title: Understanding photophysical effects of cucurbituril encapsulation: a model study with acridine orange in the gas phase.
abstract: Encapsulation of dyes by cucurbituril macrocycles has proven profitable as a strategy to alter fluorescence characteristics in useful ways. Encapsulation generally results in longer fluorescence lifetimes, enhanced brightness, and solvatochromic effects not normally seen in the condensed phase. These effects have been attributed variously to both the removal of interactions with solvent molecules and to the confined environment of extremely low polarizability provided by the cucurbituril interior. It is difficult to disentangle these effects in solution. Here, we present results from gas-phase experiments designed to separate these effects, using cucurbit[7]uril (CB7), and the cationic dye acridine orange (AOH(+)) as a probe. Fluorescence properties of gaseous AOH(+) are compared with those of the gaseous AOH(+)-CB7 complex and with the properties of the dye and complex in aqueous solution. The dependence on the local environment of several spectroscopic properties is discussed, including the fluorescence excitation and emission maxima, the size of the Stokes shift, fluorescence lifetime and relative brightness. An understanding of the modulation of fluorescence properties by the local environment, such as that promoted by this work, will aid in the rational design of improved fluorophores and fluorescent sensors.
authors: Department of Chemistry, University of Toronto, Toronto, ON M5S 3H6 (Canada).
authors: Martin F
authors: MF
authors: Czar
authors: Rebecca A
authors: RA
authors: Jockusch