Electron donor-acceptor molecules are of outstanding interest in molecular electronics and organic solar cells for their intramolecular charge transfer controlled via electrical or optical excitation. The preservation of their electronic character in the ground state upon adsorption on a surface is cardinal for their implementation in such single-molecule devices. Here, we investigate by atomic force microscopy and scanning tunneling microscopy a prototypical system consisting of a π-conjugated tetrathiafulvalene-fused dipyridophenazine molecule adsorbed on thin NaCl films on Cu(111). Depending on the adsorption site, the molecule is found either in a nearly undisturbed free state or in a bound state. In the latter case, the molecule adopts a specific adsorption site, leading to the formation of a chelate complex with a single Na+ alkali cation pulled out from the insulating film. Although expected to be electronically decoupled, the charge distribution of the complex is drastically modified, leading to the loss of the intrinsic donor-acceptor character. The chelate complex formation is reversible with respect to lateral manipulations, enabling tunable donor-acceptor molecular switches activated by on-surface coordination.

Department of Chemistry and Biochemistry University of Bern Freiestr 3 3012 Bern Switzerland

Department of Physics University of Basel Klingelbergstr 82 4056 Basel Switzerland

Institute of Physics Academy of Sciences of the Czech Republic v v i Cukrovarnická 10 162 00 Prague Czech Republic

International Center for Materials Nanoarchitectonics National Institute for Materials Science 1 1 Namiki Tsukuba Ibaraki 305 0044 Japan

PRESTO Japan Science and Technology Agency 4 1 8 Honcho Kawaguchi Saitama 332 0012 Japan

References provided by Crossref.org

Exploiting Cooperative Catalysis for the On-Surface Synthesis of Linear Heteroaromatic Polymers via Selective C-H Activation

Preservation of the donor-acceptor character of a carbazole-phenalenone dyad upon adsorption on Pt(111)

On-Surface Bottom-Up Synthesis of Azine Derivatives Displaying Strong Acceptor Behavior