摘要：

Porphyrins substituted at meso positions with aminophenyl groups undergo oxidative electropolymerization in a process analogous to the formation of polyaniline. Porphyrins that successfully generate polymer films on the electrode include those tetrasubstituted with four p-aminophenyl groups, trisubstituted, or trans-disubstituted, but not cis-disubstituted or monosubstituted. The polymerization process is monitored independently by cyclic voltammetry, absorption spectroscopy, and an electrochemical quartz crystal microbalance. The mechanism is considered analogous to aniline polymerization, except that attack of electrophilic nitrogens must occur at ortho positions of another aminophenyl group. Reflectance FT-IR and resonance Raman spectroscopy detect the presence of diphenylamine, dihydrophenazine, and phenazine linkages in the porphyrin polymer film from tetra(4-aminophenyl)porphyrin (TAPP). TAPP polymerized in dichloromethane (DCM) with added pyridine gradually passivates; i.e., electronic conductivity...

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