Hexathianonaphyrin(1.0.0.1.0.0.1.0.0): Synthesis, optical, redox and protonation induced antiaromaticity

Abstract

A simple non-rigid precursor termed as a “triheterole” comprising of 2,2[Formula: see text]-bithiophene linked to [Formula: see text]-pyrrole was prepared using a four-step synthetic strategy. This functionalized triheterole was allowed to undergo acid catalyzed condensation in the presence of Lewis acid (BF3 [Formula: see text] Et2O) to produce the [3 + 3 + 3] cyclotrimer 1 as a major product with trace formation of its higher homologues. Electronic absorption spectrum of 1exhibited a characteristic band (520 nm) and broad band in the visible region. Upon protonation, significant bathochromic shift of the band (608 nm) and the broad band towards near-IR region (ca.1250 nm) indicates its antiaromatic (4[Formula: see text] conjugated circuit. Detailed structural analyses using temperature-dependent 1D and 2D NMR along with DFT level theoretical investigations indicate that the molecule exhibits weak antiaromaticity due to its large fluxional nature.