Triplet excitation transfer through the walls of hemicarcerands: dependence of the electronic coupling on the size of the molecular cage.

Abstract

Triplet excitation transfer from biacetyl trapped inside three hemicarcerands of different size (1, 2, and 3) to acceptors in the surrounding medium was investigated. The largest hemiracerand 1 employs four butyl linkers and the intermediate hemicarcerand 2 four o-xylyl linkers. The smallest hemicarcerand 3 contains only three methylene linkers. Both neat liquid triplet acceptors and acceptors dispersed in solvents were used. The primary objective of this work was to determine the dependence of the energy transfer rate on the size and the electronic structure of the molecular cages. There is a pronounced, more than 10-fold, increase of triplet energy transfer rates with decreasing size of the cage. The corresponding electronic coupling, /V/, increases approximately by a factor of approximately 3.5 from the largest hemicarceplex 1 to the smallest hemicarceplex 3. This increase of the electronic interaction is similar to that observed in covalently bound systems when the distance between the triplet donor and the acceptor is reduced by one carbon-carbon sigma-bond. The electronic structure of the hemicarcerand appears to be of secondary importance, at least when T(1) states of the donor and the acceptor are far from a resonance with the T(1) state of the cage. A very good agreement between the results obtained in neat acceptors and in solution was found, indicating that the association between the acceptors and the molecular cages is negligible, if at all present. An unexpectedly large interaction between the guest and the polarizable walls of the hemicarcerands manifested by emission red-shifts was observed in all cases. This suggests that the entrapment within the molecular cage gives rise to an environment considerably different from that of a single molecule in the gas phase. An interesting correlation between the magnitude of the phosphorescence spectral shift, Deltanu(0-0), and the guest-to-external acceptor electronic coupling, /V/, was found.