Molecular engineering charge transfer and triplet exciton formation in donor–acceptor cocrystals

Organic donor–acceptor (D–A) cocrystals are gaining attention for their potential applications in optoelectronic devices. This study explores the dynamics of charge transfer (CT) and triplet exciton formation in various D–A cocrystals. By examining a series of D–A cocrystals composed of coronene (COR), peri-xanthenoxanthene (PXX), and perylene (PER) donors paired with N,N-bis(3′-pentyl)perylene-3,4:9,10-bis(dicarboximide) (PDI), naphthalene-1,4:5,8-tetracarboxy-dianhydride (NDA), or pyrene-4,5,9,10-tetraone (PTO) acceptors, using transient absorption microscopy and time-resolved electron paramagnetic resonance spectroscopy, we find that the strength of the CT interaction influences the nature and yield of triplet excitons produced by CT state recombination. In particular, in the PER-PDI, COR-PTO, and PER-PTO cocrystals, localized triplet excitons are lower in energy than the CT state. By contrast, no localized triplet excitons are available to the CT states of the PXX-NDA, PER-NDA, and PXX-PTO cocrystals, and as a result, the CT states rapidly decay to ground state with no triplet formation. Moreover, density functional theory calculations show that the transition between delocalized CT states to a triplet state localized to a single donor or acceptor unit provides the source of spin–orbit coupling necessary when the triplet states are energetically accessible. These findings provide insights into the design of molecular materials with tailored exciton properties for optoelectronic applications.