A Symmetry-Broken Charge-Separated State in the Marcus Inverted Region

We report a long-lived charge-separated state in a chromophoric pair (DC-PDI₂ ) that uniquely integrates the advantages of fundamental processes of photosynthetic reaction centers: i) Symmetry-breaking charge-separation (SB-CS) and ii) Marcus-inverted-region dependence. The near-orthogonal bichromophoric DC-PDI₂ manifests an ultrafast evolution of the SB-CS state with a time constant of $$ =0.35±0.02 ps and a slow charge recombination (CR) kinetics with $$ =4.09±0.01 ns in ACN. The rate constant of CR of DC-PDI₂ is 11 686 times slower than SB-CS in ACN, as the CR of the PDI radical ion-pair occurs in the deep inverted region of the Marcus parabola ( $$ >λ). In contrast, an analogous benzyloxy (BnO)-substituted DC-BPDI₂ showcases a ≈10-fold accelerated CR kinetics with $$ lowering to ≈1536 in ACN, by virtue of a decreased CR driving force. The present investigation demonstrates a control of molecular engineering to tune the energetics and kinetics of the SB-CS material, which is essential for next-generation optoelectronic devices.