Abstract
Taking the π‐conjugated polymers PBDT[2X]T (X = H, F) as model systems, the effects of fluorine substitution on main‐chain conformations, packing, and electronic couplings are examined. This combination of molecular dynamics simulations and solid‐state NMR shows that a higher propensity for backbone planarity in PBDT[2F]T leads to more pronounced, yet staggered, chain stacking, which generally leads to higher electronic couplings and binding energy between neighboring chains.