title: Tracking molecular resonance forms of donor-acceptor push-pull molecules by single-molecule conductance experiments.
abstract: The ability of molecules to change colour on account of changes in solvent polarity is known as solvatochromism and used spectroscopically to characterize charge-transfer transitions in donor-acceptor molecules. Here we report that donor-acceptor-substituted molecular wires also exhibit distinct properties in single-molecule electronics under the influence of a bias voltage, but in absence of solvent. Two oligo(phenyleneethynylene) wires with donor-acceptor substitution on the central ring (cruciform-like) exhibit remarkably broad conductance peaks measured by the mechanically controlled break-junction technique with gold contacts, in contrast to the sharp peak of simpler molecules. From a theoretical analysis, we explain this by different degrees of charge delocalization and hence cross-conjugation at the central ring. Thus, small variations in the local environment promote the quinoid resonance form (off), the linearly conjugated (on) or any form in between. This shows how the conductance of donor-acceptor cruciforms is tuned by small changes in the environment.
authors.affiliation: Department of Chemistry, University of Copenhagen, Universitetsparken 5, Copenhagen DK-2100, Denmark.
authors.forename: Henriette
authors.initials: H
authors.lastname: Lissau
authors.affiliation: Kavli Institute of Nanoscience, Delft University of Technology, GA Delft 2600, The Netherlands.
authors.forename: Riccardo
authors.initials: R
authors.lastname: Frisenda
authors.affiliation: Department of Chemistry, University of Copenhagen, Universitetsparken 5, Copenhagen DK-2100, Denmark.
authors.forename: Stine T
authors.initials: ST
authors.lastname: Olsen
authors.affiliation: Department of Chemistry, University of Copenhagen, Universitetsparken 5, Copenhagen DK-2100, Denmark.
authors.forename: Martyn
authors.initials: M
authors.lastname: Jevric
authors.affiliation: Department of Chemistry, University of Copenhagen, Universitetsparken 5, Copenhagen DK-2100, Denmark.
authors.forename: Christian R
authors.initials: CR
authors.lastname: Parker
authors.affiliation: Department of Chemistry, University of Copenhagen, Universitetsparken 5, Copenhagen DK-2100, Denmark.
authors.forename: Anders
authors.initials: A
authors.lastname: Kadziola
authors.affiliation: Department of Chemistry, University of Copenhagen, Universitetsparken 5, Copenhagen DK-2100, Denmark.
authors.forename: Thorsten
authors.initials: T
authors.lastname: Hansen
authors.affiliation: Kavli Institute of Nanoscience, Delft University of Technology, GA Delft 2600, The Netherlands.
authors.forename: Herre S J
authors.initials: HS
authors.lastname: van der Zant
authors.affiliation: Department of Chemistry, University of Copenhagen, Universitetsparken 5, Copenhagen DK-2100, Denmark.
authors.forename: Mogens
authors.initials: M
authors.lastname: Brøndsted Nielsen
authors.affiliation: Department of Chemistry, University of Copenhagen, Universitetsparken 5, Copenhagen DK-2100, Denmark.
authors.forename: Kurt V
authors.initials: KV
authors.lastname: Mikkelsen