Bidirectional
Electron Transfer Capability in Phthalocyanine–Sc<sub>3</sub>N@<i>I</i><sub><i>h</i></sub>–C<sub>80</sub> Complexes
Olga Trukhina
Marc Rudolf
Giovanni Bottari
Takeshi Akasaka
Luis Echegoyen
Tomas Torres
Dirk M. Guldi
10.1021/jacs.5b06454.s001
https://acs.figshare.com/articles/journal_contribution/Bidirectional_Electron_Transfer_Capability_in_Phthalocyanine_Sc_sub_3_sub_N_i_I_i_sub_i_h_i_sub_C_sub_80_sub_Complexes/2121832
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.
2015-10-14 00:00:00
photophysical assays
easy-to-purify endohedral metallofullerenes
milestone en-route
Zn
Sc 3 N
latter ensemble
electron transfer dichotomy
Bidirectional Electron Transfer Capability
switchable electron transfer reactivity
building block
pyridyl-substituted Sc 3 N
C 60