Redox-Associated Variation of Huckel Aromaticity from Lactam-Embedded Smallest Antiaromatic trans-Doubly N-Confused Porphyrins: Synthesis and Characterization

High-yield synthesis, spectroscopic and solid-state structural proof of the lactam-embedded smallest ever metal-free stable Huckel antiaromatic trans-doubly N-confused [16] porphyrins are reported. These new facets of trans-doubly N-confused porphyrins have been anticipated to exhibit the redox-associated variation of Huckel aromaticity as a mere consequence of the amido-like structures of the N-confused N-methyl pyrrole rings of the macrocycles. Strong aromaticity upon NaBH4 reduction leading to a resonance dipolar structure of the [18]pi-conjugated system as the reduced congener with concomitant Huckel topology are the important highlights. Excellent agreement between experimental spectroscopic measurements and the theoretically determined properties elucidate aromaticity switching upon chemical reduction. Recent years have witnessed an upsurge of demand for the experimental realization of stable antiaromatic systems because of their versatile applications in material science. The conformational rigidity and the enriched stability of these novel 16 pi antiaromatic doubly N-confused porphyrins might entitle these macrocycles toward such applications.