Synthesis and characterization of copper undecaarylcorroles and the first undecaarylcorrole free base

Abstract

The Suzuki cross-coupling reaction of copper β-octabromo-meso- triarylcorroles with arylboronic acids led to various copper peraryl-substituted corroles 4a-c, 5a-c, and 6a-c. The crystal structures of complexes 4b, 5a, 5b, 6a, 6b, and 6c show that their saddling dihedral angles strongly depend on the nature of the meso substituents, whereas the β-aryl substituents induce a significant redshift of their UV/Vis absorption maxima. Copper corrole 5c was successfully demetalated to produce the corresponding undecaarylcorrole free base 7. The crystal structure of 7 revealed that the introduction of 11 bulky aryl groups on the corrole ring did not produce unusual distortions in the macrocycle of the free base. Saddle undecaaryl copper corroles were prepared by a Suzuki cross-coupling procedure. Their saddling dihedral angles strongly depend on the meso substituents, whereas the β-aryl groups induce a redshift of their UV/Vis absorption maxima. The X-ray structure of the demetalated undecaarylcorrole free base shows that full aryl substitution has no impact on the conformation of the corrole. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.