ArticleAccounts of chemical research2025
Ion Translocation Driven by Electric Field Generated in Excited-State Reactions.
Article in Accounts of chemical research, 2025. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 1 paper.
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1 citing paper in PubMed.
- π-Stacked supramolecular contact ion pairs prohibit quenching and provide control of symmetry in fluorescent dyes.Chemical science · 2026Article
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4 authors.
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No grant is acknowledged in the PubMed record.
Abstract
ConspectusThe fundamental mechanism of ion translocation against the concentration gradient in biological systems has become a central focus of research. The variation of the electric field in response to external stimuli can be an essential trigger in this process. The introduction of molecular machines has enriched this field by providing a direct approach to converting energy into mechanical work. However, existing models mainly rely on photoisomerization dynamics that alter the location of ion-carrying molecular segments to achieve transportation. In a recent series of works, we present a new design of light-driven anion-translocating molecular machines that do not involve any conformational changes. In the designed structures, the dramatic redistribution of positive charge from the electron acceptor to the donor moiety in the dipolar cation dye is driven by excited-state intramolecular charge transfer (ESICT). This shifts the anion binding site to the opposite side of the molecule, facilitating a fast and directional ion motion. The continuous reversible cycle arises from the fact that the forward motion occurs during the excited-state lifetime on the high-energy potential energy surface, whereas the reverse reaction proceeds on the ground-state potential energy surface. Thus, the light quanta not only provide the energy source but also serve as the factor that drives the ion in the specified direction.The unexpected observation about the anomalous dual-emission behavior of various phosphonium and pyridinium salts in nonpolar solvents has prompted the proposal of such a photoinduced counterion migration mechanism. Unlike the ultrafast ESICT process, which occurs on a subpicosecond time scale, the appearance of a strongly Stokes-shifted emission band─attributed to anion translocation─is observed over tens to hundreds of picoseconds. Furthermore, it was shown that the increase in ion radius results in the retardation of anion motion, which can be adequately explained by the mechanism we proposed. The interpretation of ion motion as a relaxation process toward electrostatic equilibrium is supported by the observed monoexponential decay of the spectral response function
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