Mediating Reductive Charge Shift Reactions in Electron Transport Chains

Beitrag in einer Fachzeitschrift


Details zur Publikation

Autor(en): Wolf M, Villegas C, Trukhina O, Delgado JL, Torres T, Martin N, Clark T, Guldi DM
Zeitschrift: Journal of the American Chemical Society
Verlag: AMER CHEMICAL SOC
Jahr der Veröffentlichung: 2017
Band: 139
Heftnummer: 48
Seitenbereich: 17474-17483
ISSN: 0002-7863


Abstract

We report the synthesis of a full-fledged family of covalent electron donor-acceptor(1)-acceptor(2) conjugates and their charge-transfer characterization by means of advanced photophysical assays. By virtue of variable excited state energies and electron donor strengths, either Zn(II)Porphyrins or Zn(II)Phthalocyanines were linked to different electron-transport chains featuring pairs of electron accepting fullerenes, that is, C-60 and C-70. In this way, a fine-tuned redox gradient is established to power a unidirectional, long-range charge transport from the excited-state electron donor via a transient C-60(center dot-) toward C-70(center dot-). This strategy helps minimize energy losses in the reductive, short-range charge shift from C-60 to C-70. At the forefront of our investigations are excited-state dynamics deduced from femtosecond transient absorption spectroscopic measurements and subsequent computational deconvolution of the transient absorption spectra. These provide evidence for cascades of short-range charge-transfer processes, including reductive charge shift reactions between the two electron-accepting fullerenes, and for kinetics that are influenced by the nature and length of the respective spacer. Of key importance is the postulate of a mediating state in the charge-shift reaction at weak electronic couplings. Our results point to an intimate relationship between triplet-triplet energy transfer and charge transfer.


FAU-Autoren / FAU-Herausgeber

Clark, Timothy apl. Prof. Dr.
Computer-Chemie-Centrum
Guldi, Dirk Michael Prof. Dr.
Lehrstuhl für Physikalische Chemie I
Wolf, Maximilian
Lehrstuhl für Physikalische Chemie I


Autor(en) der externen Einrichtung(en)
Universidad Autónoma de Madrid (UAM)
Universidad Complutense de Madrid (UCM)
University of Basque Country / Universidad del Pais Vasco (UPV) / Euskal Herriko Unibersitatea (EHU)


Zitierweisen

APA:
Wolf, M., Villegas, C., Trukhina, O., Delgado, J.L., Torres, T., Martin, N.,... Guldi, D.M. (2017). Mediating Reductive Charge Shift Reactions in Electron Transport Chains. Journal of the American Chemical Society, 139(48), 17474-17483. https://dx.doi.org/10.1021/jacs.7b08670

MLA:
Wolf, Maximilian, et al. "Mediating Reductive Charge Shift Reactions in Electron Transport Chains." Journal of the American Chemical Society 139.48 (2017): 17474-17483.

BibTeX: 

Zuletzt aktualisiert 2018-20-12 um 08:53