Synthetic Metals 159 (2009) 2202–2204 Contents lists available at ScienceDirect Synthetic Metals journal homepage: www.elsevier.com/locate/synmet New derivatives of phenylamine as novel building blocks of conducting polymers Mieczyslaw Lapkowski a,b,∗ , Sylwia Golba a,∗ , Jadwiga Soloducho c , Krzysztof Idzik c a Silesian University of Technology, Faculty of Chemistry, Strzody 9, 44-100 Gliwice, Poland b PAS, Centre of Polymer and Carbon Materials, ul. M. Curie-Skolodowska 34, 41-819 Zabrze, Poland c Wroclaw University of Technology, Department of Chemistry, Faculty of Medicinal Chemistry and Microbiology, Wybrzeze Wyspianskiego 27, 50-370 Wroclaw, Poland article info Article history: Received 25 July 2008 Received in revised form 2 September 2009 Accepted 3 September 2009 Available online 22 October 2009 Keywords: Electrochemical doping Diphenylamine and triphenylamine derivatives Electroconductivity Electrochemical polymerisation abstract A novel phenylamine substituted derivatives possessing different photochromic groups were investi- gated. Using the electrochemical and spectroelectrochemical measurements the electrochemical activity of the monomers and polymers have been studied. The results indicate good film forming properties most of the monomers and stability of the forming films. The polymeric films include diphenylamine or triphenylamine unit and five member heterocycle ring moieties. © 2009 Elsevier B.V. All rights reserved. 1. Introduction The preparation and application of electrochemically active conducting polymers are still part of the research activity of many scientists nowadays. Among many methods utilised to obtain these materials electrochemical polymerisation of ben- zoid or heterocyclic monomers is the one widely used [1]. Owing to its good electrochemistry [2], electrochromic prop- erties [3] and good environmental stability [4] polyaniline has gained attention as a technologically important material as a sen- sor, electrochromic display device, corrosion protecting film. In order to improve processability [5], electrochromism [6] or ion exchange capability [7] of polyaniline the investigation of many benzene ring or N-substituted derivatives were done. Some of the N-substituted derivatives were successfully synthesised by elec- trochemical method like N-metyl, N-ethyl, N-phenyl, N-naphthyl or N-benzyl [6,8–12]. From these reports it seems clear that the oxidation potential of the monomers are lower than the parent aniline. The main reason to this seems to be the presence of elec- tron donating group at the N-position. Electropolymerisation of diphenylamine (DPN) were synthesised in acetonitrile solution ∗ Corresponding author at: Silesian University of Technology, Faculty of Chem- istry, Strzody 9, 44-100 Gliwice, Poland. E-mail address: Sylwia.Golba@polsl.pl (S. Golba). and in this case the reaction seems to differ significantly from other N-substituted derivatives. During diphenylamine polymeri- sation the C C bond is form between the two phenyl rings, while in case of the other derivatives mainly the C N coupling takes place [13]. It was stated that poly(DPN) showed new type of redox transitions in comparison to polyaniline—it revealed presence of diphenylbenzidine radical cation after first stage of oxidation (DPN •+ ) and diphenoquinone diimine unit after further oxidation (DPN ++ ) [14,15]. During last years considerable attention was paid to phenylamine derivatives such as diphenylamine and tripheny- lamine which is due to their specific electrochemical properties [13]. Poly(diphenylamine) (poly(DPA)) is electroactive and exhibit multiple and reversible color changes depending on the oxidation state. It is characterised by high doping level (0.53) and reason- able high electrical conductivity similar to those of polyaniline and poly(p-phenylene) (2  -1 cm -1 ). [13]. To improve electroactive character of polymers obtained from phenylamine derivatives it was convenient to attach heterocycle rings (for example, thiophene, furane, pyridine) in para position of the phenyl rings. According to literature some electroactive deriva- tives of poly(diphenylamine) were synthesised [13,16–19]. In the present study we describe the electrochemical and spec- troelectrochemical study of the triphenylamine and diphenylamine derivatives. Using cyclic voltammperometry (CV) and UV–vis spectroelectrochemical measurements method electrooxidation of monomers and forming films were investigated. 0379-6779/$ – see front matter © 2009 Elsevier B.V. All rights reserved. doi:10.1016/j.synthmet.2009.09.005