Interplay between Förster and Dexter Energy Transfer Rates in Isomeric Donor-Bridge-Acceptor Systems

The ability to direct the flow of excitons enable molecular systems to perform highly advanced functions. Intramolecular energy transfer in donor-bridge-acceptor systems can occur by different mechanisms, and the ability to control the excited state energy pathways depends on the capacity to favor one process over another. Here, we show an anticorrelation between the rates of Förster and Dexter types of energy transfer in two isomeric donor-bridge-acceptor systems. Both dyads display intramolecular Förster triplet-to-singlet and Dexter triplet-to-triplet energy transfers. However, as the bridge-acceptor connection point changes, the rate of one energy transfer process increases at the same time as the other one decreases, allowing us to control the energy flow direction. This work shows how rational design can be used to tune excited state energy pathways in molecular dyads, which is of importance for advanced functions such as multiplicity conversion in future molecular materials.