We use scanning tunneling microscope break-junction (STM-BJ) measurements to study the low-bias conductance and high-bias current–voltage (IV) characteristics of a series of asymmetric para–meta connected diphenyl-oligoenes. From tight-binding calculations, we determine that the quantum interference features inherent in our molecular design result in a ‘through-bond’ coupling on the para-side, and through-space coupling on the meta-side. We show that these molecular junctions form single molecule diodes, and show that the rectification results from a difference in the voltage dependence of the coupling strength on the through-bond and the through-space side. The interplay between the applied voltage and the molecule–metal coupling results from the asymmetric polarizability of the conducting orbital under an external field.