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RESEARCH PAPER · Journal of the American Chemical Society · 2013

Deep-Ultraviolet Nonlinear Optical Crystals: Ba3P3O10X (X = Cl, Br)

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Deep-Ultraviolet Nonlinear Optical Crystals: Ba3P3O10X (X = Cl, Br)OriginalGrowth and properties of a noncentrosymmetric polyphosphate CsLa(PO 3 ) 4 crystal with deep-ultraviolet transparency100Deep-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– Units354Anomalous second-harmonic generation response in SrBPO 5 and BaBPO 541Synthesis, characterization and theoretical studies of nonlinear optical crystal Sr 2 B 5 O 9 (OH)·H 2 O29Simulated pressure-induced blue-shift of phase-matching region and nonlinear optical mechanism for K3B6O10X (X = Cl, Br)165Recent 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)20Pb17O8Cl18: A Promising IR Nonlinear Optical Material with Large Laser Damage Threshold Synthesized in an Open System223Pb2Ba3(BO3)3Cl: A Material with Large SHG Enhancement Activated by Pb-Chelated BO3 Groups279First-Principles Evaluation of the Alkali and/or Alkaline Earth Beryllium Borates in Deep Ultraviolet Nonlinear Optical Applications130Synthesis, crystal structures and properties of lead phosphite compounds27Design and Synthesis of the Beryllium‐Free Deep‐Ultraviolet Nonlinear Optical Material Ba3(ZnB5O10)PO4300First example of borirane synthesis by α-olefins reaction with BCl3·SMe2 Catalyzed with (η5-C5H5)2TiCl218Li 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)19Active performance of tetrahedral groups to SHG response: theoretical interpretations of Ge/Si-containing borate crystals3Alkali 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 groups59An effective strategy to achieve deeper coherent light for LiB 3 O 529Effect of lead and caesium on the mechanical, vibrational and thermodynamic properties of hexagonal fluorocarbonates: a comparative first principles study15Experimental 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 ] 3−22Three 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 768A Cubic Non-Centrosymmetric Mixed-Valence Iron Borophosphate–Phosphite6NaBa4(GaB4O9)2X3 (X = Cl, Br) with NLO-Active GaO4 Tetrahedral Unit: Experimental and ab Initio Studies25Designing a Beryllium-Free Deep-Ultraviolet Nonlinear Optical Material without a Structural Instability Problem255Synthesis and structure of a new halophosphate Sr 3 P 3 O 10 Cl with the flexible [P 3 O 10 ] 5− anions9Electronic, Crystal Chemistry, and Nonlinear Optical Property Relationships in the Dugganite A3B3CD2O14 Family148Crystal growth and optical characteristics of beryllium-free polyphosphate, KLa(PO3)4, a possible deep-ultraviolet nonlinear optical crystal101Na 2 ZnGe 2 S 6 : A New Infrared Nonlinear Optical Material with Good Balance between Large Second-Harmonic Generation Response and High Laser Damage Threshold302Top-Seeded Solution Crystal Growth, Morphology, Optical and Thermal Properties of Ba3(ZnB5O10)PO442A Deep-Ultraviolet Nonlinear Optical Crystal: Strontium Beryllium Borate Fluoride with Planar Be(O/F)3 Groups49Application 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 Materials644Syntheses, characterization and theoretical studies of three apatite-type phosphates MPb4(PO4)3 (M = K, Rb, Cs)17Pb2BO3Cl: A Tailor‐Made Polar Lead Borate Chloride with Very Strong Second Harmonic Generation381Pb2BO3Cl: A Tailor‐Made Polar Lead Borate Chloride with Very Strong Second Harmonic Generation129Growth, 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)2Strong 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 response95LiRb 2 LaB 2 O 6 : a new rare-earth borate with a MOF-5-like topological structure and a short UV cut-off edge14A 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 groups236Low-temperature-flux syntheses of ultraviolet-transparent borophosphates Na 4 MB 2 P 3 O 13 (M = Rb, Cs) exhibiting a second-harmonic generation response23Na 2 CdGe 2 Q 6 (Q = S, Se): two metal-mixed chalcogenides with phase-matching abilities and large second-harmonic generation responses77Structure 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 units16Tailored synthesis of nonlinear optical quaternary chalcohalides: Ba 4 Ge 3 S 9 Cl 2 , Ba 4 Si 3 Se 9 Cl 2 and Ba 4 Ge 3 Se 9 Cl 252The first quaternary diamond-like semiconductor with 10-membered LiS 4 rings exhibiting excellent nonlinear optical performances104Theoretical 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)255Cp2TiCl2-catalyzed cycloboration of α-olefins with PhBCl2 in the synthesis of 2-alkyl(aryl,benzyl)-1-phenylboriranes24M4Mg4(P2O7)3 (M = K, Rb): Structural Engineering of Pyrophosphates for Nonlinear Optical Applications238Fluorooxoborates: Beryllium‐Free Deep‐Ultraviolet Nonlinear Optical Materials without Layered Growth892Fluorooxoborates: Beryllium‐Free Deep‐Ultraviolet Nonlinear Optical Materials without Layered Growth99A3Sr2P7O21 (A = Rb, Cs): Two Polyphosphates Based on Different Types of P–O Chains and Ring Structures36First-Principles Assisted Prediction of the Nonlinear Optical Behavior of Mg3B7O13Cl Crystal6(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 phosphates12A New KBBF-Family Nonlinear Optical Material with Strong Interlayer Bonding51Structurally stable borate as a UV nonlinear optical material20Linear-to-λ-Shape P–O–P Bond Transmutation in Polyphosphates with Infinite (PO3)∞ Chain15LiGaGe2S6: 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 groups31Chemical Cosubstitution-Oriented Design of Rare-Earth Borates as Potential Ultraviolet Nonlinear Optical Materials267Crystal 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 layers53Cation-tuned synthesis of the A 2 SO 4 ·SbF 3 (A = Na + , NH 4 + , K + , Rb + ) family with nonlinear optical properties78Design and synthesis of a nonlinear optical material BaAl 4 S 7 with a wide band gap inspired from SrB 4 O 763Flexible gel-state thermoelectrochemical materials with excellent mechanical and thermoelectric performances based on incorporating Sn 2+ /Sn 4+ electrolyte into polymer/carbon nanotube composites59Four new quaternary chalcogenides A 2 Ba 7 Sn 4 Q 16 (A = Li, Na; Q = S, Se): syntheses, crystal structures determination, nonlinear optical performances investigation26K 2 TeP 2 O 8 : a new telluro-phosphate with a pentagonal Te–P–O layer structure26Li 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 ) 27Copper-Phenylacetylide Nanobelt/Single-Walled Carbon Nanotube Composites: Mechanochromic Luminescence Phenomenon and Thermoelectric Performance45Synthesis, crystal structure and characterizations of a new diphosphate Rb2CaP2O719Crystallographic and optical properties of Eu3+ doped K2Na3P3O10 triphosphate8Effect of Element Substitution on Structural Transformation and Optical Performances in I2BaMIVQ4 (I = Li, Na, Cu, and Ag; MIV = Si, Ge, and Sn; Q = S and Se)63Recent advances in ultraviolet and deep-ultraviolet second-order nonlinear optical crystals257Crystal structures and theoretical studies of polyphosphate LiZnP3O9 for nonlinear optical applications18A strategy for optical properties investigation in ABe 2 BO 3 F 2 (A=K, Rb, Cs) using finite field methods12Synthesis, structure and electronic structure calculation of a new perovskite-type phosphate fluoride K2BaPO4F9MgSiAs: An Unexplored System with Promising Nonlinear Optical Properties53Rational 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 edge14Hydrogen Bonding Assisted Construction of Graphite-like Deep-UV Optical Materials with Two Types of Parallel π-Conjugated Units22Two 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 Materials195Second-order nonlinear optical crystals with mixed anions250Tailoring nonlinear optical crystal borophosphate through the introduction of transition metal d orbitals for improving optical anisotropy and SHG response: a first-principles investigation1Removal 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 Skeleton34PbCdF(SeO 3 )(NO 3 ): A Nonlinear Optical Material Produced by Synergistic Effect of Four Functional Units52Why Some Noncentrosymmetric Borates Do Not Make Good Nonlinear Optical Materials: A Case Study with K3B5O8(OH)222Centrosymmetric (NH4)2SbCl(SO4)2 and Non-centrosymmetric (NH4)SbCl2(SO4): Synergistic Effect of Hydrogen-Bonding Interactions and Lone-Pair Cations on the Framework Structures and Macroscopic Centricities89A 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 investigation26Pb 2 GaF 2 (SeO 3 ) 2 Cl: Band Engineering Strategy by Aliovalent Substitution for Enlarging Bandgap while Keeping Strong Second Harmonic Generation Response178Noncentrosymmetric cubic RbBSi2O6 polymorph with deep ultraviolet cut-off edge4BaPO3Cl: a Metal Phosphate Chloride with Infinite [PO3]∞ Chains25Experimental 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 materials98ABaSbQ 3 (A = Li, Na; Q = S, Se): diverse arrangement modes of isolated SbQ 3 ligands regulating the magnitudes of birefringences50An alkali metal phosphate RbPbBi 2 (PO 4 ) 3 with three kinds of disorder: the effect of isolated soft cation units on the crystal structure7Centrosymmetric 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 size63From centrosymmetric to noncentrosymmetric: cation-directed structural evolution in X 3 ZnB 5 O 10 (X = Na, K, Rb) and Cs 12 Zn 4 (B 5 O 10 ) 4 crystals26Hybridization-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 tetrahedra21Lone pair effects on ternary infrared nonlinear optical materials19Modulation of perovskite-related frameworks induced by alkaline earth metals in phosphate fluorides A 2 MPO 4 F (A = K, Rb; M = Ba, Ca)8RbSbSO 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 611Tb(HSO 4 )(SO 4 ) – a green emitting hydrogensulfate sulfate with second harmonic generation response21Three new phosphates, Cs8Pb4(P2O7)4, CsLi7(P2O7)2 and LiCa(PO3)3: structural comparison, characterization and theoretical calculation23Two new tin( iv )-containing phosphate fluorides with two types of Sn( iv )–P–O–F frameworks and short cutoff edges0Y 8 O(OH) 15 (CO 3 ) 3 Cl: an excellent short-wave UV nonlinear optical material exhibiting an infrequent three-dimensional inorganic cationic framework61A New Cadmium‐Based Pb2Cd3(PO4)2(P2O7) with Two Types of Isolated P–O Groups18Two Non-π-Conjugated Deep-UV Nonlinear Optical Sulfates268Targeting the Next Generation of Deep-Ultraviolet Nonlinear Optical Materials: Expanding from Borates to Borate Fluorides to Fluorooxoborates450CsSbF 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 Structure432CsLiMgP2O7: A congruently melting pyrophosphate with a [LiMgP4O18] 6-membered ring fundamental building block5Refractive Index Modulates Second-Harmonic Responses in RE 8 O(CO 3 ) 3 (OH) 15 X (RE = Y, Lu; X = Cl, Br): Rare-Earth Halide Carbonates as Ultraviolet Nonlinear Optical Materials37Rational Design and Synthesis of a Deep-Ultraviolet Nonlinear Optical Fluorinated Orthophosphate: BaZn(PO4)F16RbB 11 O 16 (OH) 2 : First Hydroxyl Rubidium Borate with the B‐O 2D Layer Featuring Large Birefringence in the Rb‐B‐O‐H System5Cs2Zn5(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 Nonlinearity369Be2CO3F2 Monolayer: A Flexible Ultraviolet Nonlinear Optical Material via Rational Design6KNa 4 B 2 P 3 O 13 : A Deep-Ultraviolet Transparent Borophosphate Exhibiting Second-Harmonic Generation Response26Synthesis, structure and characterization of a new triphosphate: CsMg2P3O102Highly Polarizable Hg2+ Induced a Strong Second Harmonic Generation Signal and Large Birefringence in LiHgPO4265Synthesis, characterization and theoretical calculation of a noncentrosymmetric compound, Cs0.92B0.92Si5.08O122

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