Designing Singlet Fission Candidates from Donor–Acceptor Copolymers

The attached document is the Accepted Manuscript version of a Published Work that appeared in final form in Chemistry of Materials, copyright © after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/full/10.1021/acs.chemmater.0c01784. ABSTRACT: Singlet fission (SF) has demonstrated significant promise for boosting the power conversion efficiency (PCE) of solar cells. Traditionally, SF is targeted as an intermolecular process, however its dependence on crystal packing makes molecular design difficult. In contrast, intramolecular SF (iSF) enables the exploration of tunable bichromophoric systems following well-defined structure-property relationships. In this work, we propose a set of parameters to screen conjugated donor-acceptor copolymer candidates with potential iSF behavior. We focus our analysis on the E(S1)>2E(T1) thermodynamic condition and on the appropriate charge transfer (CT) character of S1. We map the CT character with respect to the frontier molecular orbital (FMO) energies of the constituent monomers, providing a cost-effective protocol for an accelerated screening of promising iSF donor-acceptor pairs, while minimizing the number of computations. These parameters are applied to a chemically diverse, curated library of 81 truncated dimers of synthetically feasible donor-acceptor copolymers. From our dataset, four candidates are flagged for iSF, two of which were previously experimentally reported. This protocol is envisioned to be scaled up for the high-throughput screening of large databases of donor-acceptor dimers for the design and identification of conjugated polymers capable of iSF.