Preferential Solvation of an Asymmetric Redox Molecule

Publication Type

Journal Article

Date Published

11/2016

Abstract

The fundamental correlations between solubility and solvation structure for the electrolyte system comprising N-(ferrocenylmethyl)-N,N-dimethyl-N-ethylammonium bistrifluoromethylsulfonimide (Fc1N112-TFSI) dissolved in a ternary carbonate solvent mixture is analyzed using combined NMR relaxation and computational methods. Probing the evolution of the solvent–solvent, ion–solvent and ion–ion interactions with an increase in solute concentration provides a molecular level understanding of the solubility limit of the Fc1N112-TFSI system. An increase in solute concentration leads to pronounced Fc1N112-TFSI contact-ion pair formation by diminishing solvent–solvent and ion–solvent type interactions. At the solubility limit, the precipitation of solute is initiated through agglomeration of contact-ion pairs due to overlapping solvation shells.

Journal

The Journal of Physical Chemistry C

Volume

120

Year of Publication

2016

Issue

49

Pagination

27834 - 27839

ISSN

1932-7447

Short Title

J. Phys. Chem. C

Refereed Designation

Refereed