Proton-coupled energy transfer in molecular triads

Abstract

We experimentally discovered and theoretically analyzed a photochemical mechanism, which we term proton-coupled energy transfer (PCEnT). A series of anthracene-phenol-pyridine triads formed a local excited anthracene state after light excitation at a wavelength of ~400 nanometers (nm), which led to fluorescence around 550 nm from the phenol-pyridine unit. Direct excitation of phenol-pyridine would have required ~330-nm light, but the coupled proton transfer within the phenol-pyridine unit lowered its excited-state energy so that it could accept excitation energy from anthracene. Singlet-singlet energy transfer thus occurred despite the lack of spectral overlap between the anthracene fluorescence and the phenol-pyridine absorption. Moreover, theoretical calculations indicated negligible charge transfer between the anthracene and phenol-pyridine units. We construe PCEnT as an elementary reaction of possible relevance to biological systems and future photonic devices.