Bidirectional Electron Transfer Capability in Phthalocyanine–Sc<sub>3</sub>N@<i>I</i><sub><i>h</i></sub>–C<sub>80</sub> Complexes

To activate oxidative and/or reductive electron transfer reactions, <i>N</i>-pyridyl-substituted Sc<sub>3</sub>N@<i>I</i><sub><i>h</i></sub>–C<sub>80</sub> (<b>4</b>) and C<sub>60</sub> (<b>3</b>) fulleropyrrolidines have been prepared and axially coordinated to electron-rich (<b>1</b>) or electron-deficient (<b>2</b>) Zn­(II)­phthalocyanines (Zn­(II)­Pcs) through zinc-pyridyl, metal–ligand coordination affording a full-fledged family of electron donor–acceptor ensembles. An arsenal of photophysical assays as they were carried out with, for example, <b>1</b>/<b>4</b> and <b>2</b>/<b>4</b> show unambiguously that a Zn­(II)­Pc-to-Sc<sub>3</sub>N@<i>I</i><sub><i>h</i></sub>–C<sub>80</sub> photoinduced electron transfer takes place in the former ensemble, whereas a Sc<sub>3</sub>N@<i>I</i><sub><i>h</i></sub>–C<sub>80</sub>-to-Zn­(II)­Pc electron transfer occurs in the latter ensemble. To the best of our knowledge, this is the first time that a fullerene-based molecular building block shows an electron transfer dichotomy, namely acting both as electron-acceptor or electron-donor, and its outcome is simply governed by the electronic nature of its counterpart. In light of the latter, the present work, which involves the use of Sc<sub>3</sub>N@<i>I</i><sub><i>h</i></sub>–C<sub>80</sub>, one of the most abundant and easy-to-purify endohedral metallofullerenes, is, on one hand, a paradigmatic change and, on the other hand, an important milestone <i>en-route</i> toward the construction of easy-to-prepare molecular materials featuring switchable electron transfer reactivity.