Manipulating Triplet Yield through Control of Symmetry-Breaking Charge Transfer.

The efficiency of an organic solar cell depends on the efficacy of exciton diffusion and dissociation processes, and this can be enhanced by reducing the exciton binding energy and increasing the exciton lifetime. Zinc chlorodipyrrin (ZCl) complexes exhibit reduced exciton binding energy due to ultrafast generation of intramolecular charge transfer (ICT) states via symmetry-breaking charge transfer in polar media. This Letter explores the fate of the ICT states using nanosecond transient absorption. In cyclohexane, ZCl undergoes intersystem crossing to produce triplets with ∼8 ns time constant (∼30% yield), and no ICT states are generated. However, in more polar solvents, triplets are generated within 1 ns via ICT state recombination with ∼3 times higher yield than produced via ISC. This high triplet yield in toluene (89%) and acetonitrile (76%) via ICT state recombination is a beneficial pathway to spin-protect the excited-state decay for additional charge generation from triplet excited states.