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  Azoniaspiro salts: towards bridging the gap between room-temperature ionic liquids and molten salts

Clough, M. T., Geyer, K., Hunt, P. A., McIntosh, A. J. S., Rowe, R., Welton, T., et al. (2016). Azoniaspiro salts: towards bridging the gap between room-temperature ionic liquids and molten salts. Physical Chemistry Chemical Physics, 18(4), 3339-3351. doi:10.1039/c5cp07209c.

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 Creators:
Clough, Matthew T.1, 2, Author              
Geyer, Karolin3, Author
Hunt, Patricia A.1, Author
McIntosh, Alastair J. S.1, Author
Rowe, Rebecca1, Author
Welton, Tom1, Author
White, Andrew J. P.1, Author
Affiliations:
1Department of Chemistry, Imperial College London, London, UK , ou_persistent22              
2Research Department Schüth, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445589              
3BASF SE, Ludwigshafen, Germany , ou_persistent22              

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Free keywords: STRUCTURE-DIRECTING AGENTS; THERMAL-DECOMPOSITION; PI INTERACTIONS; MIXTURES; PAIR; MECHANISMS; EXISTENCE; ANIONSChemistry; Physics;
 Abstract: In a continued effort to improve the suitability of ionic liquids in applications operating at raised temperatures, novel spirocyclic 'azoniaspiro' salts (with cations derived from five-, six-, seven-and eight-membered rings) are prepared and characterised. The structural and thermal properties of these salts are compared against those of established analogues. The stable geometries and ion pairing behaviour of these species are investigated via a combined experimental/computational approach, employing X-ray crystallography and Density Functional Theory (DFT) methods. Subsequently, the thermal stabilities of these organic salts are characterised and compared using a broad range of techniques. Hyphenated Thermogravimetry-Mass Spectrometry investigations enable complex mechanisms underlying thermal decomposition to be elucidated. Lastly, transition state structures are optimised, corresponding to plausible decomposition mechanisms of the azoniaspiro salt, 6-azoniaspiro[6.5]dodecanium chloride, and one prototypical monocyclic species 1-butyl-1-methylpiperidinium chloride, using DFT. The observed improved thermal stabilities of the azoniaspiro salts, and their potential higher-temperature stable-liquid ranges, render them promising candidates for future ionic liquid applications.

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Language(s): eng - English
 Dates: 2015-12-222016-01-28
 Publication Status: Published in print
 Pages: 13
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1039/c5cp07209c
 Degree: -

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Title: Physical Chemistry Chemical Physics
  Abbreviation : Phys. Chem. Chem. Phys.
Source Genre: Journal
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Publ. Info: Cambridge, England : Royal Society of Chemistry
Pages: - Volume / Issue: 18 (4) Sequence Number: - Start / End Page: 3339 - 3351 Identifier: CoNE: https://pure.mpg.de/cone/journals/resource/954925272413_1
ISSN: 1463-9076