Determination of the Structural Features of a Long-Lived Electron-Transfer State of 9-Mesityl-10-methylacridinium Ion

Extensive efforts have been devoted to developing electron donor–acceptor systems that mimic the utilization of solar energy that occurs in photosynthesis. X-ray crystallographic analysis shows how absorbed photon energy is stabilized in those compounds by structural changes upon photoinduced electron transfer (ET). In this study, structural changes of a simple electron donor–acceptor dyad, 9-mesityl-10-methylacridinium cation (Acr+–Mes), upon photoinduced ET were directly observed by laser pump and X-ray probe crystallographic analysis. The N-methyl group in Acr+ was bent, and a weak electrostatic interaction between Mes and a counteranion in the crystal (ClO4) was generated by photoinduced ET. These structural changes correspond to reduction and oxidation due to photoinduced ET and directly elucidate the mechanism in Acr+–Mes for mimicking photosynthesis efficiently.