An anthracene-appended β-cyclodextrin-based dyad: Study of self-assembly and photoinduced electron-transfer processes

Abstract

The self-assembly of a β -cyclodextrin (β -CD)-based supramolecular dyad is reported, in which the donor anthracene moiety is covalently linked to the smaller rim of the β -CD and the acceptor pyromellitic diimide (PMDI) is encapsulated within the β -CD cavity. Encapsulation of the PMDI into the β -CD cavity was studied by a variety of techniques, which suggested that PMDI is encapsulated so as to position the aromatic part at the centre of the cavity with the 2-propyl end at the narrower rim among the overhanging primary OH groups and the N-ethylpyridinium end situated at the wider rim exposed to water. Photoinduced electron transfer (PET) in the system was studied by fluorescence quenching and laser flash photolysis techniques. At [PMDI]<10^-4M, the equilibrium is in favour of the free molecules, and under these conditions fluorescence quenching is negligible and diffusion-mediated electron transfer involving the triplet excited state of anthracene predominates. At higher concentrations of PMDI, the equilibrium is largely in favour of the supramolecular dyad and intra-ensemble PET processes predominate. The experimentally determined electron-transfer rate constant agrees very well with that calculated by using the Marcus equation. It was observed that a fraction of the ion pairs survived for more than 200 μ s.