Spectroelectrochemical Properties of Some Polymers of Polythiophene Series
- Russian Journal of ElectroChemistry, 41(6), p.671-680, 2005 .
The spectroelectrochemical behavior in situ of some polymers of polythiophene series, polybithiophene (PBT)and poly-3-phenylthiophene (P3PhT), is studied in the processes of anodic and cathodic doping. It is confirmed that in the case of PBT and P3PhT, the cathodic evolution of the absorption spectra, which is characteristic of the cathodic doping process, occurs in solutions of tetrabutylammonium salts, but not in solutions of lithium salts. It is shown that polymers of a more complicated structure than that of PBT, e.g. P3PhT, feature additional absorption bands, as compared to PBT, which emonstrates a single absorption band. Moreover, in the case of P3PhT, two color transitions can be observed by sight in the process of doping-undoping, unlike the single transition observed in the case of PBT and most other electron-conducting polymers. On the basis of quantum-mechanical calculations, an assumption is made that such a behavior of P3PhT is due to the decrease of the local symmetry of polythiophene chain in the presence of a bulky substituent, which causes the activation of the transitions in the electronic spectra that are forbidden in more symmetrical structures.