10.1021/jacs.5b06454.s001
Olga Trukhina
Olga
Trukhina
Marc Rudolf
Marc
Rudolf
Giovanni Bottari
Giovanni
Bottari
Takeshi Akasaka
Takeshi
Akasaka
Luis Echegoyen
Luis
Echegoyen
Tomas Torres
Tomas
Torres
Dirk M. Guldi
Dirk M.
Guldi
Bidirectional
Electron Transfer Capability in Phthalocyanine–Sc<sub>3</sub>N@<i>I</i><sub><i>h</i></sub>–C<sub>80</sub> Complexes
American Chemical Society
2015
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
2015-10-14 00:00:00
Journal contribution
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.