Interestingly, our MD trajectory captures transient extended π-stack structures (see Fig. in Supplementary Information). The extended π-π-stacked polymer-dopant structures with long-range interactions are known to exist in polymer films. The presence of these structures in solution signifies the seeding effect. Unfortunately, with current set of experimental and theoretical studies, we are unable to assign the observed decay time constants of F 4 TCNQ anion feature to specific populations with different interaction modes. Following dynamics of excited states in different configurations should provide the insight to the observed decay time constants. This valuable information can then be capitalized to monitor the evolution of different interactions during solution processing. It will also be worth to explore how the populations amongst different types of interaction modes can be controlled using systematic variation in polymers via modifications in side chains or film processing conditions.