title: Bidirectional Electron Transfer Capability in Phthalocyanine-Sc3N@I(h)-C80 Complexes.
abstract: To activate oxidative and/or reductive electron transfer reactions, N-pyridyl-substituted Sc3N@I(h)-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@I(h)-C80 photoinduced electron transfer takes place in the former ensemble, whereas a Sc3N@I(h)-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@I(h)-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.
authors.affiliation: Department of Organic Chemistry, Universidad Autónoma de Madrid , Cantoblanco, 28049 Madrid, Spain.|IMDEA Nanociencia , Faraday 9, 28049 Madrid, Spain.
authors.forename: Olga
authors.initials: O
authors.lastname: Trukhina
authors.affiliation: Department of Chemistry and Pharmacy and Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-Universität Erlangen-Nürnberg , 91058 Erlangen, Germany.
authors.forename: Marc
authors.initials: M
authors.lastname: Rudolf
authors.affiliation: Department of Organic Chemistry, Universidad Autónoma de Madrid , Cantoblanco, 28049 Madrid, Spain.|IMDEA Nanociencia , Faraday 9, 28049 Madrid, Spain.
authors.forename: Giovanni
authors.initials: G
authors.lastname: Bottari
authors.affiliation: Department of Chemistry, Tokyo Gakugei University , Koganei, Tokyo 184-8501, Japan.
authors.forename: Takeshi
authors.initials: T
authors.lastname: Akasaka
authors.affiliation: IMDEA Nanociencia , Faraday 9, 28049 Madrid, Spain.
authors.forename: Luis
authors.initials: L
authors.lastname: Echegoyen
authors.affiliation: Department of Organic Chemistry, Universidad Autónoma de Madrid , Cantoblanco, 28049 Madrid, Spain.|IMDEA Nanociencia , Faraday 9, 28049 Madrid, Spain.
authors.forename: Tomas
authors.initials: T
authors.lastname: Torres
authors.affiliation: Department of Chemistry and Pharmacy and Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-Universität Erlangen-Nürnberg , 91058 Erlangen, Germany.
authors.forename: Dirk M
authors.initials: DM
authors.lastname: Guldi