Synthesis of Pyrrole-Sharing Fused Porphyrinoid Hybrids by Post-fabrication of Ni(II) Porphyrins.

ABSTRACT

Pyrrole-sharing fused hybrids of NiII porphyrin with PdII N-confused(NC)-corrole and PdII NC-oxaporphyrin were synthesized by post-fabrication of NiII porphyrins. Specifically this consists of Friedel-Crafts type aromatic substitution reaction of meso-free NiII porphyrin with α,α'-dibromotripyrrin and Pd(OAc)2 assisted cyclization, and final heating to induce a Pd-C bond formation. NiII porphyrins fused with PdII NC-corrole and with PdII NC-oxaporphyrins show coplanar structures with a shared pyrrole unit. In these hybrids, the PdII NC-oxaporphyrin is aromatic and the PdII NC-corrole is moderately antiaromatic and these local electronic properties interact to influence the whole network.