The current knowledge about the presence of cation radicals in organic semiconductors is connected with oxidized constitutional units and their interaction with counterions. In this work, we have shown that the formation of cation radicals in poly­(3,4-ethylene­dioxythiophene) is induced by intermolecular electrostatic interactions, particularly by hydrogen-bond formation between formic acid and polymer. Raman, XPS, UV–vis, and EPR spectroscopies were used to prove that by using the simplest carboxylic acid, which can form hydrogen bonding, it is possible to form localized cation radicals. Moreover, it was shown that by replacing formic acid with o-phosphoric acid, it is possible to obtain delocalized cation radicals. The gained new understanding how to tune the formation and nature of cation radicals in organic semiconductors can be used in the design of organic electronics.

The preparation of soluble conducting polymers proceeds by the chemical oxidation method in the presence of water‐soluble polyelectrolytes. Among conducting polymers, polyethylene‐(3,4‐dioxythiophene) (PEDOT) is the most investigated due to its intrinsic properties. In this work, for the first time a simple method of ethylene‐(3,4‐dioxythiophne) self‐polymerization without applying any oxidant and with the formation of PEDOT solution at room temperature with a yield of 100% is presented. This PEDOT solution could be deposited on many desirable surfaces (by simple evaporation of the solvent) for various applications from photovoltaic cell to pseudocapacitors. Moreover, it is discovered that the self‐polymerization method does not produce byproducts, which makes the method environmentally friendly. The effect of light and different acids is explored. Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy (XPS), and Raman spectroscopy confirm the formation of PEDOT by the self‐polymerization method. Moreover, this method provides a way to obtain and study individual PEDOT chains. The self‐polymerization method may be applied for the preparation of other conducting polymers.

Polyaniline (PANI), is one of the promising candidates for utilization as electrode material in supercapacitors and its electro-and physical-chemical properties have been studied for several decades. However, there are fundamental questions that need to be answered. For example, is it possible to obtain and characterize individual PANI chains or what is the impact of

The photoluminescence and anisotropic structure of PEDOT are obtained in the presence of ions that perturb the water structure.