A Cucurbit[6]uril Analogue: Host Properties Monitored by Fluorescence Spectroscopy

Abstract

This paper describes the host properties of a new cucurbit[6]uril analogue, studied by fluorescence and ¹H NMR spectroscopy. This host has an elongated cavity with oval-shaped portals. It is intrinsically fluorescent, and more importantly, this fluorescence is sensitive to guest encapsulation, allowing for the study of the inclusion of nonfluorescent guests by fluorescence spectroscopy. In the case of benzene as guest, significant enhancement of the cucurbit[6]uril analogue host fluorescence was observed upon addition of benzene; this allowed for the determination of the binding constant for 1:1 host−guest complexation, yielding a value of K = 6900 ± 1100 M^-1. This complexation was also studied by ¹H NMR, yielding a similar value of K = 8980 ± 500 M^-1. The binding of a much larger guest, the dye Nile Red, was also studied, but in this case using guest fluorescence. Significant suppression of the Nile Red fluorescence was observed upon 1:1 complexation with the cucurbit[6]uril analogue, with an extremely large binding constant of 8.2 ± 0.5 × 10⁶ M^-1, indicating a very strong host−guest interaction and an excellent size and shape match. In both cases, binding was much stronger than in the case of the same guests with cucurbit[6]uril itself, and in the case of Nile Red, binding was also much stronger than with modified β- or γ-cyclodextrins. This is partly a result of the partial aromatic nature of the host walls, which allow for π−π interactions not possible in cucurbiturils or cyclodextrins. The ability to study its inclusion complexes using either host or guest fluorescence, and the very high binding constants observed, illustrates the versatility and potential usefulness of this new host compound.