Gating That Suppresses Charge Recombination–The Role of Mono‑<i>N</i>‑Arylated Diketopyrrolopyrrole

Suppressing the charge recombination (CR) that follows an efficient charge separation (CS) is of key importance for energy, electronics, and photonics applications. We focus on the role of dynamic gating for impeding CR in a molecular rotor, comprising an electron donor and acceptor directly linked via a single bond. The media viscosity has an unusual dual effect on the dynamics of CS and CR in this dyad. For solvents with intermediate viscosity, CR is 1.5–3 times slower than CS. Lowering the viscosity below ∼0.6 mPa s or increasing it above ∼10 mPa s makes CR 10–30 times slower than CS. Ring rotation around the donor–acceptor bond can account only for the trends observed for nonviscous solvents. Media viscosity, however, affects not only torsional but also vibrational modes. Suppressing predominantly slow vibrational modes by viscous solvents can impact the rates of CS and CR to a different extent. That is, an increase in the viscosity can plausibly suppress modes that are involved in the transition from the charge-transfer (CT) to the ground state, i.e., CR, but at the same time are not important for the transition from the locally excited to the CT state, i.e., CS. These results provide a unique example of synergy between torsional and vibronic modes and their drastic effects on charge-transfer dynamics, thus setting paradigms for controlling CS and CR

Dipole-Mediated Rectification of Intramolecular Photoinduced Charge Separation and Charge Recombination

Controlling charge transfer at a molecular scale is critical for efficient light harvesting, energy conversion, and nanoelectronics. Dipole-polarization electrets, the electrostatic analogue of magnets, provide a means for “steering” electron transduction via the local electric fields generated by their permanent electric dipoles. Here, we describe the first demonstration of the utility of anthranilamides, moieties with ordered dipoles, for controlling intramolecular charge transfer. Donor–acceptor dyads, each containing a single anthranilamide moiety, distinctly rectify both the forward photoinduced electron transfer and the subsequent charge recombination. Changes in the observed charge-transfer kinetics as a function of media polarity were consistent with the anticipated effects of the anthranilamide molecular dipoles on the rectification. The regioselectivity of electron transfer and the molecular dynamics of the dyads further modulated the observed kinetics, particularly for charge recombination. These findings reveal the underlying complexity of dipole-induced effects on electron transfer and demonstrate unexplored paradigms for molecular rectifiers