Nonlinear Active Materials: An Illustration of Controllable Phase Matchability

Lu, Hongcheng; Gautier, Romain; Donakowski, Martin D.; Tran, T. Thao; Edwards, Bryce W.; Nino, Juan C.; Halasyamani, P. Shiv; Liu, Zheng‐Tang; Poeppelmeier, Kenneth R.

doi:10.1021/ja4050604

Cited by 98 publications

(85 citation statements)

References 67 publications

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“…While a high k eff is needed for commercial applications that incorporate mechanical power, use of KNaNbOF 5 in applications such as signal filters may be more appropriate owing to the poor mechanical properties of these crystals. Compared to a previously studied oxide-fluoride system, [29] these crystals show a higher k eff value, making them a more attractive option in sensor applications.…”

Section: Piezoelectricitymentioning

confidence: 89%

Hydrothermal crystal growth, piezoelectricity, and triboluminescence of KNaNbOF5

Chang

Edwards

Frazer

et al. 2016

Journal of Solid State Chemistry

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Section: Piezoelectricitymentioning

confidence: 89%

Hydrothermal crystal growth, piezoelectricity, and triboluminescence of KNaNbOF5

Chang

Edwards

Frazer

et al. 2016

Journal of Solid State Chemistry

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“…17 The remaining vibrations may be assigned to 2,2′-dipyridylamine. 13,55 The infrared spectrum of 3 ( Figure 4c) show a strong characteristic band for [TaF 7 ] 2− at v s (Ta−F) = 507 cm −1 (with a weak shoulder at 571 cm −1 ). 17 The remaining vibrations may be assigned to ethylenediamine (see Figure S1b …”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Specific Chemistry of the Anions: [TaOF₅]^2–, [TaF₆]⁻, and [TaF₇]^2–

Gautier

Donakowski

et al. 2014

Crystal Growth & Design

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The controlled crystallization of specific tantalum oxide-fluoride and tantalum fluoride anions ([TaOF 5 ] 2− , [TaF 6 ] − , and [TaF 7 ] 2− ) is demonstrated using organic reagents with varied corresponding pK a values in the presence of aqueous hydrofluoric acid. The identity of tantalum oxide-fluoride or fluoride anions of [TaOF 5 ] 2− , [TaF 6 ] − , and [TaF 7 ] 2− are shown to crystallize successively from solution to solid state by increasing the corresponding pK a of organic reagents, which lead to the subsequent increase of fluoride concentration in the hydrofluoric acid solution.With the use of this methodology, three new hybrid crystal structures were targeted: [H 2 (2,2′-bpy)]TaOF 5 (2,2′-bpy = 2,2′-bipyridyl) 1, [Hdpa]TaF 6 (dpa = 2,2′-dipyridylamine) 2, and [H 2 En]TaF 7 (En = ethylenediamine) 3, respectively. The applicability and comparison of this methodology for tantalum and previously prepared niobium compounds show that it can be broadly used to design new materials with specific functionalities for other transition metal oxide-fluorides. ■ INTRODUCTIONHigh second-order nonlinear optical (NLO) response in noncentrosymmetric (NCS) structures often are generated from asymmetric basic building units (BBUs), such as anionic groups with π-orbital systems or stereochemically active lone pairs [(BO 3 ) 3− , (B 3 O 6 ) 3− , (IO 3 ) − , (TeO x ) n− , [AsS 3 ] 3− , [SbS 3 ] 3− , etc.] 1−7 and second-order Jahn−Teller (SOJT) distorted d 0 transition metal centers (Ti 4+ , Nb 5+ , Ta 5+ , Mo 6+ , etc.). 8−12 Materials with potentially higher second-harmonic generation (SHG) efficiencies based on the concept of two combined acentric BBUs have been shown to crystallize in one NCS structure, either by the combination of acentric cations and acentric anions 13−15 or combination of two acentric anions. 8,16−19 Thus, to incorporate specific acentric BBUs into NCS structures, a rational synthetic approach to target the crystallization of specific anions is needed.Tantalum compounds with strong SHG responses have been recently reported. 16 Owing to the good solubility of tantalum oxide in hydrofluoric acid solutions, tantalum oxide-fluoride/ fluoride anions similar to other early transition metal oxidefluoride anions have been extensively examined. 20−23 Previous tantalum compounds with different tantalum oxide-fluoride/ fluoride anions (e.g., [ TaOF 5 ] 2− , 24,25 [Ta(O 2 )F 5 ] 2− , 26,27 [TaF 6 ] − , 28 [TaF 7 ] 2− , 29−33 [Ta 2 OF 10 ] 2− dimer 34 and the adamantine-like cage [Ta 4 O 6 F 12 ] 2− anions 35 ) have been reported for their diverse coordination chemistry and interesting properties. Solution-phase NMR, Raman, and IR spectroscopy at room temperature have shown that different tantalum oxide-fluoride/fluoride species exist in different fluoride concentration conditions. 36−41 However, the controlled crystallization of specific tantalum oxide-fluoride/ fluoride anions has not been studied so far. In this article, to better understand specific chemistry of tantalum and target potential acentric units of ...

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“…[1][2][3][4][5][6][7][8][9][10][11] Recently, the compounds containing metal halides as inorganic moieties are important family of hybrid functional materials, especially the hybrid sliver (I) and copper(I) halides have received special attention due to the potential applications in photoluminescent, visible-light sensitizers for photovoltaic cell, chromism, etc. Generally speaking, the Cu(I) ion is able to adopt myriad coordination geometries including linear CuX 2 , CuX 3 triangle and CuX 4 tetrahedron (X = Br, I).…”

Section: Introductionmentioning

confidence: 99%

“…However, most of the SBUs are self-condensed to form etc [67][68][69][70][71][72][73][74][76][77][78][79][80] Occasionally, these SBUs can also be interlinked to form 2D microporous layers, for example, two isomeric 2D [Cu11 I 17 ] 6-layers are composed of [Cu 3 I 7 ], [Cu 4 I 8 ], [Cu 6 I 12 ] and [Cu 12 I 22 ] units in [deDABCO] 2 [meDABCO]Cu 11 I 17 . 74 Undoubtedly, the 2D [Cu 6 I 11 ] 5-layer reported here based on trimeric [Cu 3 I 7 ] building blocks represents new microporous layer in hybrid iodocuprate chemistry.…”

mentioning

confidence: 99%

Low-Dimensional Hybrid Cuprous Halides Directed by Transition Metal Complex: Syntheses, Crystal Structures, and Photocatalytic Properties

Lei

Yue

Zhao

et al. 2015

Crystal Growth & Design

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By using transitional metal (TM) complex cations as structure-directing agents (SDAs), a series of new hybrid cuprous halides have been solvothermally synthesized and structurally characterized. The title compounds feature abundant architectures ranging from one-dimensional (1D) chains to two-dimensional (2D) layers built from the self-condensation of [CuX4] tetrahedrons and/or [CuX3] triangles. The UV-vis diffuse-reflectance measurements reveal that the title compounds possesses semiconductor behaviors with smaller band gaps of 1.44-1.95 eV, and show highly efficient photocatalytic degradation activities over organic pollutant than N-doped P25 under visible light irradiation. 661x495mm (96 x 96 DPI) AbstractBy using transitional metal (TM) complex cations as structure-directing agents (SDAs), a series of new hybrid cuprous halides with abundant architectures ranging from one-dimensional (1D) ribbons to two-dimensional (2D) layers have been solvothermally prepared and structurally characterized.Compounds [TM(2,2-bipy) 3 ]Cu 5 I 7 (TM = Fe (1), Co(2) and Ni (3)) feature 1D [Cu 5 I 7 ] 2-chains formed by the interconnection of [Cu 5 I 10 ] units via edge-sharing. In compounds [TM(2,2-bipy) 2 I] 2 Cu 7 I 9 (TM = Mn (4), Cu(5), Ru (6)), the [Cu 5 I 9 ] units and [Cu 2 I 6 ] dimers are alternately interlinked via edge-sharing to form the 1D [Cu 7 I 9 ] 2-chains. Compound [Cu(2,2-bipy) 2 I][(Me) 2 -2,2-bipy]Cu 8 I 11 (7) contains a new 1D [Cu 8 I 11 ] 3-chain composed of complex [Cu 8 I 13 ] units based on CuI 4 tetrahedra and CuI 3 triangles. Compound [Co(2,2-bipy) 3 ]Cu 5 Br 8 (8) features 1D [Cu 5 Br 8 ] 3-anionic chain built form the interconnection of [Cu 6 Br 10 ] units and linear [Cu 4 Br 8 ] tetramers. In compound K[Mn(2,2-bipy) 3 ] 2 Cu 6 I 11 (9), the [Cu 3 I 7 ] secondary building units (SBUs) are directly interconnected to form 2D [Cu 6 I 11 ] 5-layers, which are further interconnected by K + ions via weak K-I bonds to generate a 3D [K@Cu 6 I 11 ] 4-framework with 1D large channels occupied by [Mn(2,2-bipy) 3 ] 2+ complexes. The UV-vis diffusereflectance measurements reveal that the title compounds possess semiconductor behaviors with smaller band gaps of 1.44-1.95 eV, and samples 4, 5 and 9 show highly efficient photocatalytic degradation activities over organic pollutant than N-doped P25 under visible light irradiation.

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Nonlinear Active Materials: An Illustration of Controllable Phase Matchability

Cited by 98 publications

References 67 publications

Hydrothermal crystal growth, piezoelectricity, and triboluminescence of KNaNbOF5

Hydrothermal crystal growth, piezoelectricity, and triboluminescence of KNaNbOF5

Specific Chemistry of the Anions: [TaOF₅]^2–, [TaF₆]⁻, and [TaF₇]^2–

Low-Dimensional Hybrid Cuprous Halides Directed by Transition Metal Complex: Syntheses, Crystal Structures, and Photocatalytic Properties

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Nonlinear Active Materials: An Illustration of Controllable Phase Matchability

Cited by 98 publications

References 67 publications

Hydrothermal crystal growth, piezoelectricity, and triboluminescence of KNaNbOF5

Hydrothermal crystal growth, piezoelectricity, and triboluminescence of KNaNbOF5

Specific Chemistry of the Anions: [TaOF5]2–, [TaF6]−, and [TaF7]2–

Low-Dimensional Hybrid Cuprous Halides Directed by Transition Metal Complex: Syntheses, Crystal Structures, and Photocatalytic Properties

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Specific Chemistry of the Anions: [TaOF₅]^2–, [TaF₆]⁻, and [TaF₇]^2–