Excited-state dynamics of dipyrrolyldiketone difluoroboron complexes

Anion-responsive photofunctional materials have been extensively studied because anions are important for biotic activity and constitute the building blocks of elegant supramolecular architectures. A number of fluorescent anion receptors that can probe anions in their environments have been reported, but the excited states of many of these molecules remain elusive. Studies on excited-state dynamics provide fruitful information for optimizing the emission properties, minimizing the photodegradation and photorelease of anions, and exploring novel photofunctions. In this study, we investigated the excited-state dynamics of an aryl-substituted dipyrrolyldiketone difluoroboron complex, a pi-conjugated anion receptor, by time-resolved visible and infrared absorption spectroscopy and emission decay measurements combined with quantum chemical calculations. Anion binding was found to alter the radiative and nonradiative rate constants and the excited-state absorption of the anion receptor. In contrast, the molecular structures and binding abilities were similar in the S-0 and S-1 states.