The frantic race towards nanotechnologies led to the development of modified electrodes having smaller and smaller thicknesses. The ultimate state is the self-assembled monolayer (SAM).

In the field of electrochemistry, the nanometric dimensionality has never been a problem because the limiting factor is not the thickness of the layer, but the surface of the electrode. However, the nanometric scale of the electroactive layer limits the possibility to characterize the SAM via “standard” absorption and emission spectroscopic methods.

Here, we are going to present a pioneering spectroelectrochemical study on thiophene1 and perylendiimide2 based SAMs, illustrating the benefits provided by the latest technological breakthroughs and providing a promising tool to probe nanomaterials.