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Two-Step Charge-Separation Passing Through the Partial Charge-Transfer State in a Molecular Dyad.

Charge-separation (CS) in molecular systems usually takes place in weakly-coupled donor-acceptor dyads where an electron charge moves from the donor to the acceptor in the local excited-state of a chromophore. Herein, we present a two-step charge-separation process in a newly synthesized diketopyrrolopyrrole-pyrrolopyrrole (DPP-PP) dyad (AD) which starts from the initial photo-excited bright exciton and goes through a partial charge-transfer (CT) state before finally reaching the charge-separated (CS) state. The evolving CT character in the excited state is demonstrated through the complementary use of transient absorption, broadband fluorescence up-conversion, and transient impulsive stimulated Raman spectroscopy. The bright exciton state of the dyad relaxes to a partial CT state with 1 and 20 ps during solvent and structural fluctuations in toluene, respectively, and with 700 fs for the solvent fluctuations occurring in tetrahydrofuran. This is evident from the characteristic excited-state absorption spectra and the reduced fluorescence intensity observed on the adiabatic potential energy surface. AD in THF additionally evolves to the diabatic potential energy surface of the CS state, whose absorption spectrum converges to that of a DPP anion for which fluorescence is completely quenched. The trend of shifting for certain vibrational frequencies also supports the proposed CT dynamics and mechanism; furthermore, it gives quantitative insight into the CT characters of the bright state (0.1 e) and intermediate partial CT state (0.5 e), as determined by the linear relationship that exists between the vibrational frequency of the marker modes and the CT character. We have found that as the structure of the bridge between donor and acceptor enables an intermediate level of electronic communication, the charge-separation can rapidly occur through a distinct partial charge-transfer state. It seems that the exceptionally strong electronic communication at positions 2 and 5 of pyrrolo[3,2-b]pyrrole core is a crucial element for this charge-transfer mechanism which would be applied to organic photovoltaics or light-emitting diodes requiring efficient charge-separation.