Competitive Charge Separation Pathways in a Flexible Molecular Folda-Dimer

We report the photophysical properties of a molecular folda-dimer system PDI-AnEt-PDI, where the electron-donating N,N-diethylaniline (AnEt₂) moiety bridges two electron-accepting perylene diimide (PDI) chromophores. The conformationally flexible PDI-AnEt-PDI adopts either an open (two PDIs far apart) or folded (two PDIs within π-stacking distance) conformation, depending on the solvent environment. We characterized the photoinduced charge separation dynamics of both open and folded forms in solvents of varying polarity. The open form undergoes charge separation to give PDI (Bridge electron transfer) independent of solvent polarity. The folded form exhibits two charge separation photoproducts, yielding both PDI and PDI, the latter of which is formed via symmetry-breaking charge separation (SBCS) between the two π-stacked PDI chromophores. Our results further indicate that the conformational flexibility of the folda-dimer leads to unexpected excimer formation in some open form conditions. In contrast, no excimer formation is observed in the folded form, indicating that this geometry preferentially yields the SBCS instead. Our results provide insight into how conformationally flexible folda-dimer systems can be designed and built to tune competitive photophysical pathways.