Excited-state properties of fluorenones: influence of substituents, solvent and macrocyclic encapsulation

Abstract

A comprehensive investigation of the photophysics of a broad set of fluorenones substituted with methoxy groups at different positions brings out the importance of the location of substituents on the fluorenone core in modulating fluorescence and radiationless deactivation by way of modification of the singlet-excited state energy and its character. While the substituents at para positions are found to affect neither the fluorescence quantum yield nor the lifetime, those at meta positions are found to significantly modify the latter. A cumulative effect is observed for the substituents in that the nonradiative decay (k_nr) becomes progressively dominant with an increasing number of meta-methoxy substituents. For example, the trimethoxy substitution in 2,4,7-trimethoxyfluorenone (8) is found to increase k_nr by ca. 30 fold relative to that of the parent fluorenone (1) in a polar aprotic solvent such as acetonitrile. The predominance of nonradiative decay (k_nr) is rationalized from stabilization of the singlet-excited state via partial charge transfer from meta-methoxy substituents to the carbonyl group. Accordingly, a nice correlation is observed for the nonradiative (k_nr) rate constants versus singlet-excitation energies derived from fluorescence emission maxima of all fluorenones in acetonitrile. The macrocyclic host cucurbit[7]uril (CB7) is found to not only enhance the fluorescence of the parent fluorenone (1) significantly, but also increase the singlet lifetime considerably. Based on the changes observed in the absorption spectra and the lifetimes determined, a 1 : 1 host–guest complex has been proposed with CB7. The fluorescence lifetime observed in the presence of CB7 suggests that the hydrophobic fluorenone (1) can be employed as a probe to report on a polar microenvironment shielded from hydrogen bonding interactions in a polar protic solvent.