Global Antiaromaticity Induced by Installation of 3,5-Di(pyrrol-2-yl)BODIPY across the meso Position of Porphyrinoids.

Installations of the 3,5-di(pyrrol-2-yl)BODIPY strap across the meso position of B(III) submonoazaporphyrin, B(III) subporphyrin, and Ni(II) porphyrin resulted in the formation of expanded porphyrins with a dual electronic network consisting of a local diatropic ring current of the original aromatic segments and a newly formed global paratropic ring current as evinced by 1H NMR spectroscopy, UV-vis-NIR absorption spectra, small electrochemical HOMO-LUMO gaps, and NICS and ACID calculations. This synthetic protocol is useful for modulating the aromatic character of meso-aza and meso-free aromatic porphyrinoids.