A simple rigid precursor termed as a "diheterole"bearing thiophene linked to α-pyrrole at 4-position was prepared using a three-step synthetic strategy. This functionalized diheterole was allowed to undergo acid-catalyzed condensation in the presence of Lewis acid (BF3. Et2O) to produce the [2+2+2] cyclotrimer 1 as a major product with trace formation of 2and higher homologues.Various 1D and 2D NMR analyses along with theoretical investigations indicate that the molecule 1exhibits nonaromaticity due to its non-conjugated annulenic structure. The optical properties and electronic structures were analyzed using UV-vis absorption spectroscopy and time-dependent density functional theory calculations. Detailed structural analyses revealed that the conformationally rigid triply S-confused hexaphyrin 1adopts nearly planar geometry with three thiophene rings inverted. Upon protonation, the individual rings are tilted largely due to the steric congestion by both β-CH's and pyrrolic NH's inside the core. The calculated NICS(0) values of +1.73 ppm for the protonated species, 1.3H+ indicates the distinct non-aromatic feature as observed in 1 (NICS value of +2.34 ppm).
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