Molecular Dynamics Simulations Reveal Inhomogeneity-Enhanced Stacking of Violanthrone-78-Based Polyaromatic Compounds in n-Heptane–Toluene Mixtures

We elucidated the effect of inhomogeneity in solutes on the aggregation of our representative polyaromatic (PA) compounds through a series of molecular dynamics simulations. Two kinds of solutes, a single type of PA compounds and a mixture of four types of PA compounds, were simulated in toluene, n-heptane, and heptol (mixture of toluene and n-heptane). The geometries of the resultant aggregates were quantified using gyradius ratios. Our results revealed that in toluene, while a single type of PA compound can only form short-cylinder-like aggregates, by having a solute mixture, parallel stacking of PA cores is enhanced, leading to the formation of one-dimensional (1D) rod-like structure. The enhanced stacking is caused by collective arrangement of the PA molecules; i.e., PA compounds of different types appear in an alternating manner in the aggregate. In addition, while the aggregated geometries of a single type of PA compounds were found to be affected by the composition of the solvents, the existence of the 1D structure formed by mixture seems to be insensitive to the solvents. On the other hand, the longest range of stacking is achieved by having a small amount of toluene ("good" solvent) in n-heptane ("bad" solvent).