Electrochemical and spectroscopic characterization of niobium {Nb6Cl12}z+ chloride clusters in the aluminum chloride-1-methyl-3-ethylimidazolium chloride molten salt

Quigley, Robert M.; Barnard, Paul; Hussey, Charles L.; Seddon, Kenneth R.

doi:10.1021/ic00033a024

Cited by 40 publications

(25 citation statements)

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“…24,25 To our knowledge the ionic species formed in mixtures of alkyl imidazolium chloride and niobium or zinc halides have been scarcely studied so far. Nb 6 26 Electrochemical and electronic absorption spectroscopy of the melts have identified anionic complexes of the type [ Nb 6 Cl 12 Cl 6 ] 6 z . Ionic mixtures of 1-butyl-2,3-dimethylimidazolium chloride/ ZnCl 2 were investigated by electron-spray mass spectroscopy (EMS) and the presence of ZnCl 3 , Zn 2 Cl 5 2 , and Zn 3 Cl 7 2 species were identified according to the acidity of the mixture.…”

Section: Introductionmentioning

confidence: 99%

Raman spectroscopy of ionic liquids derived from 1‐n‐butyl‐3‐methylimidazolium chloride and niobium chloride or zinc chloride mixtures

Alves¹,

Santos²,

Soares³

et al. 2008

J Raman Spectroscopy

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Anionic species formed in mixtures of 1-n-butyl-3-methylimidazolium chloride (BMICl) with different amounts of niobium pentachloride (NbCl 5 ) or zinc dichloride (ZnCl 2 ) were investigated by Raman spectroscopy. In the BMICl and NbCl 5 ionic mixtures the presence of the anion NbCl 6 − was detected for all compositions (molar fraction, X NbCl 5 ) and a mixture of this anion and the neutral Nb 2 Cl 10 in acid ones. Two different anions were observed for basic mixtures of BMICl and ZnCl 2 : ZnCl 4 2− .0 < X ZnCl 2 < 0.35/ and Zn 2 Cl 6 2− .X ZnCl 2 > 0.3/, whereas for acidic ones three species were detected: Zn 2 Cl 6 2− .X ZnCl 2 < 0.7/, Zn 3 Cl 8 2− .X ZnCl 2 > 0.7/ and Zn 4 Cl 10 2− .X ZnCl 2 > 0.7/. It has also been observed that in both cases, the formation of larger anions causes a shift of the C-H stretching modes to higher wavenumbers as the result of a decrease in the hydrogen bond between Cl and the hydrogens from the cation.

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Section: Introductionmentioning

confidence: 99%

Raman spectroscopy of ionic liquids derived from 1‐n‐butyl‐3‐methylimidazolium chloride and niobium chloride or zinc chloride mixtures

Alves¹,

Santos²,

Soares³

et al. 2008

J Raman Spectroscopy

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“…[35,[38][39][40][41][42][43][44][45][46][47][48][49]. Both units exhibit reversible electron-oxidation processes and magnetic properties when they carry unpaired valence electrons [30,32,35,39,[50][51][52][53][54][55][56][57][58][59][60][61][62]. Compared with other metal-based solid state complexes, the added value of [(M 6 L i 12 )L a 6 ] nand [(M 6 L i 8 )L a 6 ] nis that the inorganic L a ligands can be exchanged by other L' a inorganic ones or functional organic ligands [29,31,[63][64][65][66][67][68].…”

mentioning

confidence: 99%

Advances in the Engineering of Near Infrared Emitting Liquid Crystals and Copolymers, Extended Porous Frameworks, Theranostic Tools and Molecular Junctions Using Tailored Re6 Cluster Building Blocks

et al. 2014

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International audienceAt the occasion of the fiftieth birthday of the introduction of the term 'metal atom cluster' by F. A. Cotton in inorganic chemistry, it is the good time to make a review on the advances in the engineering of molecular assemblies and nanomaterials based on octahedral Re6 metal atom clusters. The latter exhibit unique intrinsic structural and physicochemical properties (orthogonal disposition of metallic sites that can be selectively functionalized, photoluminescence, redox, generation of singlet oxygen) that make them relevant building blocks for the structuration at the nanometric scale and functionalization of hybrid organic-inorganic materials and supramolecular frameworks. After synthesis by solid state chemistry techniques at high temperature, inorganic precursors built up on face-capped [(Re6Yi8)Ya6] cluster units (Y = chalcogen and/or halogen) can be functionalized via solution chemistry techniques or organic melts to form [(Re6Yi8)La6] (L = CN, OH, various organic ligands...). This work reports advances in the synthesis of [(Re6Yi8)Ya6] and [(Re6Yi8)La6] cluster units as well as on their use in the elaboration of supramolecular frameworks, nanoparticles, hybrid nanomaterials (co-polymers and liquid crystals) and active molecular junctions

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“…falsefalse{Nnormalb6normalL12normalifalsefalse}n+ cluster core (L = Br, Cl; n = 3 or 4)) (figure 2 b ). These units are indeed known for reversible oxidation, causing drastic modulation of their optical properties in the UV–Vis-NIR range yielding yellow-brownish solutions [69–71]. The absorption bands of both clusters followed similar changes in acetone, the three strong transitions at 350 nm, 450 nm and in NIR sharply decreased and new bands appeared in the NIR.…”

Section: Resultsmentioning

confidence: 99%

“…open sci. 6: 181647 modulation of their optical properties in the UV-Vis-NIR range yielding yellow-brownish solutions [69][70][71]. The absorption bands of both clusters followed similar changes in acetone, the three strong transitions at 350 nm, 450 nm and in NIR sharply decreased and new bands appeared in the NIR.…”

Section: Characterization Of Metal Atom Clusters Suspensionsmentioning

confidence: 95%

Transparent functional nanocomposite films based on octahedral metal clusters: synthesis by electrophoretic deposition process and characterization

et al. 2019

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Transparent optical thin films have recently attracted a growing interest for functional window applications. In this study, highly visible transparent nanocomposite films with ultraviolet (UV)-near-infrared (NIR)-blocking capabilities are reported. Such films, composed of Mo 6 and Nb 6 octahedral metal atom clusters (MC) and polymethylmethacrylate polymer (PMMA), were prepared by electrophoretic deposition on indium tin oxide-coated glass (ITO glass). PMMA was found to improve both the chemical and physical stability of Mo 6 and Nb 6 MCs, resulting in a relatively homogeneous distribution of the clusters within the PMMA matrix, as seen by microstructural observations. The optical absorption spectrum of these transparent MC@polymer nanocomposite films was marked by contributions from their Mo 6 and Nb 6 -based clusters (absorption in the UV range) and from the ITO layer on silica glass (absorption in the NIR range). Mo 6 @PMMA nanocomposite films also exhibited excellent photoluminescence properties, which were preserved even after exposure to 50°C at a relative humidity of 70% for one month. These films cumulate high transparency in the visible range with remarkable UV-NIR blocking properties and represent interesting candidates for functional glass application.

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Electrochemical and spectroscopic characterization of niobium {Nb6Cl12}z+ chloride clusters in the aluminum chloride-1-methyl-3-ethylimidazolium chloride molten salt

Cited by 40 publications

References 0 publications

Raman spectroscopy of ionic liquids derived from 1‐n‐butyl‐3‐methylimidazolium chloride and niobium chloride or zinc chloride mixtures

Raman spectroscopy of ionic liquids derived from 1‐n‐butyl‐3‐methylimidazolium chloride and niobium chloride or zinc chloride mixtures

Advances in the Engineering of Near Infrared Emitting Liquid Crystals and Copolymers, Extended Porous Frameworks, Theranostic Tools and Molecular Junctions Using Tailored Re6 Cluster Building Blocks

Transparent functional nanocomposite films based on octahedral metal clusters: synthesis by electrophoretic deposition process and characterization

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