ja5b06454_si_001.pdf (3.37 MB)
Bidirectional Electron Transfer Capability in Phthalocyanine–Sc3N@Ih–C80 Complexes
journal contribution
posted on 2015-10-14, 00:00 authored by Olga Trukhina, Marc Rudolf, Giovanni Bottari, Takeshi Akasaka, Luis Echegoyen, Tomas Torres, Dirk M. GuldiTo 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.