Abstract

Reactions of photochemically or radiolytically generated radicals with tetrakis(x-aminophenyl)porphyrin, tapp2-, initiate the polymerization of the porphyrin complexes Mtapp, where M = Ni or Zn. In the photochemical process, the porphyrin-centered excited state of Mtapp reacts with the ground state to generate oxidized and reduced radical species. The cationic radical, M(tapp{radical dot}+), appears to be the initiator of the porphyrin polymerization. An electron transfer reaction between the excited state of Mtapp and a Co(III) complex generates also the cation radical and initiates the polymerization process. Pulse radiolytically generated multiscripts(Cl, 2, mml:none(), mml:none(), -) and OH{radical dot} radicals were also able to initiate the polymerization of the porphyrin complexes. © 2006 Elsevier B.V. All rights reserved.