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.

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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.

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