The surface wettability, such as superhydrophobic properties, of nanofibrous structures is highly depending on their size, length, spacing or orientation to the surface. Finding a way to control all these characteristics is extremely important in a theoretical point of view and for various applications. Here, we report the possible tuning of all these characteristics by adjusting the length (n) of the alkyl chains of electrodeposited poly(3,3‐dialkyl‐3,4‐propylenedioxythiophene), which allows the formation of horizontally or vertically oriented nanofibers of various dimensions and spacings. Here, we play especially on the hydrophilic/hydrophobic characteristics of the polymer to change the growth of a polymer on a substrate and the distance between the polymer backbones. For example, a change in the fiber orientation from horizontal to vertical is observed for n = 2. For n < 2, the polymer fibers are mainly horizontally aligned while for n > 2, the polymer fibers are vertically aligned.

The influence of the substituent size and position of 3,4‐propylenedioxythiophene (ProDOT) on the surface properties of the corresponding electrodeposited polymer films is shown. The study investigates the influence on the formation of hydrophobic nanofibers using two substituents (isopropyl and tert‐butyl). The 3‐position of ProDOT is the best for the formation of nanofibers, because it leads to the longest polymer chains while also leading to the highest intrinsic hydrophobicity, two effects that increase the formation of surface structures.

Inspired by surface properties in nature, we develop for the first time nanofibers of poly(3,4‐ethylenedioxypyrrole) (PEDOP) and poly(3,4‐propylenedioxypyrrole) (PProDOP) with superhydrophobic and highly oleophobic properties via electropolymerization. This was achieved by grafting fluorinated chains onto the alkylenedioxy cycle of PEDOP and PProDOP, while keeping NH groups free. We use a novel strategy to prepare EDOP and ProDOP with a hydroxyl group on the cycle by reaction with epibromohydrin, which is followed by grafting of fluorinated chains. The highest surface properties are obtained with the shortest fluorinated chains (C4F9) due to the formation of nanofibers and the dimension of these nanofibers can be controlled by changing the base monomer (EDOP or ProDOP). This work can be of interest to researchers working in many fields such as the control of wetting properties but also in the development of conducting polymers, membranes, and sensors. For example, EDOT and ProDOT are actually the most‐employed monomers to obtain conducting polymers and here we show that EDOP and ProDOP derivatives have similar electropolymerization properties, which shows the importance of this manuscript for the scientific community. Moreover, the possibility to substitute on the NH groups will be another possiblity to obtain multifunctional polymers, while the NH groups can also be used to obtain pH‐sensitive polymers.

In nature, superhydrophobic (low adhesion) and parahydrophobic (high adhesion) properties exist in lotus leaves and red roses, for example. The control in the water adhesion is extremely important for applications in water harvesting, for example. Here, we report the obtaining of parahydrophobic properties through the electropolymerization of 3,4-ethylenedioxypyrrole (EDOP) derivatives. We report for the first time an electrochemical study of EDOP derivatives bearing aromatic cycles (phenyl, naphthalene, biphenyl, and pyrene). Eight novel EDOP monomers are studied with and without the presence of an ethyl acetate spacer in order to give more mobility to the aromatic substituents. Surprinsgly, higher steric hindrance are observed during electropolymerization with spacer. However, the polymers are more insoluble with spacer, which is an important point for electropolymerization. The highest parahydrophobic properties are obtained with biphenyl groups and with the spacer, which are due to the presence of both micro-and nanostructures.