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RESEARCH PAPER · Chemistry of Materials · 2018

A Series of Rare-Earth Borates K 7 MRE 2 B 15 O 30 (M = Zn, Cd, Pb; RE = Sc, Y, Gd, Lu) with Large Second Harmonic Generation Responses

Zhiqing Xie, Miriding Mutailipu, Guijie He, Guopeng Han, Ying Wang, Zhihua Yang, Min Zhang, Shilie Pan

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A Series of Rare-Earth Borates K 7 MRE 2 B 15 O 30 (M = Zn, Cd, Pb; RE = Sc, Y, Gd, Lu) with Large Second Harmonic Generation ResponsesOriginalBa 2 ZnSc(BO 3 ) 3 and Ba 4 Zn 5 Sc 2 (BO 3 ) 8 : first examples of borates in the Zn–Sc–B–O system featuring special structure configurations15Beryllium-Free Nonlinear-Optical Crystals A 3 Ba 3 Li 2 Ga 4 B 6 O 20 F (A = K and Rb): Members of the Sr 2 Be 2 (BO 3 ) 2 O Family with a Strong Covalent Connection between the ∞ 2 [Li 2 Ga 4 B 6 O 20 F] 9– Double Layers27Flux growth and optical properties of K7CaY2(B5O10)3 nonlinear crystal28Crystal growth, crystal structure and anisotropic magnetic properties of KBaR(BO3)2 (R = Y, Gd, Tb, Dy, Ho, Tm, Yb and Lu) triangular lattice materials32Two Lanthanide Borate Chlorides LnB4O6(OH)2Cl (Ln = La, Ce) with Wide Ultraviolet Transmission Windows and Large Second-Harmonic Generation Responses25Characterization of LuGdVO3 mixed crystal prepared by one new method9Three Cadmium Tartratoborates with Good Second Harmonic Generation (SHG) or Luminescence Performances10Cs 2 CdV 2 O 6 Cl 2 and Cs 3 CdV 4 O 12 Br: two new non-centrosymmetric oxyhalides containing d 0 and d 10 cations and exhibiting second harmonic generation activity19From 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 crystals26K 6 ACaSc 2 (B 5 O 10 ) 3 (A = Li, Na, Li 0.7 Na 0.3 ): Nonlinear-Optical Materials with Short UV Cutoff Edges37A new disordered langbeinite-type compound, K2Tb1.5Ta0.5P3O12, and Eu3+-doped multicolour light-emitting properties10NaCa5BO3(SiO4)2 with Interesting Isolated [BO3] and [SiO4] Units in Alkali- and Alkaline-Earth-Metal Borosilicates14Refractive 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 Materials37Synthesis, characterization, and theoretical analysis of three new nonlinear optical materials K7MRE2B15O30 (M= Ca and Ba, RE= La and Bi)28Nonlinear optical crystals K7CaR2(B5O10)3 (R = Nd, Yb), growth and properties27Rb7SrY2(B5O10)3: A Rare-Earth Pentaborate with Moderate Second-Harmonic Response and Interesting Phase-Matching Behavior29Research and Development of Zincoborates: Crystal Growth, Structural Chemistry and Physicochemical Properties20Novel compounds in the MMeR(BO3)2 borate family (M = alkali metal, Me = alkaline earth metal, R = rare-earth element): Syntheses, crystal structures and luminescent properties48Ionothermal Synthesis of Metal Chalcogenides M2Ag3Sb3S7 (M = Rb, Cs) Displaying Nonlinear Optical Activity in the Infrared Region33Effect of anion dimensionality on optical properties: the ∞ [B 7 O 10 (OH) 2 ] layer in CsB 7 O 10 (OH) 2 vs. the ∞ [B 7 O 12 ] framework in CsBaB 7 O 1219A new non-centrosymmetric Gd-based borate crystal Rb 7 SrGd 2 (B 5 O 10 ) 3 : growth, structure, and nonlinear optical and magnetic properties24High-temperature, high-pressure hydrothermal synthesis, crystal structure, and infrared and NMR spectroscopy of a barium lead borate with a 2D layer structure: [Ba 3 Pb(H 2 O)][B 11 O 19 (OH) 3 ]6Hydroisocyanurates X 2 Y(H 2 C 3 N 3 O 3 ) 4 ·4H 2 O (X = K, Cs; Y = Zn, Cd) with large birefringence stemming from π-conjugated (H 2 C 3 N 3 O 3 ) − anions28Synthesis and characterization of three new rare-earth orthoborates: Ba 2 MgY 2 (BO 3 ) 4 , Ba 2 CdY 2 (BO 3 ) 4 , and Ba 2 CdSc(BO 3 ) 310Two new ammonium/alkali-rare earth metal difluorophosphates ALa(PO 2 F 2 ) 4 (A = NH 4 and K) with moderate birefringence and short cutoff edges26Designing Sulfide Borate as a Novel Type of Second-Order Nonlinear-Optical Material91A Promising Fluorooxoborate Framework with Flexibile Capability for Diverse Cations to Enhance the Second Harmonic Generation14New double holmium borates: Rb3HoB6O12 and Rb3Ho2B3O910Obtaining of luminescent material based on NaBaY(BO3)2 doped with terbium and europium ions0Синтез, структура и люминесцентные свойства нового двойного бората K3Eu3B4O121Nonlinear-Optical Crystal Rb3YB6O12 with Condensed B5O10 Blocks That Exhibits an Intriguing Structural Arrangement and a Short Ultraviolet Absorption Edge26La1-Eu B4O6(OH)2Cl (0 ≤ x ≤ 0.54): Strong 4f-4f excitations due to the noncentrosymmetric and oxychloride coordination of Eu3+3Synthesis and crystal structures of novel alkali rare-earth orthoborates K3RE3(BO3)4 (RE = Pr, Nd, Sm–Lu)19KLi2RE(BO3)2 (RE = Dy, Ho, Er, Tm, Yb, and Y): Structural, Spectroscopic, And Thermogravimetric Studies on a Series of Mixed-Alkali Rare-Earth Orthoborates11Borates: A Rich Source for Optical Materials1089Site preference and the optical thermometry strategy by different temperature response from two sites environment of Mn2+ in K7ZnSc2B15O3075Computationally assisted multistage design and prediction driving the discovery of deep-ultraviolet nonlinear optical materials41Efficient Bi 3+ to Eu 3+ energy transfer and color tunable emissions in K 7 CaY 2 (B 5 O 10 ) 3 -based phosphors22Na 2 La 2 B 10 O 19 : a new lanthanum sodium borate with infinite 2D layer 2∞[B 10 O 19 ] 8− and moderate birefringence4Halonitrides Zn 2 NX (X=Cl,Br): Novel Mid-Infrared Nonlinear Optical Materials30Tin Chloride Sulfates A3Sn2(SO4)3–xCl1+2x (A = K, Rb, Cs; x = 0, 1) as Multifunctional Optical Materials33BaYOBO3: A deep-ultraviolet rare-earth oxy-borate with a large second harmonic generation response45Recent advances in nonlinear optical rare earth structures63A non–centrosymmetric compound K7Li2Y2B15O30 by introducing more alkali metals into A7MRe2B15O30 family10Site occupancies, photoluminescence, and temperature sensing properties of a K7ZnSc2B15O30:Ce3+, Tb3+ phosphor3A3A′3Zn6Te4O24 (A = Na, A′ = Rare Earth) Garnets: A-Site Ordered Noncentrosymmetric Structure, Photoluminescence, and Na-Ion Conductivity10Ba 2 B 5 O 8 (OH) 2 (NO 3 )·3H 2 O: the design of an alkaline earth metal borate-nitrate optimized from a hydroxylic borate4Inducing large birefringence by enhancing asymmetric electron distribution of Y–O polyhedra21Li 7 SrScB 12 O 24 and Li 7 Ba 0.6 Ca 0.4 ScB 12 O 24 : two new quaternary rare-earth borates with short UV cutoff edges4Na 3 YB 8 O 15 : a new rare-earth borate with an infinite one-dimensional [B 8 O 15 ] ∞ chain and a short ultraviolet cutoff edge8Quaternary Noncentrosymmetric Rare-Earth Sulfides Ba4RE2Cd3S10 (RE = Sm, Gd, or Tb): A Joint Experimental and Theoretical Investigation17Two non-centrosymmetric scandium borate nonlinear optical crystals containing the B5O10 anion group26New double nonlinear-optical borate Rb3SmB6O12: Synthesis, structure and spectroscopic properties26Cd4InO(BO3)3: A New Nonlinear Optical Crystal Exhibiting Strong Second Harmonic Generation Effect and Moderate Birefringence2One-Side Capping in Two-Dimensional WO 3 -Type Materials Leading to Strong Second-Harmonic Response29Directional Construction of New Nonlinear Optical Bifunctional Units through Molecular Engineering Design Inspired by the B 3 O 7 -Typed Configuration23Deep Ultraviolet-Transparent Materials with Strong Second-Harmonic Response50Ln2(SeO3)2(SO4)(H2O)2 (Ln=Sm, Dy, Yb): A Mixed‐Ligand Pathway to New Lanthanide(III) Multifunctional Materials Featuring Nonlinear Optical and Magnetic Anisotropy Properties36Ln2(SeO3)2(SO4)(H2O)2 (Ln=Sm, Dy, Yb): A Mixed‐Ligand Pathway to New Lanthanide(III) Multifunctional Materials Featuring Nonlinear Optical and Magnetic Anisotropy Properties2Large second harmonic generation in a penta-CdO 2 sheet exfoliated from its bulk phase16KREP2Se6 (RE = Sm, Gd, Tb): The First Rare‐Earth Selenophosphates with Remarkable Nonlinear Optical Activities Realized by Synergistic Effect of RE‐ and P‐Based Motifs39Achieving broadband ultraviolet to mid-infrared transparency in germanate-based nonlinear optical crystals Cs 3 REGe 3 O 9 (RE = Y, Gd)16Exploration of the oxygen reduction reaction activity of four transition metal borates: synthesis, structure and characterization10Hg 3 O 2 (NO 3 )F: a mercury nitrate oxyfluoride with an unprecedented [(Hg 3 O 2 F) + ] ∞ cationic framework and excellent optical anisotropy21KNa 2 La 2 (BO 3 ) 3 : a shortite-type lanthanide borate exhibiting strong nonlinear optical activity induced by isolated [BO 3 ] triangles and distorted [LaO 9 ] polyhedra26Two non-centrosymmetric mixed alkali metal and alkaline earth metal scandium borate nonlinear optical materials with short ultraviolet cutoff edges14Structural Motif Cosubstitution Strategy for Designing Fluoroaluminoborate with the Sr2Be2B2O7-Type Double-Layered Structure14Fluorooxoborate Promoting the Exploration of Short-Wavelength Linear and Nonlinear Optical Crystals with Expected Properties and Versatile Structures27Three Borates Belonging to the A(I)7Ae(II)Re(III)2B15O30 Family as Promising Nonlinear Optical Crystals12Rare-Earth Scandium Borate Fluoride with a Deep-Ultraviolet Cutoff Edge12A bifunctional primitive strategy induces enhancements of large second harmonic generation and wide UV transmittance in rare-earth borates containing [B 5 O 10 ] groups22A-site cation manipulation of exemplary second harmonic generation response and optical anisotropy in rare-earth borates18Chromium iodate: the structure and origin of optical second harmonic generation1Equivalent cation-tuning to realize a new Ce( iv ) fluoride with excellent comprehensive nonlinear optical performances12KNa 2 Lu(BO 3 ) 2 : A Rare-Earth Borate Crystal Characterized by an Enhanced Birefringence and Wide Ultraviolet Transparency Range19Li13YGe4O16: A Mid-infrared Rare-Earth Germanate Nonlinear Optical Crystal Featuring a Broad Transmission Range and an Enlarged Band Gap10Pioneering Exploration in the Na–Lu–B–O System: Na3LuB8O15 with Polyborate Structure and Short UV Cutoff Edge1Synthesis, structure, and oxygen reduction reaction activity of 1-isopropylimidazole and 1-propylimidazole ligand-nickel borate crystals2Recent advances and future perspectives on rare-earth-based nonlinear optical materials with π-conjugated [XO3] (X = B, C, N) units66Tailoring optical temperature sensing performance of K7MgSc2B15O30:Mn2+ via structure modulation3Wide‐Bandgap RBa3(B3O6)3 (R = Nd, Sm, Tb, Dy, and Er) Single Crystals for Ultraviolet Nonlinear Optics6Structure and optical properties of alkali rare-earth double phosphates of M3RE(PO4)2 (M = K, Rb; RE = Y, La, and Lu)4Chemical substitution towards a rare-earth borate ultraviolet NLO crystal exhibiting a strong SHG response17K 15 La 7 (BO 3 ) 12 : A KBBF-Like Nonlinear-Optical Material with a Short Cutoff Edge and a Strong Second-Harmonic-Generation Response10K6NaCaRe2(B5O10)3 (Re = Y, Lu): Two NLO Compounds Exhibiting a Short Absorption Edge in the A7–xA’xAeRe2(B5O10)3 (x = 0, 1) Family4Synthesising a series of promising ultraviolet nonlinear optical materials with the aid of the flexibility of isolated [B 5 O 10 ] groups3Crystal Structures, Phase Transition, and Optical Properties of Two Rare Earth Borate Fluorides: α- and β-BaGdBO3F26Rb 7 PbY 2 (B 5 O 10 ) 3 : A Noncentrosymmetric Rare-Earth Borate Nonlinear Optical Crystal with [B 5 O 10 ] Unit16Two-Step Substitutions of Square Pyramidal VO5 with CdO4Br to Achieve Higher Laser-Induced Damage Threshold from Polar Oxybromides Rb4CdV5O15Br to Rb3CdV4O12Br10The self-activated K7CaY2(B5O10)3 phosphor and the effect of trivalent dopants on the emission properties4Alkali Metal Substitution-Induced Structural Transformation for RbREP2Se6 (RE = Gd, Tb, Dy) with Second-Harmonic Generation Responses6Promising UV/DUV nonlinear optical materials with X-membered (X = multiples of 6) rings in anhydrous inorganic borates20Search for new nonlinear optical materials via chemical substitution and combined structural studies in alkali metal rare-earth borates3Tailoring ordered structures with distorted [TeO 3 ] and aligned [ScO 6 ] motifs for balanced nonlinear optical properties in rare-earth tellurate crystals5Centrosymmetric to noncentrosymmetric structure transition of the RbREP 2 Se 6 (RE = La–Nd, Sm, Ho–Yb) series: crystal growth, magnetic and optical properties4K 7 MgY 2 (B 5 O 10 ) 3 : a novel ultraviolet nonlinear optical crystal based on the [B 5 O 10 ] functional unit2Two scandium borate UV NLO crystals designed through chemical element substitution1Beating the concentration quenching: A review0K 3 YGe 3 O 9 : A Rare-Earth Germanate Nonlinear Optical Crystal with a Short Ultraviolet Cutoff Edge and Moderate Second-Harmonic Generation Response1Thermally robust dual-band anti-thermal quenching in alkali-co-doped K7SrGd2(B5O10)3:Tb3+ phosphors1Host sensitisation of Tb 3+ emission in K 7 CaY 2 (B 5 O 10 ) 31Birefringence and Photocurrent Response of A Series of Rare-Earth Selenophosphates Cs4RE2(PSe4)2(P2Se6) (RE = La–Nd, Sm, Gd, Tb) Synthesized by the Metal Oxide–Boron–Chalcogen (MOBQ) Method0Host sensitized luminescence of Pb 2+ in K 7 CaY 2 (B 5 O 10 ) 3 borate for nUV applications0

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