Interaction between encapsulated excited organic molecules and free nitroxides: communication across a molecular wall.

Communication between two molecules, one confined and excited (triplet or singlet) and one free and paramagnetic, has been explored through quenching of fluorescence and/or phosphorescence by nitroxides as paramagnetic radical species. Quenching of excited states by nitroxides has been investigated in solution, and the mechanism is speculated to involve charge transfer and/or exchange processes, both of which require close orbital interaction between excited molecule and quencher. We show in this report that such a quenching, which involves electron-electron spin communication, can occur even when there is a molecular wall between the two. The excited state molecule is confined within an organic capsule made up of two molecules of a deep cavity cavitand, octa acid, that exists in the anionic form in basic aqueous solution. The nitroxide is kept free in aqueous solution. (1)H NMR and EPR experiments were carried out to ascertain the location of the two molecules. The distance between the excited molecule and the paramagnetic quencher was manipulated by the use of cationic, anionic, and neutral nitroxide and also by selectively including the cationic nitroxide within the cavity of cucurbituril. Results presented here highlight the role of the lifetime of the encounter complex in electron-electron spin communication when the direct orbital overlap between the two molecules is prevented by the intermediary wall.