Aggregation and Solubility of a Model Conjugated Donor-Acceptor Polymer

In conjugated polymers, solution-phase structure and aggregation exert a strong influence on device morphology and performance, making understanding solubility crucial for rational design. Using atomistic molecular dynamics (MD) and free-energy sampling algorithms, we examine the aggregation and solubility of the polymer PTB7, studying how side-chain structure can be modified to control aggregation. We demonstrate that free-energy sampling can be used to effectively screen polymer solubility in a variety of solvents but that solubility parameters derived from MD are not predictive. We then study the aggregation of variants of PTB7 including those with linear (octyl), branched (2-ethylhexyl), and cleaved (methyl) side chains, in a selection of explicit solvents and additives. Energetic analysis demonstrates that while side chains do disrupt polymer backbone stacking, solvent exclusion is a critical factor controlling polymer solubility.