Search

We here disclose that the incorporation of thiophene rings into a seven‐membered 8π azepine in a fused fashion produces a useful antiaromatic core for near‐infrared (NIR) dyes. In contrast to dibenzazepine derivatives with bent structures, dithieno‐fused derivatives with electron‐accepting groups adopt flat conformations in the ground state. The dithieno‐fused derivatives exhibited broad absorption spectra that cover the visible region as well as sharp emission bands in the NIR region, which are considerably red‐shifted relative to those of the dibenzo‐fused congeners. Theoretical study revealed two contradictory effects of the less‐aromatic thiophene‐fused structure, i.e. the enhancement of the antiaromaticity of the adjacent azepine ring and the relief of the antiaromaticity through the contribution of a quinoidal resonance form. The combination of the dithienoazepine core with cationic electron‐accepting groups produced a NIR fluorescent dye with an emission at 878 nm in solution. [ABSTRACT FROM AUTHOR]

This article, titled "Inside Cover: Dithienoazepine-Based Near-Infrared Dyes: Janus-Faced Effects of a Thiophene-Fused Structure on Antiaromatic Azepines," discusses a design strategy for creating near-infrared (NIR) dyes using antiaromatic azepine. The authors, Masahito Murai, Takahiro Enoki, and Shigehiro Yamaguchi, explain that while benzo-fused azepines have bent conformations that become planar in the excited state, thieno-fused azepines with electron-accepting groups remain flat even in the ground state, resulting in NIR emissions beyond 850 nm. The article includes cover art by Dr. Issey Takahashi at ITbM, Nagoya University. [Extracted from the article]