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RESEARCH PAPER · Angewandte Chemie International Edition · 2018

Rb 3 VO(O 2 ) 2 CO 3 : A Four‐in‐One Carbonatoperoxovanadate Exhibiting an Extremely Strong Second‐Harmonic Generation Response

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Rb 3 VO(O 2 ) 2 CO 3 : A Four‐in‐One Carbonatoperoxovanadate Exhibiting an Extremely Strong Second‐Harmonic Generation ResponseOriginalCation-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 Units52Synthesis, crystal structures and nonlinear optical properties of polymorphism: α- and β-RbHgI3·H2O18Centrosymmetric (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 Centricities89Li2BaSc(BO3)2F and LiBa2Pb(BO3)2F with Layered Structures featuring Special Li−O/F Configurations11A 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]∞ Chains25Y2(CO3)3·H2O and (NH4)2Ca2Y4(CO3)9·H2O: Partial Aliovalent Cation Substitution Enabling Evolution from Centrosymmetry to Noncentrosymmetry for Nonlinear Optical Response37A Facile Route to Nonlinear Optical Materials: Three‐Site Aliovalent Substitution Involving One Cation and Two Anions137A Facile Route to Nonlinear Optical Materials: Three‐Site Aliovalent Substitution Involving One Cation and Two Anions23Changes of optical transition models caused by crystal structural changes in CaSe2O50A 2 SrM IV S 4 (A = Li, Na; M IV = Ge, Sn) concurrently exhibiting wide bandgaps and good nonlinear optical responses as new potential infrared nonlinear optical materials78A new ultraviolet transparent hydra-cyanurate K 2 (C 3 N 3 O 3 H) with strong optical anisotropy from delocalized π-bonds56A rich structural chemistry in π-conjugated hydroisocyanurates: layered structures of A 2 B(H 2 C 3 N 3 O 3 ) 4 · n H 2 O (A = K, Rb, Cs; B = Mg, Ca; n = 4, 10) with high ultraviolet transparency and strong optical anisotropy47An 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 arrangement17Centrosymmetric 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 groups16From 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 crystals26Functional layered materials with heavy metal lone pair cations, Pb 2+ , Bi 3+ , and Te 4+90K 2 SrP 4 O 12 : a deep-UV transparent cyclophosphate as a nonlinear optical crystal79LiO 4 tetrahedra lock the alignment of π-conjugated layers to maximize optical anisotropy in metal hydroisocyanurates44Mn-Based tin sulfide Sr 3 MnSn 2 S 8 with a wide band gap and strong nonlinear optical response30Pb 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 framework61Broadening Frontiers of Infrared Nonlinear Optical Materials with π-Conjugated Trigonal-Planar Groups67Bi2Te2O6(NO3)2(OH)2(H2O): A layered bismuth tellurium nitrate hydroxide with multiple noncentrosymmetric chromophores14Exploration of New Birefringent Crystals in Bismuth d0 Transition Metal Selenites35Li2CsB7O10(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 Properties37KLi(HC 3 N 3 O 3 )·2H 2 O: Solvent-drop Grinding Method toward the Hydro-isocyanurate Nonlinear Optical Crystal314CsSbF 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 Structure432Refractive 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 Materials37Balanced 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 applications53RbB 11 O 16 (OH) 2 : First Hydroxyl Rubidium Borate with the B‐O 2D Layer Featuring Large Birefringence in the Rb‐B‐O‐H System5Cs3Na(H2C3N3O3)4·3H2O: A Mixed Alkali‐Metal Hydroisocyanurate Nonlinear Optical Material Containing π‐Conjugated Six‐Membered‐Ring Units68Deep-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 Edges16β‐CsB9O14: A Triple‐Layered Borate with Edge‐Sharing BO4 Tetrahedra Exhibiting a Short Cutoff Edge and a Large Birefringence30Centrosymmetric 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)33Facile Growth of an Ultraviolet Hydroisocyanurate Crystal with Strong Nonlinearity and a Wide Phase-Matching Region from π-Conjugated (HC3N3O3)2– Groups45Cs2Bi2O(Ge2O7) (CBGO): A Larger SHG Effect Induced by Synergistic Polarizations of BiO5 Polyhedra and GeO4 Tetrahedra73Cs2Bi2O(Ge2O7) (CBGO): A Larger SHG Effect Induced by Synergistic Polarizations of BiO5 Polyhedra and GeO4 Tetrahedra18Sn2B5O9Cl: A Material with Large Birefringence Enhancement Activated Prepared via Alkaline‐Earth‐Metal Substitution by Tin255Sn2B5O9Cl: A Material with Large Birefringence Enhancement Activated Prepared via Alkaline‐Earth‐Metal Substitution by Tin33A x Ce 9 (IO 3 ) 36 (A = K, La): the effects of a change in the intermediate valence on the second-harmonic generation response7Li[LiCs2Cl][Ga3S6]: A Nanoporous Framework of GaS4 Tetrahedra with Excellent Nonlinear Optical Performance172Li[LiCs2Cl][Ga3S6]: A Nanoporous Framework of GaS4 Tetrahedra with Excellent Nonlinear Optical Performance40KMg(H 2 O)PO 4 : A Deep-Ultraviolet Transparent Nonlinear Optical Material Derived from KTiOPO 483A new iodate-phosphate Pb 2 (IO 3 )(PO 4 ) achieving great improvement in birefringence activated by (IO 3 ) − groups53K5(W3O9F4)(IO3): An Efficient Mid-Infrared Nonlinear Optical Compound with High Laser Damage Threshold114A new family of quaternary thiosilicates SrA 2 SiS 4 (A = Li, Na, Cu) as promising infrared nonlinear optical crystals48Emergent Deep‐Ultraviolet Nonlinear Optical Candidates324Neue Kandidaten für die nichtlineare Optik im Tief‐UV‐Bereich43Na2Mg1−xZnxSiO4 (0 ≤ x ≤ 1): Noncentrosymmetric Sodium Metal Silicate Solid Solutions with Ultraviolet Nonlinear Optical Properties71Structural Diversity and Giant Birefringence in Cyanates BaCNOX (X = Cl, Br, I, and CNO) Containing Linear π-Conjugated Units: A Combined Experimental and Theoretical Study13(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 motifs29[O 2 Pb 3 ] 2 (BO 3 )I: a new lead borate iodide with 1∞[O 2 Pb 3 ] double chains6Coordinated regulation on critical physiochemical performances activated from mixed tetrahedral anionic ligands in new series of Sr 6 A 4 M 4 S 16 (A = Ag, Cu; M = Ge, Sn) nonlinear optical materials28Inorganic 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 design302Optimal arrangement of π-conjugated anionic groups in hydro-isocyanurates leads to large optical anisotropy and second-harmonic generation effect42Polar polymorphism: α- and β-KCsWP 2 O 9 nonlinear optical materials with a strong second harmonic generation response25Similarities and differences between Mn( ii ) and Zn( ii ) coordination polymers supported by porphyrin-based ligands: synthesis, structures and nonlinear optical properties24Two-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 triangles146Infrared Nonlinear Optical Polymorphs α- and β-SrCu 2 SnS 4 Exhibiting Large Second Harmonic Generation Responses with Requisite Phase-Matching Behavior44Ultraviolet nonlinear optical crystal: (NH4)ZnPO47CsVO2F(IO3): An Excellent SHG Material Featuring an Unprecedented 3D [VO2F(IO3)]− Anionic Framework132CsVO2F(IO3): An Excellent SHG Material Featuring an Unprecedented 3D [VO2F(IO3)]− Anionic Framework22Alignment of Polar Moieties Leading to Strong Second Harmonic Response in KCsMoP2O951An Exceptional Peroxide Birefringent Material Resulting from d–π Interactions99An Exceptional Peroxide Birefringent Material Resulting from d–π Interactions15Synthesis, characterizations and theoretical analysis of a noncentrosymmetric sulfate8Strong Second Harmonic Generation in a Tungsten Bronze Oxide by Enhancing Local Structural Distortion48Aliovalent-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 birefringence61Hydrogen-Bond-Assisted Reinforcement of Interlayer Connections in Zn2BO3X·H2O (X = Cl, Br): Two UV Nonlinear Optical Crystals with KBBF-Type Structure9A6Sb4F12(SO4)3 (A = Rb, Cs): Two Novel Antimony Fluoride Sulfates with Unique Crown-like Clusters50Two Pyrophosphates with Large Birefringences and Second‐Harmonic Responses as Ultraviolet Nonlinear Optical Materials137Two Pyrophosphates with Large Birefringences and Second‐Harmonic Responses as Ultraviolet Nonlinear Optical Materials29Second-order nonlinear optical-active selenide borate Zn8Se2(BO2)12: Experimental and theoretical analysis9K 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 properties98Sr5[BO2(OH)]3(OH)3F: First hydroxyborate fluoride with the [BO2(OH)]2− unit2CsHgNO3Cl2: A New Nitrate UV Birefringent Material Exhibiting an Optimized Layered Structure49Ba3(BO3)(CO3)F: The First Borate Carbonate Fluoride Synthesized by the High‐Temperature Solution Method19Explorations of Second-Order Nonlinear Optical Materials in the Alkaline Earth Barbiturate System: Noncentrosymmetric Ca(H3C4N2O3)2·H2O and Centrosymmetric Sr(H5C8N4O5)2·4H2O23KSnI 3 ⋅ H 2 O: A New Compound with One‐Dimensional SnI 3 Chains of Pyramidal SnI 5 Polyhedra2An Antimony(III) Fluoride Oxalate with Large Birefringence45Sb6O7(SO4)2: A Promising Ultraviolet Nonlinear Optical Material with an Enhanced Second‐Harmonic‐Generation Response Activated by SbIII Lone‐Pair Stereoactivity62Hydrogen-Bond-Assisted Alignment of [MCu(SeO 3 ) 4 Cl(H 2 O)] 4– (M = Fe, Ga) Anionic Layers to Form Two Polar Oxychlorides: Pb 2 MCu(SeO 3 ) 4 Cl(H 2 O)10Barium fluoroiodate crystals with a large band gap and birefringence22Computationally assisted multistage design and prediction driving the discovery of deep-ultraviolet nonlinear optical materials41From thiophosphate to chalcohalide: mixed-anion AgS x Cl y ligands concurrently enhancing nonlinear optical effects and laser-damage threshold10K 2 Pb(H 2 C 3 N 3 O 3 ) 4 (H 2 O) 4 : a potential UV nonlinear optical material with large birefringence50M 6 PS 5 X (M = Ag, Cu; X = Cl, Br) chalcohalides exhibiting strong nonlinear optical responses and high laser damage resistances9Pb 2 TiFO(SeO 3 ) 2 Br: a new polar compound with the strongest second harmonic generation in the selenite bromide family29Systematic centricity control using a chiral template: novel noncentrosymmetric polar niobium oxyfluorides and tantalum fluorides directed by chiral histidinium cations, [( l -hisH 2 )NbOF 5 ], [( d -hisH 2 )NbOF 5 ], [( l -hisH 2 )TaF 7 ], and [( d -hisH 2 )TaF 7 ]8Zn(NH 3 )CO 3 : a “three-in-one” UV nonlinear optical crystal built by a polar molecule bonding strategy18Second-order nonlinear optical and photoelectric properties of Zn4B6O12S20[C(NH2)3]3PO4·2H2O: A new metal-free ultraviolet nonlinear optical phosphate with large birefringence and second-harmonic generation response70A Deep‐UV Nonlinear Optical Borosulfate with Incommensurate Modulations71A Deep‐UV Nonlinear Optical Borosulfate with Incommensurate Modulations13π‑Conjugated Trigonal Planar [C(NH2)3]+ Cationic Group: A Superior Functional Unit for Ultraviolet Nonlinear Optical Materials52LiZn(OH)CO3: A Deep‐Ultraviolet Nonlinear Optical Hydroxycarbonate Designed from a Diamond‐like Structure180LiZn(OH)CO3: A Deep‐Ultraviolet Nonlinear Optical Hydroxycarbonate Designed from a Diamond‐like Structure10Molecular Engineering toward an Enlarged Optical Band Gap in a Bismuth Sulfate via Homovalent Cation Substitution26Relationship Between Structure and Electroluminescent, Photochromic, or Second‐Order Nonlinear Optical Property1Relationship Between Structure and Electroluminescent, Photochromic, or Second‐Order Nonlinear Optical Property1Tin Chloride Sulfates A3Sn2(SO4)3–xCl1+2x (A = K, Rb, Cs; x = 0, 1) as Multifunctional Optical Materials33Unique Unilateral-Chelated Mode-Induced d–p−π Interaction Enhances Second-Harmonic Generation Response in New Ln3LiMS7 Family41Fluorine‐Driven Enhancement of Birefringence in the Fluorooxosulfate: A Deep Evaluation from a Joint Experimental and Computational Study139Theoretical study for determining the type of interactions between a GG block of an alginate chain with metals Cu2+, Mn2+, Ca2+ and Mg2+25Noncentrosymmetric Rb3(COOH)3(H3BO3)2 vs Centrosymmetric Cs3(COOH)3(H3BO3)214A Lead Mixed Halide with Three Different Coordinated Anions and Strong Second‐Harmonic Generation Response10Two molybdenyl carbonates with different dimensional structures exhibiting huge differences in band gaps7( R )- and ( S )-[C 8 H 10 NO 3 ] 2 [NbOF 5 ]: noncentrosymmetric niobium oxyfluorides with large optical anisotropy3[C(NH 2 ) 3 ] 2 S 2 O 8 : combining delocalized and localized π-conjugate units to achieve strong optical anisotropy21[C(NH 2 ) 3 ]BiCl 2 SO 4 : an excellent birefringent material obtained by multifunctional group synergy40First polar quaternary sulphide CsLiGa 6 S 10 with mixed ordered alkali cations displaying excellent infrared nonlinear optical properties16K 2 S 4 O 6 : improving birefringence and nonlinear optical properties with the [O 3 S–S–S–SO 3 ] 2− group5KLi 2 CO 3 F: a beryllium-free KBBF-type deep-UV carbonate with an enhanced interlayer interaction and large birefringence20Sc 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 groups38Flux synthesis, crystal structure, and characterization of a gamma-vanadate selenite polymorph1Chiral Ligand‐Driven Systematic Synthesis of Coordination Polymers with Non‐centrosymmetric Structures12Potential optical functional crystals with large birefringence: Recent advances and future prospects322Advances in second-order nonlinear optical sulfates38LiB5O5F2(OH)4: A new deep-ultraviolet birefringent crystal with [B5O5F2(OH)4] anionic group28Maximizing the linear and nonlinear optical responses of alkaline tricyanomelaminate28Cation-anion synergetic interactions achieving tunable birefringence in quasi-one-dimensional antimony(III) fluoride oxalates58BaSb(H2PO2)3Cl2: An excellent UV nonlinear optical hypophosphite exhibiting strong second-harmonic generation response32SbHPO3F: 2D van der Waals Layered Phosphite Exhibiting Large Birefringence32Achieving Large Second Harmonic Generation Effects via Optimal Planar Alignment of Triangular Units64Quasi phase matched second order reflection and transmission coefficients1

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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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  3. Remarkable 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 structures

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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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  6. Synthesis, crystal structures and nonlinear optical properties of polymorphism: α- and β-RbHgI3·H2O

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  7. Centrosymmetric (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 Centricities

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  10. Ba2NaClP2O7: Unprecedented Phase Matchability Induced by Symmetry Breaking and Its Unique Fresnoite-Type Structure

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  11. BaPO3Cl: a Metal Phosphate Chloride with Infinite [PO3]∞ Chains

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  12. Y2(CO3)3·H2O and (NH4)2Ca2Y4(CO3)9·H2O: Partial Aliovalent Cation Substitution Enabling Evolution from Centrosymmetry to Noncentrosymmetry for Nonlinear Optical Response

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  15. Changes of optical transition models caused by crystal structural changes in CaSe2O5

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  16. A 2 SrM IV S 4 (A = Li, Na; M IV = Ge, Sn) concurrently exhibiting wide bandgaps and good nonlinear optical responses as new potential infrared nonlinear optical materials

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  17. A new ultraviolet transparent hydra-cyanurate K 2 (C 3 N 3 O 3 H) with strong optical anisotropy from delocalized π-bonds

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  18. A rich structural chemistry in π-conjugated hydroisocyanurates: layered structures of A 2 B(H 2 C 3 N 3 O 3 ) 4 · n H 2 O (A = K, Rb, Cs; B = Mg, Ca; n = 4, 10) with high ultraviolet transparency and strong optical anisotropy

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  21. Centrosymmetric 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 size

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  29. Rb 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 design

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  30. RbSbSO 4 Cl 2 : an excellent sulfate nonlinear optical material generated due to the synergistic effect of three asymmetric chromophores

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  31. Y 8 O(OH) 15 (CO 3 ) 3 Cl: an excellent short-wave UV nonlinear optical material exhibiting an infrequent three-dimensional inorganic cationic framework

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