Exceptionally Strong Effect of Small Structural Variations in Functionalized 3,4-Phenylenedioxythiophenes on the Surface Nanostructure and Parahydrophobic Properties of Their Electropolymerized Films

Electropolymerization of electron-rich aromatics/heteroaromatics to form conducting polymers is an easy and powerful technique to form surfaces of different nanostructures and hydrophobicity/wettability. Understanding the factors governing the growth of the polymer nanostructures and controlling the surface morphology are the big challenges for the surface and materials science. In this paper, we report the design and synthesis of a series of 3,4-phenylenedioxythiophenes (PheDOTs) substituted at the benzene ring with 2-naphthylmethyl-, 1-naphthylmethyl-, and 9-anthracenylmethyl-groups (2Na-PheDOT, 1Na-PheDOT, and 9Ant-PheDOT). They have been electropolymerized in either potentiostatic or potentiodynamic conditions to form the polymer surfaces of different morphologies. Even small changes in the structure of PheDOT monomers by varying the side groups (2-/1-naphthyl- or 9-anthracenyl-) result in the formation of very different polymer surface nanostructures: from monodirectionally growing (one-dimensional) ...