Endohedral metallofullerenes - filled fullerene derivatives toward multifunctional reaction center mimics

• Antragsteller: Professor Dr. Dirk M. Guldi
• Fachliche Zuordnung: Physikalische Chemie von Festkörpern und Oberflächen, Materialcharakterisierung ; Physikalische Chemie von Molekülen, Flüssigkeiten und Grenzflächen, Biophysikalische Chemie
• Förderung: Förderung von 2010 bis 2019
• Projektkennung: Deutsche Forschungsgemeinschaft (DFG) - Projektnummer 163372219

• Erstellungsjahr: 2019

Zusammenfassung der Projektergebnisse

Our earlier starting point was the reduction of endohedral metallofullerenes in electron-donor acceptor systems; a reactivity pathway similar to that established for fullerenes. As a complement, we demonstrated in a few cases that endohedral metallofullerenes also act as electron donors, namely undergoing one-electron oxidation, when combined with strong electron acceptors. A direct comparison between these two opposing pathways was, however, impeded by the fact that too many parameters were changed at the same time; electron donor/acceptor strength, electron-donor acceptor distance, excited state energy, reorganization energy, to name just a few. To this end, the first milestone of the current project was to limit the variables to just one, that is, the electron donor/acceptor strength in a series of phthalocyanines. This turned out to be essential in terms of either photo-oxidizing or -reducing Sc3N@Ih-C80 as a representative case for endohedral metallofullerenes. The second milestone was to take that concept further and focus on electron deficient subphthalocyanines to photo-oxidize endohedral metallofullerenes such as La2@C80. As a matter of fact, the oxidizing power of these electron deficient subphthalocyanines was so high that it enabled the third milestone, that is, for the first time the photo-oxidation of empty fullerenes. All of the aforementioned set the stage for the fourth milestone that is photo-oxidation of endohedral metallofullerenes and photoreduction of empty fullerenes in one and the same electron-donor acceptor system: We designed, synthesized, and probed a Lu3N@Ih-C80-C60 electron-donor acceptor system and demonstrated that the presence of Lu3N facilitatest triplet radical ion state formation and that that this triplet radical ion state is longer-lived by nearly two orders of magnitude when compared to the corresponding singlet radical ion state.

Projektbezogene Publikationen (Auswahl)

• (2019) All-Fullerene Electron Donor-Acceptor Conjugates. Angewandte Chemie (International ed. in English) 58 (21) 6932–6937
  Izquierdo, Marta; Platzer, Benedikt; Stasyuk, Anton J.; Stasyuk, Olga A.; Voityuk, Alexander A.; Cuesta, Sergio; Solà, Miquel; Guldi, Dirk M.; Martín, Nazario
  
• Chem. Comm. 2015, 41, 330
  L. Feng, M. Rudolf, O. Trukhina, Z. Slanina, F. Uhlik, X. Lu, T. Torres, D.M. Guldi, T. Akasaka
  
• Chem. Eur. J. 2015, 21, 746
  B. Liu, H. Fang, X. Li, W. Cai, L. Bao, M. Rudolf, F. Plass, L. Fan, X. Lu, D.M. Guldi
  
• Chem. Sci. 2015, 6, 4141
  M. Rudolf, O. Trukhina, J. Perles, L. Feng, T. Akasaka, T. Torres, D.M. Guldi
  
• J. Am. Chem. Soc. 2015, 137, 12914
  O. Trukhina, M. Rudolf, G. Bottari, T. Akasaka, L. Echegoyen, T. Torres, D.M. Guldi
  
• Chem. Soc. Rev. 2016, 45, 612
  M. Rudolf, S.V. Kirner, D.M. Guldi