A Templateless Electropolymerization Approach to Nanorings Using Substituted 3,4‐Naphthalenedioxythiophene (NaPhDOT) Monomers

Abstract The formation of highly ordered surface structures is fundamental for various applications. Due to their rapidity of implementation and their cost, templateless processes are extremely interesting alternatives to the use of templates or lithographic processes. With the aim to prepare porous structures such as nanotubes, templateless electropolymerization was found to be a unique process. Based on previous works, we have synthesized 3,4‐naphthalenedioxythiophene (NaPhDOT) monomers substituted with alkyl chains (n=2 to 10), phenyl and naphthalene substituents. In particular, NaphDOT substituted with naphthalene (NaphDOT−Na) leads for the first time to relatively densely packed nanorings while their internal diameter is controllable with the number of deposition scans. Compared to previous works, which lead to nanotubes from non‐substituted NaphDOT and 3,4‐phenylenedioxythiophene substituted with naphthalene (PheDOT−Na), with NaphDOT−Na we observe a very important decrease in the polymer growth. As a consequence, only the initial peripherical nucleation around the gas bubbles is possible, leading to nanorings, because their growth into nanotubes is impeded by their low conductivity.