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RESEARCH PAPER · Chemical Communications · 2018

Perfect balance harmony in Ba 2 NO 3 (OH) 3 : a beryllium-free nitrate as a UV nonlinear optical material

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Perfect balance harmony in Ba 2 NO 3 (OH) 3 : a beryllium-free nitrate as a UV nonlinear optical materialOriginalCation-tuned synthesis of the A 2 SO 4 ·SbF 3 (A = Na + , NH 4 + , K + , Rb + ) family with nonlinear optical properties78Cs 3 VO(O 2 ) 2 CO 3 : an exceptionally thermostable carbonatoperoxovanadate with an extremely large second-harmonic generation response129Remarkable multimember-ring configurations in a new family of Na 7 M II Sb 5 S 12 (M II = Zn, Cd, Hg) exhibiting various three-dimensional tunnel structures25Hydrogen Bonding Assisted Construction of Graphite-like Deep-UV Optical Materials with Two Types of Parallel π-Conjugated Units22PbCdF(SeO 3 )(NO 3 ): A Nonlinear Optical Material Produced by Synergistic Effect of Four Functional Units52Centrosymmetric (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 review on structure-performance relationship toward the optimal design of infrared nonlinear optical materials with balanced performances252A Langbeinite-Type Yttrium Phosphate LiCs2Y2(PO4)336BaPO3Cl: a Metal Phosphate Chloride with Infinite [PO3]∞ Chains25ABaSbQ 3 (A = Li, Na; Q = S, Se): diverse arrangement modes of isolated SbQ 3 ligands regulating the magnitudes of birefringences50An energy band engineering design to enlarge the band gap of KTiOPO 4 (KTP)-type sulfates via aliovalent substitution66Ba 3 B 10 O 17 F 2 ·0.1KF: the first mixed alkali/alkaline-earth metal fluorooxoborate with unprecedented double-layered B–O/F anionic arrangement17Ba 3 Ca 4 (BO 3 ) 3 (SiO 4 )Cl: a new non-centrosymmetric complex alkaline-earth metal borosilicate chloride with a deep-ultraviolet cut-off edge19Centrosymmetric 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 size63CO(NH 2 ) 2 ·NH 4 Cl: an ultraviolet birefringent material with conjugated CO groups16K 2 SrP 4 O 12 : a deep-UV transparent cyclophosphate as a nonlinear optical crystal79Pb 2 Cd(SeO 3 ) 2 X 2 (X = Cl and Br): two halogenated selenites with phase matchable second harmonic generation27Rb 3 SbF 3 (NO 3 ) 3 : an excellent antimony nitrate nonlinear optical material with a strong second harmonic generation response fabricated by a rational multi-component design44RbSbSO 4 Cl 2 : an excellent sulfate nonlinear optical material generated due to the synergistic effect of three asymmetric chromophores79Y 8 O(OH) 15 (CO 3 ) 3 Cl: an excellent short-wave UV nonlinear optical material exhibiting an infrequent three-dimensional inorganic cationic framework61Li2CsB7O10(OH)4: A Deep-Ultraviolet Nonlinear-Optical Mixed-Alkaline Borate Constructed by Unusual Heptaborate Anions98Pb4B6O13: A Polar Lead Oxyborate with Uncommon ∞(B6O12)6– Layers Exhibiting a Large Second Harmonic Generation Response15Layered Bismuth Oxyfluoride Nitrates Revealing Large Second-Harmonic Generation and Photocatalytic Properties37CsSbF 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 Structure432Balanced Second-Order Nonlinear Optical Properties of Adducts CHI3·(S8)3 and AsI3·(S8)3: A Systematic Survey48Synthesis, characterization, and theoretical analysis of three new nonlinear optical materials K7MRE2B15O30 (M= Ca and Ba, RE= La and Bi)28Tunable nonlinear optical absorption in amorphous and crystalline Sb2Se3 thin films27Synthesis and characterization of nickel doped zinc selenide nanospheres for nonlinear optical applications53Deep-Ultraviolet Mixed-Alkali-Metal Borates with Induced Enlarged Birefringence Derived from the Structure Rearrangement of the LiB3O545K9[B4O5(OH)4]3(CO3)X·7H2O (X = Cl, Br): Syntheses, Characterizations, and Theoretical Studies of Noncentrosymmetric Halogen Borate–Carbonates with Short UV Cutoff Edges16Centrosymmetric Rb2Mg3(SO4)4 and non-centrosymmetric Cs2Mg3(SO4)4 with a phase-matching nonlinear optical response35Two Indium Sulfate Tellurites: Centrosymmetric In 2 (SO 4 )(TeO 3 )(OH) 2 (H 2 O) and Non-centrosymmetric In 3 (SO 4 )(TeO 3 ) 2 F 3 (H 2 O)33Nitrate nonlinear optical crystals: A survey on structure-performance relationships146KMg(H 2 O)PO 4 : A Deep-Ultraviolet Transparent Nonlinear Optical Material Derived from KTiOPO 483Emergent Deep‐Ultraviolet Nonlinear Optical Candidates324Neue Kandidaten für die nichtlineare Optik im Tief‐UV‐Bereich43Rb3Na(H2C3N3O3)4·3H2O with Large Birefringence28(NH 4 ) 3 [B(OH) 3 ] 2 (COOH) 3 : a graphite-like UV nonlinear optical material with a large birefringence via structural optimization31[Al(H 2 O) 6 ](IO 3 ) 2 (NO 3 ): a material with enhanced birefringence induced by synergism of two superior functional motifs292(C 3 H 7 N 6 ) + ·2Cl − ·H 2 O: an ultraviolet nonlinear optical crystal with large birefrigence and strong second-harmonic generation78Enhancement of χ(3) by Sb substitution in As40Se50Ge10 amorphous semiconducting thin films0Inorganic planar π-conjugated groups in nonlinear optical crystals: review and outlook145K 4 (PO 2 F 2 ) 2 (S 2 O 7 ): first fluorooxophosphorsulfate with mixed-anion [S 2 O 7 ] 2− and [PO 2 F 2 ] − groups14Novel ultraviolet (UV) nonlinear optical (NLO) materials discovered by chemical substitution-oriented design302Role of annealing temperature on optimizing the linear and nonlinear optical properties of As 40 Se 50 Ge 10 films83Second-order nonlinear optical materials with a benzene-like conjugated π system49Two-stage evolution from phosphate to sulfate of new KTP-type family members as UV nonlinear optical materials through chemical cosubstitution-oriented design51Structure-property relationship in nonlinear optical materials with π-conjugated CO3 triangles146Noncentrosymmetric Fluorooxoborates A10B13O15F19 (A = K and Rb) with Unexpected [B10O12F13]7– Units and Deep-Ultraviolet Cutoff Edges26Linear and nonlinear optical properties change in Ag/GeS heterostructure thin films by thermal annealing and laser irradiation35Synthesis, Crystal Structure, and Characterization of a Noncentrosymmetric Sulfate Cs2Ca2(SO4)320Lead Mixed Oxyhalides Satisfying All Fundamental Requirements for High‐Performance Mid‐Infrared Nonlinear Optical Materials164Lead Mixed Oxyhalides Satisfying All Fundamental Requirements for High‐Performance Mid‐Infrared Nonlinear Optical Materials55Synthesis, characterizations and theoretical analysis of a noncentrosymmetric sulfate8Aliovalent-substituted synthesis for a non-centrosymmetric phosphate with enhanced nonlinear-optical response5K4Sb(SO4)3Cl: The first apatite-type sulfate ultraviolet nonlinear optical material with sharply enlarged birefringence61A6Sb4F12(SO4)3 (A = Rb, Cs): Two Novel Antimony Fluoride Sulfates with Unique Crown-like Clusters50New Alkaline-Earth Metal Fluoroiodates Exhibiting Large Birefringence and Short Ultraviolet Cutoff Edge with Highly Polarizable (IO 3 F) 2– Units63K 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 Performance38The study of structure evolvement of KTiOPO4 family and their nonlinear optical properties98CsHgNO3Cl2: A New Nitrate UV Birefringent Material Exhibiting an Optimized Layered Structure49Giant Optical Anisotropy in the UV‐Transparent 2D Nonlinear Optical Material Sc(IO 3 ) 2 (NO 3 )212Giant Optical Anisotropy in the UV‐Transparent 2D Nonlinear Optical Material Sc(IO 3 ) 2 (NO 3 )57Sb6O7(SO4)2: A Promising Ultraviolet Nonlinear Optical Material with an Enhanced Second‐Harmonic‐Generation Response Activated by SbIII Lone‐Pair Stereoactivity62The synthesis, characterization, and theoretical analysis of (NH 4 ) 3 PbCl 52BaTi(BO 3 ) 2 : an excellent birefringent material with highly coplanar isolated [BO 3 ] groups16Centrosymmetric RbSnF 2 NO 3 vs. noncentrosymmetric Rb 2 SbF 3 (NO 3 ) 254Computationally assisted multistage design and prediction driving the discovery of deep-ultraviolet nonlinear optical materials41From BaCl 2 to Ba(NO 3 )Cl: significantly enhanced birefringence derived from π-conjugated [NO 3 ]14Influence of top layer on the linear and nonlinear optical parameters of Ag(Te)/As50Se50 bilayer thin films11M(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 Birefringence27[C(NH2)3]3PO4·2H2O: A new metal-free ultraviolet nonlinear optical phosphate with large birefringence and second-harmonic generation response70Second-order nonlinear optical property of the ultraviolet transparent alkali metal-rare earth metal carbonate Na3Y(CO3)3.3H2O5Investigation of amorphous-crystalline transformation induced optical and electronic properties change in annealed As50Se50 thin films23Cyanurates consisting of intrinsic planar π-conjugated 6-membered rings: An emerging source of optical functional materials111Tin Chloride Sulfates A3Sn2(SO4)3–xCl1+2x (A = K, Rb, Cs; x = 0, 1) as Multifunctional Optical Materials33Structure-performance relationship in tri-coordinated nonlinear optical materials toward optimal second harmonic generation and phase matching31Hydroxyfluorooxoborate Na[B3O3F2(OH)2]⋅[B(OH)3]: Optimizing the Optical Anisotropy with Heteroanionic Units for Deep Ultraviolet Birefringent Crystals146Hydroxyfluorooxoborate Na[B3O3F2(OH)2]⋅[B(OH)3]: Optimizing the Optical Anisotropy with Heteroanionic Units for Deep Ultraviolet Birefringent Crystals16Two Tellurium(IV)-Based Sulfates Exhibiting Strong Second Harmonic Generation and Moderate Birefringence as Promising Ultraviolet Nonlinear Optical Materials28Synthesis, characterization and optical properties of three novel lanthanide sulfates10A Photochromic Zinc–Viologen Framework with a High-Contrast Nonlinear Optical Switchable Behavior24A General Principle for DUV NLO Materials: π‐Conjugated Confinement Enlarges Band Gap**175A General Principle for DUV NLO Materials: π‐Conjugated Confinement Enlarges Band Gap**27Noncentrosymmetric Rb3(COOH)3(H3BO3)2 vs Centrosymmetric Cs3(COOH)3(H3BO3)214Synergistic Effect of π-Conjugated [C(NH 2 ) 3 ] Cation and Sb(III) Lone Pair Stereoactivity on Structural Transformation and Second Harmonic Generation58NH4Sb2(C2O4)F5: A novel UV nonlinear optical material synthesized in deep eutectic solvents38Two molybdenyl carbonates with different dimensional structures exhibiting huge differences in band gaps7Ba2B13O19(OH)5·5H2O: A promising nonlinear optical material with a unique 2[B13O19(OH)5]∞ two-dimensional layer9Guanidinium Fluorooxoborates as Efficient Metal-free Short-Wavelength Nonlinear Optical Crystals140Hierarchical Modulation of Optical Anisotropy Driven by Metal Cation Polyhedra in Fluorooxoborates MIIB4O6F2 (MII=Be, Mg, Pb, Zn, Cd)6(C 3 N 6 H 7 ) 2 SiF 6 ·H 2 O: an ultraviolet birefringent crystal exceeding the intrinsic energy gap of an organic reagent38Large optical anisotropy differentiation induced by the anion-directed regulation of structures29Performance of optical materials with the derivative of planar π-conjugated groups: Recent advances and future prospects37Sc 2 F 2 (B 2 O 5 ): a deep ultraviolet scandium borate fluoride exhibiting large birefringence induced by the synergistic effect of B 2 O 5 and ScO n F 2 groups38Sn 9O 4Br 9X (X = Cl, Br): Two New Sn(II) Oxyhalides Exhibiting Large Birefringence Derived from Highly Distortive Polyhedra of Lone Pair Cations0Unprecedented boat-shaped [Mo 2 O 5 (IO 3 ) 4 ] 2− polyanions induced a strong second harmonic generation response31High‐Performance Sulfate Optical Materials Exhibiting Giant Second Harmonic Generation and Large Birefringence21High‐Performance Sulfate Optical Materials Exhibiting Giant Second Harmonic Generation and Large Birefringence199First-principles study of the influence of lone pair electrons and molecular groups on the birefringence of phosphate and fluorophosphate13The dependence of crystal structure and ultraviolet nonlinear optical property of KBe2BO3F2 by density functional theory and π-conjugate confinement2Impact on nonlinear/linear optical and structural parameters in quaternary In15Ag10S15Se60 thin films upon annealing at different temperatures27Layered Perovskite-like Nitrate Cs2Pb(NO3)2Br2 as a Multifunctional Optical Material40CsY(SO4)2·4H2O: A Deep-Ultraviolet Birefringent Crystal Induced by an Edge-Sharing Connection26Noncentrosymmetric (C3H7N6)6(H2PO4)4(HPO4)·4H2O and Centrosymmetric (C3H7N6)2SO4·2H2O: Exploration of Acentric Structure by Combining Planar and Tetrahedral Motifs via Hydrogen Bonds37(C3N6H7)2SbF5·H2O Exhibiting Strong Optical Anisotropy from the Optimal Arrangement of π-Conjugated (C3N6H7)+ Groups31A lithium–scandium sulfate with second-harmonic generation response and deep-ultraviolet transparency7An effective pathway to design and synthesize UV birefringent crystals via rational assembly of π-conjugated [CO 3 ] 2− and [NO 3 ] − triangles32Annealing-induced phase transformation in In 10 Se 70 Te 20 thin films and its structural, optical and morphological changes for optoelectronic applications64Constructing ultraviolet nonlinear optical crystals with large second harmonic generation and short absorption edges by using polar tetrahedral S 2 O 3 groups14Enhancing birefringence of non-π-conjugated sulfate systems through rare-earth metal-centered polyhedra10Hg 3 O 2 (NO 3 )F: a mercury nitrate oxyfluoride with an unprecedented [(Hg 3 O 2 F) + ] ∞ cationic framework and excellent optical anisotropy21Influence of time dependent laser-irradiation for tuning the linear–nonlinear optical response of quaternary Ag 10 In 15 S 15 Se 60 films for optoelectronic applications30K 5 [B 3 O 3 F 4 (OH)] 2 (NO 3 ): the first hydroxyfluorooxoborate-nitrate with a short ultraviolet cutoff edge and large birefringence18KRb 2 (NO 3 ) 2 Cl: a new birefringent crystal exhibiting a perovskite-related framework and a short cutoff edge6Low temperature molten salt synthesis of noncentrosymmetric (NH 4 ) 3 SbF 3 (NO 3 ) 3 and centrosymmetric (NH 4 ) 3 SbF 4 (NO 3 ) 234New Ultraviolet Nonlinear Optical Crystal Rb3Hg2(SO4)3Cl3Pb2Cl2(HPO3)(H2O) and Pb3Br2(HPO3)2: Two Phosphite Halides with 3D Structural Networks and Enlarged Birefringence18Sn9O4Br9X (X = Cl, Br): Two new Sn(II) oxyhalides exhibiting large birefringence derived from highly distortive polyhedra of lone pair cations9“Cation Activation”: An Effective Strategy for the Enhancement of Birefringence36Hg3(SeO3)2(SO4): A UV Nonlinear Optical Mercury Selenite Sulfate Constructed by Neat [Hg6O8(SeO3)4]∞ Layers and SO4 Tetrahedra27SrCl2·6H2O: 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 Crystal16Quadruple‐Bidentate Nitrate‐Ligated A 2 Hg(NO 3 ) 4 (A=K, Rb): Strong Second‐Harmonic Generation and Sufficient Birefringence59Quadruple‐Bidentate Nitrate‐Ligated A 2 Hg(NO 3 ) 4 (A=K, Rb): Strong Second‐Harmonic Generation and Sufficient Birefringence2Sr(NO 3 )(NH 2 SO 3 )·H 2 O: First Nitrate Sulfamate Revealing Remarkable Second Harmonic Generation and Optimized Birefringence25(SO3CF3)−: A Non‐π‐Conjugated Motif for Nonlinear Optical Crystals Transparent into the Deep‐Ultraviolet Region23Sr(NH2SO3)(NO3)·H2O: An Ultraviolet Nonlinear Optical Material Exhibiting Strong Second-Harmonic Generation Response and Sufficient Birefringence10Two UV organic-inorganic hybrid antimony-based materials with superior optical performance derived from cation-anion synergetic interactions30Na 10 Zn(NO 3 ) 4 (SO 3 S) 4 : a nonlinear optical crystal combining inorganic π-conjugated and non-π-conjugated heteroanion groups8Two van der Waals Layered Antimony(III) Phosphites as UV Optical Materials11Deep‐Ultraviolet Transparent Mixed Metal Sulfamates with Enhanced Nonlinear Optical Properties and Birefringence11Deep‐Ultraviolet Transparent Mixed Metal Sulfamates with Enhanced Nonlinear Optical Properties and Birefringence75Fluorination Strategy Towards Symmetry Breaking of Boron‐centered Tetrahedron for Poly‐fluorinated Optical Crystals15Fluorination Strategy Towards Symmetry Breaking of Boron‐centered Tetrahedron for Poly‐fluorinated Optical Crystals70A2Hgx(SeO3)y (A = K, Rb, Cs): Three Alkali Metal Mercury Selenites Featuring Unique 1D [HgOm(SeO3)n]∞ Chains13C 8 H 6 IN 3 O 4 : a birefringent crystal induced by uniformly aligned hybrid groups10Designing excellent UV birefringent materials through the synergistic interaction of two highly distorted functional groups23From BaAlBO 3 F 2 to BaAlB 3 O 6 F 2 and BaAl 2 (B 3 O 6 ) 2 F 2 : the enhancement of birefringence and band gap by extending the π-conjugated system combined with [Al–O/F] functional groups13Fully tricoordinated assembly unveils a pioneering nonlinear optical crystal (SbTeO 3 )(NO 3 )25Hydrogen bonding bolstered head-to-tail ligation of functional chromophores in a 0D SbF 3 ·glycine adduct for a short-wave ultraviolet nonlinear optical material32Synthesis, structures and properties of two new nitrate optical materials: Rb3ZnNO3Cl4 and Rb5Na(NO3)4Cl24Designing Optical Anisotropy: Silver-Aminoalkylpyridine Nitrate Complexes with Tunable Structures3RbY(SO4)2·4H2O: A new ultraviolet birefringent crystal3Guanidinium Vanadate [C(NH2)3]3VO4·2H2O Revealing Enhanced Second-Harmonic Generation and Wide Band Gaps13A Noncentrosymmetric Metal‐Free Borophosphate: Achieving a Large Birefringence and Excellent Stability by Covalent‐Linkage27Na3K6(CO3)3(NO3)2X·6H2O (X = NO3, Cl, Br): Exploring High-Performance UV Birefringent Crystals Induced by Coplanar π-Conjugated CO3 and NO3 Groups15

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  1. Cation-tuned synthesis of the A 2 SO 4 ·SbF 3 (A = Na + , NH 4 + , K + , Rb + ) family with nonlinear optical properties

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  2. Cs 3 VO(O 2 ) 2 CO 3 : an exceptionally thermostable carbonatoperoxovanadate with an extremely large second-harmonic generation response

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  4. Hydrogen Bonding Assisted Construction of Graphite-like Deep-UV Optical Materials with Two Types of Parallel π-Conjugated Units

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  5. PbCdF(SeO 3 )(NO 3 ): A Nonlinear Optical Material Produced by Synergistic Effect of Four Functional Units

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  13. Ba 3 Ca 4 (BO 3 ) 3 (SiO 4 )Cl: a new non-centrosymmetric complex alkaline-earth metal borosilicate chloride with a deep-ultraviolet cut-off edge

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  16. K 2 SrP 4 O 12 : a deep-UV transparent cyclophosphate as a nonlinear optical crystal

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  17. Pb 2 Cd(SeO 3 ) 2 X 2 (X = Cl and Br): two halogenated selenites with phase matchable second harmonic generation

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  21. Li2CsB7O10(OH)4: A Deep-Ultraviolet Nonlinear-Optical Mixed-Alkaline Borate Constructed by Unusual Heptaborate Anions

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  22. Pb4B6O13: A Polar Lead Oxyborate with Uncommon ∞(B6O12)6– Layers Exhibiting a Large Second Harmonic Generation Response

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  24. CsSbF 2 SO 4 : An Excellent Ultraviolet Nonlinear Optical Sulfate with a KTiOPO 4 (KTP)‐type Structure

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  30. Deep-Ultraviolet Mixed-Alkali-Metal Borates with Induced Enlarged Birefringence Derived from the Structure Rearrangement of the LiB3O5

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  31. K9[B4O5(OH)4]3(CO3)X·7H2O (X = Cl, Br): Syntheses, Characterizations, and Theoretical Studies of Noncentrosymmetric Halogen Borate–Carbonates with Short UV Cutoff Edges

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