Internally 2,5‐Thienylene‐Bridged [46]Decaphyrin: (Annuleno)annulene Network Consisting of Möbius Aromatic Thia[28]hexaphyrins and Strong Hückel Aromaticity of its Protonated Form

Abstract

Internally 1,3-phenylene-and 2,5-thienylenebridged [46]decaphyrins 2 and 3 have been synthesized. While 2 shows modest aromatic character derived from the global 46p-conjugated circuit, 3 displays larger aromatic character owingt ot he contribution of an (annuleno)annulene-type network consisting of two twisted Mçbius aromatic thia [28]hexaphyrin segments in addition to the global 46pnetwork. Upon protonation, these [46]decaphyrins underwent large structural changes to acquire strong aromaticity.Protonated 3 has been revealed to take on ap lanar structure composed of fused two triangular thia[28]hexaphyrin segments.Scheme 1. The structures of decaphyrins and their precursors.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: http://dx.

Synthesis of (bis)Silicon Complexes of [38], [37], and [36]Octaphyrins: Aromaticity Switch and Stable Radical Cation

“…[21] Thed ecay profile of 3 shows double exponential decay (0.2 ps and 12.5 ps). [21] Thed ecay profile of 3 shows double exponential decay (0.2 ps and 12.5 ps).…”

“…Communications 5878 www.angewandte.org aromatic nature of 2. [21] Thed ecay profile of 3 shows double exponential decay (0.2 ps and 12.5 ps). Theu ltrafast time component (0.2 ps) can be assigned as relaxation to the near-IR dark state which was suggested in the TD-DFT calculations with an optically forbidden vertical transition at 1637 nm (see Figure S24) and followed by relaxation to the ground state (12.5 ps).…”