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

We report a long-lived charge-separated state in a chromophoric pair (DC-PDI 2 ) 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-PDI 2 manifests an ultrafast evolution of the SB-CS state with a time constant of τ S B - C S ${{\tau }_{{\rm S}{\rm B}-{\rm C}{\rm S}}}$ =0.35±0.02 ps and a slow charge recombination (CR) kinetics with τ C R ${{\tau }_{{\rm C}{\rm R}}}$ =4.09±0.01 ns in ACN. The rate constant of CR of DC-PDI 2 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 ( - Δ G C R ${{-{\rm \Delta }G}_{{\rm C}{\rm R}}}$ >λ). In contrast, an analogous benzyloxy (BnO)-substituted DC-BPDI 2 showcases a ≈10-fold accelerated CR kinetics with τ C R / τ S B - C S ${{\tau }_{{\rm C}{\rm R}}/{\tau }_{{\rm S}{\rm B}-{\rm C}{\rm S}}}$ 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.