Two new functionalized pi-extended benzofuran catechol porphyrins and nanostructured Mn-porphyrins have been synthesized by a green one-pot method and structurally characterized by spectroscopic analysis. The electro-oxidation of 5,10,15,20-tetrakis(2,3-dihydroxyphenyl) porphyrins(1a-b) with four catechol units in the presence of 3-hydroxy-1H-phenalene-1-one (3) as bidentate nucleophile has been done and benzofuran rings have formed by the intermolecular and intramolecular Michel addition reactions. Coulometry and voltammetry results allowed us to propose four independent ECEC mechanisms for the electrochemical oxidation pathway. Functionalization of the porphyrins affected their photophysical properties such as the efficiency of the fluorescence that would support the energy transfer between the porphyrin core and the substituted subunits. (C) 2011 Elsevier B.V. All rights reserved.