We determine and compare, at the single molecule level and under identical environmental conditions, the electrical conductance of four conjugated phenylene oligomers comprising terminal sulfur anchor groups with simple structural and conjugation variations. The comparison shows that the conductance of oligo(phenylene vinylene) (OPV) is slightly higher than that of oligo(phenylene ethynylene) (OPE). We find that solubilizing side groups do neither prevent the molecules from being anchored within a break junction nor noticeably influence the conductance value.

The realization of molecular-scale electronic devices will require the development of novel strategies for controlling electrical properties of metal/molecule/metal junctions, down to the single molecule level. Here, we show that it is possible to exert chemical control over the formation of metal/molecule...molecule/metal junctions in which the molecules interact by pi-stacking. The tip of an STM is used to form one contact, and the substrate the other; the molecules are conjugated oligophenyleneethynylenes (OPEs). Supramolecular pi-pi interactions allow current to flow through the junction, but not if bulky tert-butyl substituents on the phenyl rings prevent such interactions. For the first time, we find evidence that pi-stacked junctions can form even for OPEs with two thiol contacts. Furthermore, we find evidence for metal|molecule|metal junctions involving oligophenyleneethynylene monothiols, in which the second contact must be formed by the interaction of the pi-electrons of the terminal phenyl ring with the metal surface.