Systematic variation of cyanobuta-1,3-dienes and expanded tetracyanoquinodimethane analogues as electron acceptors in photoactive, rigid porphyrin conjugates

Urner LM, Sekita M, Trapp N, Schweizer WB, Woerle M, Gisselbrecht JP, Boudon C, Guldi DM, Diederich F (2015)

Publication Type: Journal article

Publication year: 2015

Journal

European Journal of Organic Chemistry Wiley

Book Volume: 2015

Pages Range: 91-108

Journal Issue: 1

DOI: 10.1002/ejoc.201403252

Abstract

We report on a homologous series of nine electron donor-acceptor systems featuring push-pull chromophores as electron acceptors, which are accessible by a cycloaddition-retroelectrocyclization (CA-RE) reaction. The conjugates comprise a Zn^II porphyrin as electron donor, which is connected through either a rigid phenylene-ethynylene-phenylene (PEP)-bicyclo[2.2.2]octane or a PEP-trans-decahydroquinoline spacer to different anilino-substituted multicyanobutadienes or extended tetracyanoquinodimethane analogues with first reduction potentials ranging from-1.78 to-0.58 V vs. Fc⁺/Fc. Characterization of the conjugates includes X-ray crystallography, electrochemistry, DFT calculations, and fluorescence spectroscopy. The extent of Zn^II porphyrin fluorescence quenching correlates with the strength of the electron acceptor. Overall, we demonstrate the synthetic feasibility of rationally modulating the acceptor strength by means of the CA-RE reaction in geometrically well-defined electron donor-acceptor conjugates.

Authors with CRIS profile

Michael Sekita Lehrstuhl für Physikalische Chemie I Dirk Michael Guldi Lehrstuhl für Physikalische Chemie I

Involved external institutions

Eidgenössische Technische Hochschule Zürich (ETHZ) / Swiss Federal Institute of Technology in Zurich

Switzerland (CH) Université de Strasbourg (UDS)

France (FR)

How to cite

APA:

Urner, L.M., Sekita, M., Trapp, N., Schweizer, W.B., Woerle, M., Gisselbrecht, J.-P.,... Diederich, F. (2015). Systematic variation of cyanobuta-1,3-dienes and expanded tetracyanoquinodimethane analogues as electron acceptors in photoactive, rigid porphyrin conjugates. European Journal of Organic Chemistry, 2015(1), 91-108. https://doi.org/10.1002/ejoc.201403252

MLA:

Urner, Lorenz M., et al. "Systematic variation of cyanobuta-1,3-dienes and expanded tetracyanoquinodimethane analogues as electron acceptors in photoactive, rigid porphyrin conjugates." European Journal of Organic Chemistry 2015.1 (2015): 91-108.

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