Impact of Fluorine Substituents on -Conjugated Polymer Main-Chain Conformations, Packing, and Electronic Couplings

Taking the pi-conjugated polymers PBDT-[2X]T (X = H, F) as model systems, the effects of fl uorine substitution on mainchain 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.