Template Synthesis of Alkyl-Substituted Metal Isocorroles: Template Synthesis of Alkyl-Substituted Metal Isocorroles

Five metal complexes of 10,10-dimethylisocorrole ligands with full β-pyrrolic substitution is have been synthesized. The preparation of nickel(II), palladium(II), and copper(II) complexes was achieved by metal-templated oxidative macrocyclization of tetrapyrrolic 5,15-biladiene precursors. The reaction conditions for successful macrocycle formation in yields of 18–32 % depended strongly on the type of metal ion used. In the case of palladium, three different macrocyclic products were observed by varying the cyclization protocol. The ring-contracted metal 10-isocorroles were fully characterized by single-crystal X-ray diffraction, optical and resonance spectroscopy, and electrochemical methods. All the compounds belong to the class of nonaromatic porphyrinoids and their structural and spectroscopic properties as well as their redox behavior were found to show the characteristic features of both ring-contracted aromatic porphyrinoids and linear tetrapyrrole complexes.

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