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RESEARCH PRODUCT

Synthesis and Physicochemical Characterization of Bis(macrocycles) Involving a Porphyrin and a meso ‐Substituted Corrole – X‐ray Crystal Structure of a [(Free‐base porphyrin)–corrole]bis(pyridine)cobalt Complex

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A very efficient, simple synthesis of face-to-face porphyrin–corrole free-bases bearing substituents at the meso positions of the corrole ring is reported. Starting from the (porphyrin–aldehyde)zinc species 1Zn, porphyrin–corrole free-bases (3M, 3C) are obtained in two steps, in fairly good yields (40–43 %), compared to 11 steps for their corrole β-pyrrole-substituted counterparts. Moreover, the possibility to directly synthesize the free-base (porphyrin–corrole)cobalt complex (5M or 5C) allows for the further preparation of heterodimetallic derivatives. Crystals of the bis(pyridine) adduct of 5M have been grown; the molecular structure clearly shows that the two pyridine molecules are coordinated to the cobalt ion in endo and exo positions, leading to an open-mouth geometry of the bis(macrocycle). The structure of 5M(py)2also shows intermolecular π–π interactions along the [1 0 0] direction, leading to stacking of the complexes. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)