Federico Cruciani

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

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.

F-Substituted oligothiophenes serve as nonfullerene acceptors in polymer solar cells with open-circuit voltages >1 V

We report on a set of two analogous, F-substituted oligothiophene derivatives (D5T6F-M and D7T8F-M), in which systematic fluorination at the thienyl moieties is shown to induce a sufficient increase in electron affinity (EA; i.e. suppressed LUMO level) and in ionization potential (IP; i.e. deeper HOMO) to (i) impart the molecules with electron-accepting and -transporting characteristics, and (ii) yield high open-circuit voltages >1 V in BHJ solar cells when combined with a low-bandgap polymer donor (PCE10) commonly used with fullerenes. The nonfullerene BHJ devices with the SM acceptor D5T6F-M achieve power conversion efficiencies (PCEs) of up to ca. 4.5% (vs. ca. 2% for D7T8F-M-based devices). Our study shows that –F substitutions in SM systems – otherwise used as donors – is an effective approach in the design of nonfullerene acceptors for efficient BHJ solar cells with polymer donors.