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In this study, pyrolysis mass spectrometry has been applied for the investigation of thermal characteristics of $\hbox{PF}_{6}^{-}$‐doped polythiophene (PTh) films. Thermal degradation of PTh showed behaviour identical with $\hbox{BF}_{4}^{-}$‐doped polythiophene (BF4‐PTh), indicating that the effects of the dopants in question on the thermal characteristics of the PTh are not significant. Besides the oligomer peaks (up to hexamer), peaks indicating decomposition of the thiophene ring have also been detected as in the case of BF4‐PTh. However, the data also indicated that the oxidation of the $\hbox{PF}_{6}^{-}$ dopant was much more effective, yielding mainly POF3, H3PO4 compounds even for the freshly prepared samples. Upon ageing, the yield of these products increased and exposure to air for more than 50 days also caused degradation of the PTh chains. Furthermore, substitution of the thiophene (Th) ring by fluorine has been recorded and was associated with reactions of Th with the reactive oxidation products of the dopant. Analyses of the de‐doped samples showed that although de‐doping was effective to a certain extent, inward diffusion of the counter ion (C4H9)4N+ has also occurred. This diffusion was more efficient than that was observed for BF4‐PTh samples. Copyright © 2004 Society of Chemical Industry

Electrospray ionization mass spectrometry (ESI/MS) has allowed the discovery of novel dimer ions emerging from solutions of metalloporphyrin salts and their investigation by collision-induced dissociation (CID) with N(2) molecules. ESI mass spectra have been recorded for the formation of the oxygen or chloride-bridged dimer ions [(FeTPP)(2)OH](+), [(MnTPP)(2)OH](+), [(FeTPP)(2)Cl](+) and [(MnTPP)(2)Cl](+) derived from various solutions of FeTPPCl and MnTPPCl salts. The CID of [(FeTPP)(2)OH](+) proceeds mainly by neutral loss of (FeTPP)OH to form [FeTPP](+) and, to a minor extent, to form the charge-reversed products. The CID of [(MnTPP)(2)OH](+) exhibits exclusively the product ion [MnTPP](+) by loss of neutral (MnTPP)OH. [(FeTPP)(2)Cl](+) and [(MnTPP)(2)Cl](+) dissociate by loss of (Fe/MnTPP)Cl to give rise to [Fe/MnTPP](+). [(FeTPP)(2)O](+) and [(FeTPP)(2)OH](+) were generated from a solution of the dimer, (FeTPP)(2)O. Dissociation of [(FeTPP)(2)O](+) yields two product ions, [FeTPP](+) and [(FeTPP)O](+), with higher onsets compared to the equivalent fragments formed from [(FeTPP)(2)OH](+).

Pyrolysis of electrochemically prepared BF 42 doped polythiophene (PTh) by direct insertion probe and Currie point pyrolysis gas chromatography mass spectrometry techniques indicated that thermal decomposition of PTh occurs in two steps. In accordance with literature results, the first step is assigned to the loss of the dopant, and the second step to the degradation of the polymer backbone producing segments of various conjugation lengths. At elevated temperatures, detection of products such as H 2 S and C 2 H 2 indicating cleavage of the thiophene (Th) ring was associated with a network structure. For the dedoped samples, a significant increase in the relative intensities of the peaks characteristic to the counter ion of the dopant, N(C 4 H 9 ) 4 þ pointed out the inward diffusion of (C 4 H 9 ) 4 N þ during the dedoping process.