Syntheses and Characterization of Molybdenum/Zinc Porphyrin Dimers Bridged by Aromatic Linkers

Two new heterobinuclear porphyrin dimers, namely [{MoVIO2}‐DBPA‐Zn] (1; H4DBPA = N,N′‐dibenzylidenebis[4‐(10,15,20‐triphenyl‐21H,23H‐porphin‐5‐yl)phenylamine]) and [{MoVIO2}‐PBDA‐Zn] (2; H4PBDA = N,N′‐bis[4‐(10,15,20‐triphenyl‐21H,23H‐porphin‐5‐yl)phenyl]‐1,3‐benzenedicarboxamide), have been synthesized. These bis(porphyrin)s were obtained by treating 5‐(p‐aminophenyl)‐10,15,20‐triphenylporphyrinatomolybdenum and ‐zinc with benzene‐1,4‐dicarboxaldehyde or benzene‐1,3‐dicarboxylic acid. They have been characterized by UV/Vis, IR, X‐ray photoelectron, luminescence, and 1H NMR spectroscopy, and their TG‐DTA behavior and molar conductances have also been determined. Th cis‐dioxomolybdenum(VI) unit in these complexes is contained in one of the porphyrin moieties and zinc(II) ion is tetracoordinated in the other. Their electrochemical properties have also been investigated in detail. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)