Bidirectional Electron Transfer Capability in Phthalocyanine–Sc3N@Ih–C80 Complexes
2015-10-14T00:00:00Z (GMT) by
To activate oxidative and/or reductive electron transfer reactions, N-pyridyl-substituted Sc3N@Ih–C80 (4) and C60 (3) fulleropyrrolidines have been prepared and axially coordinated to electron-rich (1) or electron-deficient (2) 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, 1/4 and 2/4 show unambiguously that a Zn(II)Pc-to-Sc3N@Ih–C80 photoinduced electron transfer takes place in the former ensemble, whereas a Sc3N@Ih–C80-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 Sc3N@Ih–C80, 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 en-route toward the construction of easy-to-prepare molecular materials featuring switchable electron transfer reactivity.