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.
BT - The Journal of Physical Chemistry C DA - 11/2016 DO - 10.1021/acs.jpcc.6b09114 IS - 49 LA - eng N2 -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.
PY - 2016 SP - 27834 EP - 27839 ST - J. Phys. Chem. C T2 - The Journal of Physical Chemistry C TI - Preferential Solvation of an Asymmetric Redox Molecule VL - 120 SN - 1932-7447 ER -