Post-Installation of Fused Benzoheptagons at the Periphery of NiII Porphyrins: Helical Structures and Conformation-Adjustable Fullerenes Binding.

Fused-benzoheptagon-installed NiII porphyrins were synthesized by a protocol consisting of (2-formyl)arylation at the meso-position(s) of NiII porphyrins, conversion of formyl group to methoxyethene group by Wittig reaction, and final Bi(OTf)3-catalyzedcyclization. The structures of these porphyrins have been revealed by X-ray analysis. Owing to the installed heptagon ring(s), these porphyrins show curved structures with conformational flexibility. Dimer 9 has been shown to have a small activation barrier for inversion and to capture C60 and C70 with large association constants with adjustable conformational changes.