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Stabilizing ion and radical ion pair states in a paramagnetic endohedral metallofullerene/π-extended tetrathiafulvalene conjugate.

Electron donor-acceptor conjugates of paramagnetic endohedral metallofullerenes and π-extended tetrathiafulvalene (exTTF) were synthesized, characterized, and probed with respect to intramolecular electron transfer involving paramagnetic fullerenes. UV-vis-NIR absorption spectroscopy complemented by electrochemical measurements attested to weak electronic interactions between the electron donor, exTTF, and the electron acceptor, La@C(82), in the ground state. In the excited state, photoexcitation powers a fast intramolecular electron transfer to yield an ion and radical ion pair state consisting of one-electron-reduced La@C(82) and of one-electron-oxidized exTTF.