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Royal Society of Chemistry, Physical Chemistry Chemical Physics, 15(17), p. 10200-10208, 2015

DOI: 10.1039/c5cp00695c

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Modeling the structure and thermodynamics of ferrocenium-based ionic liquids

This paper is available in a repository.
This paper is available in a repository.

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Abstract

A new force-field for the description of ferrocinium-based ionic liquids is reported. The proposed model was validated by confronting Molecular Dynamics simulations results with available experimental data —enthalpy of fusion, crystalline structure and liquid density— for a series of 1-alkyl-2,3,4,5,6,7,8,9-octamethylferrocenium bis(trifluoromethylsulfonyl)imide ionic liquids, [CnFc][NTf2] (3≤n≤10). The model is able to reproduce the densities and enthalpies of fusion with deviations smaller than 2.6% and 4.8 kJ∙mol-1, respectively. The MD simulation trajectories were also used to compute relevant structural information for the different [CnFc][NTf2] ionic liquids. The results show that, unlike other ILs, the alkyl side chains present in the cations are able to interact directly with the ferrocinium core of other ions. Even the ferrocinium charged cores (with relatively mild charge densities) are able to form small contact aggregates. This causes the partial rupture of the polar network and precludes the formation of extended nano-segregated polar-nonpolar domains normally observed in other ionic liquids.