Computational Design of Cyclic Nitroxides as Efficient Redox Mediators for Dye‐Sensitized Solar Cells

Cyclic nitroxide radicals represent promising alternatives to the iodine‐based redox mediator commonly used in dye‐sensitized solar cells (DSSCs). To date DSSCs with nitroxide‐based redox mediators have achieved energy conversion efficiencies of just over 5 % but efficiencies of over 15 % might be achievable, given an appropriate mediator. The efficacy of the mediator depends upon two main factors: it must reversibly undergo one‐electron oxidation and it must possess an oxidation potential in a range of 0.600–0.850 V (vs. a standard hydrogen electrode (SHE) in acetonitrile at 25 °C). Herein, we have examined the effect that structural modifications have on the value of the oxidation potential of cyclic nitroxides as well as the reversibility of the oxidation process. These included alterations to the N‐containing skeleton (pyrrolidine, piperidine, isoindoline, azaphenalene, etc.), as well as the introduction of different substituents (alkyl‐, methoxy‐, amino‐, carboxy‐, etc.) to the ring. Standard oxidation potentials were calculated using high‐level ab initio methodology that was demonstrated to be very accurate (with a mean absolute deviation from experimental values of only 16 mV). An optimal value of 1.45 for the electrostatic scaling factor for UAKS radii in acetonitrile solution was obtained. Established trends in the values of oxidation potentials were used to guide molecular design of stable nitroxides with desired ${E{{{circ}hfill atop {rm ox}hfill}}}$ , and a number of compounds were suggested for potential use as enhanced redox mediators in DSSCs.