- Title
- Bulk nanostructure of the prototypical 'good' and 'poor' solvate ionic liquids [Li(G4)][TFSI] and [Li(G4)][NO₃]
- Creator
- Murphy, Thomas; Callear, Sam K.; Yepuri, Nageshwar; Shimizu, Karina; Watanabe, Masayoshi; Lopes, José N. Canongia; Darwish, Tamim; Warr, Gregory G.; Atkin, Rob
- Relation
- ARC.DP120102708 http://purl.org/au-research/grants/arc/DP120102708
- Relation
- Physical Chemistry Chemical Physics Vol. 18, Issue 26, p. 17224-17236
- Publisher Link
- http://dx.doi.org/10.1039/c6cp00176a
- Publisher
- Royal Society of Chemistry
- Resource Type
- journal article
- Date
- 2016
- Description
- The bulk nanostructures of a prototypical ‘good’ solvate ionic liquid (SIL) and ‘poor’ SIL have been examined using neutron diffraction and empirical potential structure refinement (EPSR) simulated fits. The good SIL formed by a 1:1 mixture of lithium bis(trifluoromethylsulfonyl)imide (Li[TFSI]) in tetraglyme (G4), denoted [Li(G4)][TFSI], and the poor SIL formed from a 1:1 mixture of lithium nitrate (Li[NO₃]) in G4, denoted [Li(G4)][NO₃], have been studied. In both SILs there are strong Lewis acid–base interactions between Li⁺ and ligating O atoms. However, the O atoms coordinated to Li⁺ depend strongly on the counter anion present. Li⋯O coordination numbers with G4 are 2–3 times higher for [Li(G4)][TFSI] than [Li(G4)][NO₃], and conversely the Li⋯O anion coordination number is 2–3 times higher in [Li(G4)][NO₃]. In both solvates the local packing of Li around G4 O atoms are identical but these interactions are less frequent in [Li(G4)][NO₃]. In both SILs, Li⁺ has a distribution of coordination numbers and a wide variety of different complex structures are present. For [Li(G4)][NO₃], there is a significant proportion uncoordinated G4 in the bulk; ∼37% of glyme molecules have no Li⋯O contacts and each G4 molecule coordinates to an average of 0.5 Li⁺ cations. Conversely, in [Li(G4)][TFSI] only ∼5% of G4 molecules lack Li⋯O contacts and G4 molecules coordinates to an average of 1.3 Li⁺ cations. Li⁺ and G4 form polynuclear complexes, of the form [Lix(G4)y]x⁺, in both solvates. For [Li(G4)][TFSI] ∼35% of Li⁺ and G4 form 1 polynuclear complexes, while only ∼10% of Li⁺ and G4 form polynuclear complexes in [Li(G4)][NO₃].
- Subject
- bulk nanostructures; solvate ionic liquid; [Li(G4)][TFSI]; [Li(G4)][NO₃]
- Identifier
- http://hdl.handle.net/1959.13/1337036
- Identifier
- uon:27760
- Identifier
- ISSN:1463-9076
- Language
- eng
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