65 research outputs found

    Tracking molecular resonance forms of donor-acceptor push-pull molecules by single-molecule conductance experiments

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    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

    Formation of higher-order fullerene dianions in collisions with Na atoms

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    We have measured electron capture cross sections in collisions between higher order fullerene anions Cn- (n=76, 78, 82, 84, 86, 90 and 96) and Na atoms. The ions were produced in an electrospray ion source (ESI) and accelerated to an energy of 50 keV. The measured cross section for dianion formation is three times larger for C96 than that for C60. The latter cross section was earlier found to be 36 Å2. The dramatic increase of the cross section with fullerene size is explained by means of the curve crossing model for electron transfer
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