Abstract
The polymeric, fluoro-bridged phthalocyanine complex [Al(Pc)F] n [J.P. Linksy, T.R. Paul, R.A. Nohr and M.E. Kenney, Inorg. Chem., 19 (1980) 3131] has attracted considerable attention since it can be doped using a variety of oxidizing agents to give conducting materials [R.S. Nohr, P.M. Kuznesof, K.J. Wynne, M.E. Kenney and P.G. Sieberman, J. Am. Chem. Soc., 103 (1981) 4371; P. Brant, D.C. Weber, S.G. Haupt, R.S. Nohr and K.J. Wynne, J. Chem. Soc. Dalton Trans. (1985) 269; D. Djurado, A. Hamai and C. Fabre, Synth. Met., 29 (1989) 71F and refs therein]. However, many features of the doping process, particularly structural aspects, remain unclear. Evaporation of [Al(Pc)F] n onto single crystal KCl results in an epitaxial film which has been structurally characterized by high resolution transmission electron microscopy [J.R. Fryer and M.E. Kenney, Macromolecules, 21 (1988) 259]. In the present work oxidation of [Al(PC)F] n supported on KCl or silica wafers had been compared with oxidations performed on polycrystalline material in the presence of MeCN. Oxidizing agents used include hexafluorides (UF 6, MoF 6, WF 6), pentafluorides (AsF 5, PF 5, IF 5) halogens (Cl 2, Br 2, I 2) and the NO + cation. The colour change, blue→purple occurs in all cases. There are spectroscopic similarities between film and polycrystalline reactions and the oxidized products are freely soluble in MeCN. The spectroscopic and TEM data suggest that in many cases oxidation is accompanied by depolymerization. Depolymerization appears to be important also when [Al(Pc)F] n is protonated by CF 3CO 2H and CF 3SO 3H.
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