Keywords: Diporphyrins / Electrochemistry / UV/Vis spectroscopy / Electrostatic interactions / ConjugationA novel series of biaryl-type, meso,meso-linked and planar, triply fused diporphyrin derivatives was prepared and fully characterized together with the corresponding monoporphyrin control compounds. They feature peripheral meso-3-cyanophenyl and meso-3,5-cyanophenyl groups, which have previously been shown to undergo transformation into malonates without perturbation of the porphyrin core and subsequent Bingel addition to fullerene C 60 . The tetrapyrrolic metal binding sites in the diporphyrin arrays are either complexed to two Zn II or Cu II ions, or, in a mixed coordination, to one Cu II and one Zn II ion; alternatively, one or both sites remain unoccupied. The interaction between the differen-