C-H···π interactions disrupt electrostatic interactions between non-aqueous electrolytes to increase solubility.

Grid-scale energy storage applications, such as redox flow batteries, rely on the solubility of redox-active organic molecules. Although redox-active pyridiniums exhibit exceptional persistence in multiple redox states at low potentials (desirable properties for energy storage applications), their solubility in non-aqueous media remains low, and few practical molecular design strategies exist to improve solubility. Here we convey the extent to which discrete, attractive interactions between C-H groups and π electrons of an aromatic ring (C-H···π interactions) can describe the solubility of N-substituted pyridinium salts in a non-aqueous solvent. We find a direct correlation between the number of C-H···π interactions for each pyridinium salt and its solubility in acetonitrile. The correlation presented in this work highlights a consequence of disrupting strong electrostatic interactions with weak dispersion interactions, showing how minimal structural change can dramatically impact pyridinium solubility.