Porphyrin Donor and Tunable Push-Pull Acceptor ConjugatesExperimental Investigation of Marcus Theory

Journal article


Publication Details

Author(s): Reekie TA, Sekita M, Urner LM, Bauroth S, Ruhlmann L, Gisselbrecht JP, Boudon C, Trapp N, Clark T, Guldi DM, Diederich F
Journal: Chemistry - A European Journal
Publisher: WILEY-V C H VERLAG GMBH
Publication year: 2017
Volume: 23
Journal issue: 26
Pages range: 6357-6369
ISSN: 0947-6539
eISSN: 1521-3765


Abstract

We report on a series of electron donor-acceptor conjugates incorporating a Zn-II-porphyrin-based electron donor and a variety of non-conjugated rigid linkers connecting to push-pull chromophores as electron acceptors. The electron acceptors comprize multicyanobutadienes or extended tetracyanoquinodimethane analogues with first reduction potentials ranging from -1.67 to -0.23V vs. Fc(+)/Fc in CH2Cl2, which are accessible through a final-step cycloaddition-retroelectrocyclization (CA-RE) reaction. Characterization of the conjugates includes electrochemistry, spectroelectrochemistry, DFT calculations, and photophysical measurements in a range of solvents. The collected data allows for the construction of multiple Marcus curves that consider electron-acceptor strength, linker length, and solvent, with data points extending well into the inverted region. The enhancement of electron-vibration couplings, resulting from the rigid spacers and, in particular, multicyano-groups in the conformationally highly fixed push-pull acceptor chromophores affects the charge-recombination kinetics in the inverted region drastically.


FAU Authors / FAU Editors

Bauroth, Stefan
Lehrstuhl für Physikalische Chemie I
Clark, Timothy apl. Prof. Dr.
Computer-Chemie-Centrum
Guldi, Dirk Michael Prof. Dr.
Lehrstuhl für Physikalische Chemie I
Sekita, Michael Dr.
Lehrstuhl für Physikalische Chemie I


External institutions
École Polytechnique Fédérale de Lausanne (EPFL)
Université de Strasbourg (UDS)


How to cite

APA:
Reekie, T.A., Sekita, M., Urner, L.M., Bauroth, S., Ruhlmann, L., Gisselbrecht, J.-P.,... Diederich, F. (2017). Porphyrin Donor and Tunable Push-Pull Acceptor ConjugatesExperimental Investigation of Marcus Theory. Chemistry - A European Journal, 23(26), 6357-6369. https://dx.doi.org/10.1002/chem.201700043

MLA:
Reekie, Tristan A., et al. "Porphyrin Donor and Tunable Push-Pull Acceptor ConjugatesExperimental Investigation of Marcus Theory." Chemistry - A European Journal 23.26 (2017): 6357-6369.

BibTeX: 

Last updated on 2018-19-12 at 17:08