Electronic Tuning of Host-Guest Interactions within the Cavities of Fluorophore-Appended Calix[4]arenes

A series of fluorescent calix[4]arene scaffolds bearing electron-rich carbazole moiety conjugated at the lower rim have been prepared. Studies of the fluorescence quenching in the presence of the N-methyl pyridinium guest revealed that the electronic properties of the distal phenolic ring play a major role in the host-guest complexation. In particular, placing an electron-donating piperidine fragment at that ring significantly increased the host-guest interactions, while introducing the same fragment into the proximal phenolic ring weakened the fluorescence response. These results suggest that the dominant interactions between the guest and calixarene cavity involve the oxygen-depleted fluorophore-bearing aromatic ring and not the more electron-rich unsubstituted phenolic fragments.