ab initiostudies13Growth, anisotropic spectroscopy and laser operation of the monoclinic Nd:KGd(PO 3 ) 4 crystal6Li 3 AlSiO 5 : the first aluminosilicate as a potential deep-ultraviolet nonlinear optical crystal with the quaternary diamond-like structure54Bidenticity-Enhanced Second Harmonic Generation from Pb Chelation in Pb3Mg3TeP2O14169“XA 6 ” octahedra influencing the arrangement of anionic groups and optical properties in inverse-perovskite [B 6 O 10 ]XA 3 (X = Cl, Br; A = alkali metal)19Alkali metal–alkaline earth metal borate crystal LiBa 3 (OH)(B 9 O 16 )[B(OH) 4 ] as a new deep-UV nonlinear optical material34AMgPO 4 ·6H 2 O (A = Rb, Cs): strong SHG responses originated from orderly PO 4 groups59Experimental and theoretical studies on the linear and nonlinear optical properties of lead phosphate crystals LiPbPO 474KPb 2 (PO 3 ) 5 : a novel nonlinear optical lead polyphosphate with a short deep-UV cutoff edge109Li 3 Cs 2 M 2 B 3 P 6 O 24 (M = Pb, Sr): borophosphates with double six-membered ring of [BP 2 O 8 ] 3−22Nonlinear optical response mechanism of noncentrosymmetric lead borate Pb 6 [B 4 O 7 (OH) 2 ] 3 with three crystallographically independent [B 4 O 7 (OH) 2 ] 4− chains8Three new phosphates with isolated P 2 O 7 units: noncentrosymmetric Cs 2 Ba 3 (P 2 O 7 ) 2 and centrosymmetric Cs 2 BaP 2 O 7 and LiCsBaP 2 O 768Supramolecular Interactions Induced Chirality Transmission, Second Harmonic Generation Responses, and Photoluminescent Property of a Pair of Enantiomers from in Situ [2 + 3] Cycloaddition Synthesis18A Cubic Non-Centrosymmetric Mixed-Valence Iron Borophosphate–Phosphite6KMg6(P2O7)2P3O10: A novel phosphate with two distinct anions22Designing a Beryllium-Free Deep-Ultraviolet Nonlinear Optical Material without a Structural Instability Problem255Electronic, Crystal Chemistry, and Nonlinear Optical Property Relationships in the Dugganite A3B3CD2O14 Family148The Flexibility of P2O7 Dimers in Soft Structures: M2CdP2O7 (M = Rb, Cs)13Crystal growth and optical characteristics of beryllium-free polyphosphate, KLa(PO3)4, a possible deep-ultraviolet nonlinear optical crystal101Unusual Sequential Reversible Phase Transitions Containing Switchable Dielectric Behaviors in Cyclopentyl Ammonium 18-Crown-6 Perchlorate110Application of the Dimensional Reduction Formalism to Pb12[Li2(P2O7)2(P4O13)2](P4O13): a Phosphate Containing Three Types of Isolated P–O Groups21A New Deep-Ultraviolet Transparent Orthophosphate LiCs 2 PO 4 with Large Second Harmonic Generation Response384Deep Ultraviolet Nonlinear Optical Materials644K5Ba10(BO3)8F: A New Potassium Barium Borate Fluoride with a Perovskite-Like Structure43A new congruent-melting double phosphate PbCd(PO3)4 with photocatalytic activity10Syntheses, characterization and theoretical studies of three apatite-type phosphates MPb4(PO4)3 (M = K, Rb, Cs)17Growth, Properties, and Theoretical Analysis of KBa2(PO3)5 Single Crystal51Deep-Ultraviolet Transparent Cs 2 LiPO 4 Exhibits an Unprecedented Second Harmonic Generation160Syntheses and Characterizations of Three Bismuth(III)‐Containing Mixed‐Metal Phosphates:Ba 2 Bi 2 M II (PO 4 ) 4 (M= Mn, Ni, Cu)2Role of reaction time in tuning the morphology and third order nonlinear optical properties of barium borate7Strong 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 response95Cooperation of Three Chromophores Generates the Water‐Resistant Nitrate Nonlinear Optical Material Bi3TeO6OH(NO3)2113Cooperation of Three Chromophores Generates the Water‐Resistant Nitrate Nonlinear Optical Material Bi3TeO6OH(NO3)220A new method for the preparation of a [Sn 2 (H 2 PO 2 ) 3 ]Br SHG-active polar crystal via surfactant-induced strategy12A new phase-matchable nonlinear optical silicate: Rb 2 ZnSi 3 O 825Application of the dimensional reduction formalism to Pb 9−x Ba x [Li 2 (P 2 O 7 ) 2 (P 4 O 13 ) 2 ] (x = 0, 2, 6, 7): a series of phosphates with two types of isolated polyphosphate groups13Enhancing optical anisotropy of crystals by optimizing bonding electron distribution in anionic groups236Reversible structural phase transition, ferroelectric and switchable dielectric properties of an adduct molecule of hexamethylenetetramine ferrocene carboxylic acid23Solvent-controlled syntheses of mixed-alkali-metal borates exhibiting UV nonlinear optical properties23Structure 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 units16Theoretical investigation on the balance between large band gap and strong SHG response in BMO 4 (M = P and As) crystals22Theoretical perspectives on the structure, electronic, and optical properties of titanosilicates Li 2 M 4 [(TiO)Si 4 O 12 ] (M = K + , Rb + )13Two Phosphates: Noncentrosymmetric Cs6Mg6(PO3)18 and Centrosymmetric Cs2MgZn2(P2O7)255Facile Syntheses of Ba2[B4O7(OH)2] and Na[B5O7(OH)2](H2O) Borate Salts Exhibiting Nonlinear Optical Activity in the Ultraviolet50M4Mg4(P2O7)3 (M = K, Rb): Structural Engineering of Pyrophosphates for Nonlinear Optical Applications238A3Sr2P7O21 (A = Rb, Cs): Two Polyphosphates Based on Different Types of P–O Chains and Ring Structures36(H 3 O)Ca 2 Zn 3.5 (PO 4 ) 4 and Ba 2 Cd 3 (PO 4 ) 2 (HPO 4 ) 2 : Syntheses, crystal structures and characterizations of two mixed metal phosphates12Improvement of second-harmonic generation induced by structural distortions in Nb doped YCa9(VO4)7 crystals13Linear-to-λ-Shape P–O–P Bond Transmutation in Polyphosphates with Infinite (PO3)∞ Chain15CsB 4 O 6 F: A Congruent‐Melting Deep‐Ultraviolet Nonlinear Optical Material by Combining Superior Functional Units184CsB4O6F: A Congruent‐Melting Deep‐Ultraviolet Nonlinear Optical Material by Combining Superior Functional Units895Viewpoint: Inorganic Materials for UV and Deep-UV Nonlinear-Optical Applications207LiGaGe2S6: A Chalcogenide with Good Infrared Nonlinear Optical Performance and Low Melting Point56Li1.52Na4.48Cd8(PO4)2(P2O7)4: A new mixed-anion diphosphate containing four types of dimensions groups9K2[B3O3(OH)5]: A new deep-UV nonlinear optical crystal with isolated [B3O3(OH)5]2- anionic groups31An optoelectronic duple bistable phosphate with ultrahigh thermal stability7Crystal Growth and Optical Properties of Beryllium-Free Nonlinear Optical Crystal K3Ba3Li2Al4B6O20F35A beryllium-free deep-UV nonlinear optical material CsNaMgP 2 O 7 with honeycomb-like topological layers53Design and synthesis of a nonlinear optical material BaAl 4 S 7 with a wide band gap inspired from SrB 4 O 763Li 8 NaRb 3 (SO 4 ) 6 ·2H 2 O as a new sulfate deep-ultraviolet nonlinear optical material93Oxyhalides: prospecting ore for optical functional materials with large laser damage thresholds76A Joint Strategy To Evaluate the Microscopic Origin of the Second-Harmonic-Generation Response in Nonpolar ABCO3F Compounds32Non-Centrosymmetric RbNaMgP 2 O 7 with Unprecedented Thermo-Induced Enhancement of Second Harmonic Generation239Syntheses, Crystal Structures and Luminescent Properties of Two New Heterometallic Phosphates: Sn 2 Ge(PO 4 ) 2 (OH) 2 and Sn 2 Mn(PO 4 ) 27Synthesis, crystal structure and characterizations of a new diphosphate Rb2CaP2O719Pushing Nonlinear Optical Oxides into the Mid-Infrared Spectral Region Beyond 10 μm: Design, Synthesis, and Characterization of La3SnGa5O14145The 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 crystals257Crystal structures and theoretical studies of polyphosphate LiZnP3O9 for nonlinear optical applications18CaB5O7F3: A Beryllium-Free Alkaline-Earth Fluorooxoborate Exhibiting Excellent Nonlinear Optical Performances192Polar Fluorooxoborate, NaB4O6F: A Promising Material for Ionic Conduction and Nonlinear Optics494Polar Fluorooxoborate, NaB4O6F: A Promising Material for Ionic Conduction and Nonlinear Optics67The relationship between covalent bonds and the optical response in a nonpolar family ATeMoO 6 (A=Mg, Zn, Cd): A Berry-phase investigation14Crystal packing, high-temperature phase transition, second-order nonlinear optical and biological activities in a hybrid material: [(S) C7H16N2][CuBr4]12Synthesis, structure and electronic structure calculation of a new perovskite-type phosphate fluoride K2BaPO4F9Exploring Potential Beryllium-free, Deep-Ultraviolet Optical Crystals in the Rare Earth Fluoride Carbonate–Water System34Rational Design of the First Lead/Tin Fluorooxoborates MB2O3F2 (M = Pb, Sn), Containing Flexible Two-Dimensional [B6O12F6]∞ Single Layers with Widely Divergent Second Harmonic Generation Effects211MIMIIP3O9 (MI = Rb, MII = Cd, Mg, Ca; MI = Cs, MII = Pb, Sr; MI = K, MII = Mg): Cation Substitution Application in Cyclophosphate Family and Nonlinear Optical Properties35Non-centrosymmetric BaNaP3O9 with a short deep-ultraviolet cutoff edge14Two noncentrosymmetric polyphosphates featuring infinite one-dimensional (PO3)∞ chain, LiMP2O6 (M = Rb, Cs): Synthesis, structure and optical properties8Module-Guided Design Scheme for Deep-Ultraviolet Nonlinear Optical Materials195Removal of A-Site Alkali and Alkaline Earth Metal Cations in KBe2BO3F2-Type Layered Structures To Enhance the Deep-Ultraviolet Nonlinear Optical Capability46ALiZnP2O7 (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 Structure245Monofluorophosphates: A New Source of Deep-Ultraviolet Nonlinear Optical Materials257The linear and nonlinear optical response of CsGeX3 (X=Cl, Br, and I): The finite field and first-principles investigation26Ce(IO3)2F2⋅H2O: The First Rare‐Earth‐Metal Iodate Fluoride with Large Second Harmonic Generation Response66BaPO3Cl: a Metal Phosphate Chloride with Infinite [PO3]∞ Chains25A UV Transmittable NLO crystal Hydrofluoric Acid Mixed Sulphamic acid (FASA) : Synthesis, Growth and Characterization0Experimental characterization and first principles calculations of linear and nonlinear optical properties of two orthophosphates A 3 Al 2 (PO 4 ) 3 (A = Rb, K)36A 2 Bi 2 (SO 4 ) 2 Cl 4 (A = NH 4 , K, Rb): achieving a subtle balance of the large second harmonic generation effect and sufficient birefringence in sulfate nonlinear optical materials98Centrosymmetric K 2 SO 4 ·(SbF 3 ) 2 and noncentrosymmetric Rb 2 SO 4 ·(SbF 3 ) 2 resulting from cooperative effects of lone pair and cation size63Fluoroborophosphates: a family of potential deep ultraviolet NLO materials43From CuFeS 2 to Ba 6 Cu 2 FeGe 4 S 16 : rational band gap engineering achieves large second-harmonic-generation together with high laser damage threshold22Growth 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 tetrahedra21Mn-Based tin sulfide Sr 3 MnSn 2 S 8 with a wide band gap and strong nonlinear optical response30Modulation of perovskite-related frameworks induced by alkaline earth metals in phosphate fluorides A 2 MPO 4 F (A = K, Rb; M = Ba, Ca)8Non-concentration quenching, good thermal stability and high quantum efficiency of K 5 Y(P 2 O 7 ) 2 :Eu 3+ /Tb 3+ phosphors with a novel two-dimensional layer structure78RbSbSO 4 Cl 2 : an excellent sulfate nonlinear optical material generated due to the synergistic effect of three asymmetric chromophores79Structural insights into three phosphates with distinct polyanionic configurations20Syntheses, structures, anomalous phase transition and optical properties of two new polymorphic α- and β-LiMoPO 611Abrupt Structural Transformation in Asymmetric ABPO4F (A = K, Rb, Cs)21A New Cadmium‐Based Pb2Cd3(PO4)2(P2O7) with Two Types of Isolated P–O Groups18Lone‐Pair Enhanced Birefringence in an Alkaline‐Earth Metal Tin(II) Phosphate BaSn 2 (PO 4 ) 2130Two Non-π-Conjugated Deep-UV Nonlinear Optical Sulfates268CsSbF 2 SO 4 : An Excellent Ultraviolet Nonlinear Optical Sulfate with a KTiOPO 4 (KTP)‐type Structure87CsSbF2SO4: An Excellent Ultraviolet Nonlinear Optical Sulfate with a KTiOPO4 (KTP)‐type Structure432Four new deep ultraviolet borates with isolated B12O24 groups: Synthesis, structure, and optical properties9CsLiMgP2O7: A congruently melting pyrophosphate with a [LiMgP4O18] 6-membered ring fundamental building block5Cs2Zn5(PO4)4 and Cs3La(PO4)2: Two Cs‐Containing Phosphates with Three‐Dimensional Frameworks14Deep-Ultraviolet Mixed-Alkali-Metal Borates with Induced Enlarged Birefringence Derived from the Structure Rearrangement of the LiB3O545Uniform Alignment of Non-π-Conjugated Species Enhances Deep Ultraviolet Optical Nonlinearity369LiGaP 2 O 7 : A Potential UV Nonlinear-Optical Crystal14KNa 4 B 2 P 3 O 13 : A Deep-Ultraviolet Transparent Borophosphate Exhibiting Second-Harmonic Generation Response26In situ [2 + 3] cycloaddition synthesis, crystal structures, strong SHG responses and fluorescence properties of three novel Zn coordination polymers13Highly Polarizable Hg2+ Induced a Strong Second Harmonic Generation Signal and Large Birefringence in LiHgPO4265Centrosymmetric 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 RbLiMgP2O710LiCsPbP2O7: A new alkali metal lead pyrophosphate featuring two dimensional [LiP2O7]∞ layer2KMg(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 RbNaMgP2O721Synthesis, characterization, and properties of two new phosphate crystals MZnAl(PO4)2 (M = Na, K) with 3D framework tunnel structures14β-Ba(PO3)2 with DUV cut-off edge and large birefringence5A new iodate-phosphate Pb 2 (IO 3 )(PO 4 ) achieving great improvement in birefringence activated by (IO 3 ) − groups53Emergent Deep‐Ultraviolet Nonlinear Optical Candidates324Neue Kandidaten für die nichtlineare Optik im Tief‐UV‐Bereich43(NH 4 ) 3 [B(OH) 3 ] 2 (COOH) 3 : a graphite-like UV nonlinear optical material with a large birefringence via structural optimization31M 4 LiBe 4 P 7 O 24 and M 4 Li(Li 3 P)P 7 O 24 (M = Cs, Rb): deep-ultraviolet nonlinear-optical phosphates with a tetrahedra-substituted paracelsian-like framework9Na 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 birefringence49PbSrSiO 4 : a new ultraviolet nonlinear optical material with a strong second harmonic generation response and moderate birefringence37Polar polymorphism: α- and β-KCsWP 2 O 9 nonlinear optical materials with a strong second harmonic generation response25

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