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

Reekie TA, Sekita M, Urner LM, Bauroth S, Ruhlmann L, Gisselbrecht JP, Boudon C, Trapp N, Clark T, Guldi DM, Diederich F (2017)

Publication Status: Published

Publication Type: Journal article

Publication year: 2017

Journal

Publisher: WILEY-V C H VERLAG GMBH

Book Volume: 23

Pages Range: 6357-6369

Journal Issue: 26

DOI: 10.1002/chem.201700043

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.

Authors with CRIS profile

Involved external institutions

École Polytechnique Fédérale de Lausanne (EPFL) Switzerland (CH) Université de Strasbourg (UDS) France (FR)

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://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.

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