title: Porphyrin Donor and Tunable Push-Pull Acceptor Conjugates-Experimental Investigation of Marcus Theory.
abstract: We report on a series of electron donor-acceptor conjugates incorporating a ZnII-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 -0.23 V 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.affiliation: Laboratorium für Organische Chemie, ETH Zürich, Vladimir-Prelog-Weg 3, 8093, Zürich, Switzerland.
authors.forename: Tristan A
authors.initials: TA
authors.lastname: Reekie
authors.affiliation: Department of Chemistry and Pharmacy and, Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-University Erlangen-Nuremberg, Egerlandstrasse 3, 91058, Erlangen, Germany.
authors.forename: Michael
authors.initials: M
authors.lastname: Sekita
authors.affiliation: Laboratorium für Organische Chemie, ETH Zürich, Vladimir-Prelog-Weg 3, 8093, Zürich, Switzerland.
authors.forename: Lorenz M
authors.initials: LM
authors.lastname: Urner
authors.affiliation: Department of Chemistry and Pharmacy and, Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-University Erlangen-Nuremberg, Egerlandstrasse 3, 91058, Erlangen, Germany.
authors.forename: Stefan
authors.initials: S
authors.lastname: Bauroth
authors.affiliation: Laboratoire d'Electrochimie et de Chimie Physique du Corps Solide, Institut de Chimie-UMR 7177, C.N.R.S., Université de Strasbourg, 4, rue Blaise Pascal, 67000, Strasbourg, France.
authors.forename: Laurent
authors.initials: L
authors.lastname: Ruhlmann
authors.affiliation: Laboratoire d'Electrochimie et de Chimie Physique du Corps Solide, Institut de Chimie-UMR 7177, C.N.R.S., Université de Strasbourg, 4, rue Blaise Pascal, 67000, Strasbourg, France.
authors.forename: Jean-Paul
authors.initials: JP
authors.lastname: Gisselbrecht
authors.affiliation: Laboratoire d'Electrochimie et de Chimie Physique du Corps Solide, Institut de Chimie-UMR 7177, C.N.R.S., Université de Strasbourg, 4, rue Blaise Pascal, 67000, Strasbourg, France.
authors.forename: Corinne
authors.initials: C
authors.lastname: Boudon
authors.affiliation: Laboratorium für Organische Chemie, ETH Zürich, Vladimir-Prelog-Weg 3, 8093, Zürich, Switzerland.
authors.forename: Nils
authors.initials: N
authors.lastname: Trapp
authors.affiliation: Department of Chemistry and Pharmacy, Computer Chemistry Center, Friedrich-Alexander-University Erlangen-Nuremberg, Nägelsbachstraße 25, 91052, Erlangen, Germany.
authors.forename: Timothy
authors.initials: T
authors.lastname: Clark
authors.affiliation: Department of Chemistry and Pharmacy and, Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-University Erlangen-Nuremberg, Egerlandstrasse 3, 91058, Erlangen, Germany.
authors.forename: Dirk M
authors.identifier: http://orcid.org/0000-0002-3960-1765
authors.initials: DM
authors.lastname: Guldi
authors.affiliation: Laboratorium für Organische Chemie, ETH Zürich, Vladimir-Prelog-Weg 3, 8093, Zürich, Switzerland.
authors.forename: François
authors.initials: F
authors.lastname: Diederich
keywords: Marcus theory; donor-acceptor systems; electron transfer; photochemistry; porphyrinoids