Can aromaticity enhance the electron transport in molecular wires?

Abstract

Abstract An interesting debate has been recently raised around the role played by aromaticity in the electron transport ability of molecular wires. Normally, it is associated to destructive interference effects, so that the more aromatic the wire the less conductor. This rule was observed experimentally in a series of homologous wires containing ring units of different aromaticity, but theoretical calculations and other recent experiments demonstrate the rule cannot be generalized and depends, for instance, in the type of molecule-electrode contact. However, neither chemical explanation nor qualitative rules were given yet to allow predicting the specific behavior of different molecular junctions. In this work, using series of polymeric molecular wires of different length and formed by different aromatic units, it is proven how it is possible to change from an expected destructive to a constructive interference effect of the aromaticity in the electron transport. Thus, aromaticity may be also employed to enhance the electron transport in a molecular wire. A chemical explanation to the experimental and theoretical observations is given and a simple way of tuning the response of a molecular wire to an external electric voltage by increasing/decreasing its aromaticity and changing its type of molecule-electrode contact is provided.