Donor-acceptor molecules are a subject of great attention due to their immense potential in molecular electronics and photovoltaics. Despite numerous extensive studies demonstrating their functionality in solution, the donor-acceptor character is usually lost upon adsorption on a conducting substrate. Here the concept of breaking the conjugation between the donor and acceptor unit by insertion of a bridge is used. Furthermore, the bridge introduces a kink into the dyad and thus, reduces the possibility of hybridization with the substrate. A donor-bridge-acceptor dyad composed of carbazole and phenalenone units joined through a flexible bridge is synthesized and deposited on a Pt(111) surface. Its electronic properties are investigated with a combination of low temperature scanning tunneling microscope measurements and density functional theory simulations. Two preferential adsorption configurations are identified, in which individual molecules form strong bonds to the substrate and to a Pt adatom. Differential conductance measurements and atomistic simulations evidence the preservation of a reduced donor-acceptor character upon adsorption of the molecule, where this reduction is ascribed to the strong molecule-metal hybridization. Our results highlight the changes in donor-acceptor character of the dyad induced by the substrate and provide guidelines for the use of donor-bridge-acceptor molecules as functional units in solid-state devices.

Department of Condensed Matter Physics Faculty of Mathematics and Physics Charles University CZ 12116 Prague 2 Czech Republic

Faculty 1 Mathematics Computer Science and Natural Science RWTH Aachen University 52056 Aachen Germany

Institut für Organische Chemie und Makromolekulare Chemie Heinrich Heine Universität Düsseldorf Universitätsstrasse 1 40225 Düsseldorf Germany

Institute of Physics Academy of Sciences of the Czech Republic CZ 162 00 Prague 6 Czech Republic

Peter Grünberg Institut JARA FIT Forschungszentrum Jülich GmbH 52425 Jülich Germany

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