Synthesis and Properties of Benzo-Fused Indeno[2,1-c]fluorenes

Chem Asian J. 2019 May 15;14(10):1737-1744. doi: 10.1002/asia.201801684. Epub 2019 Jan 7.

Abstract

A set of fully-conjugated indenofluorenes has been synthesized and confirmed by solid-state structure analysis. The indeno[2,1-c]fluorenes and their benzo-fused analogues all contain the antiaromatic as-indacene core. The molecules possess high electron affinities and show a broad absorption that reaches into the near-IR region of the electromagnetic spectrum. All of the featured compounds reversibly accept up to two electrons as revealed by cyclic voltammetry. Analysis of molecule tropicity using NICS-XY scan calculations shows that, while the as-indacene core is less paratropic than s-indacene, benz[a]-annulation further reduces the antiaromaticity of the core. Antiaromatic strength of the as-indacene core can also be tuned by the position of fusion of additional arenes on the outer rings.

Keywords: Friedel-Crafts acylation; NICS calculations; antiaromaticity; diacenoindacenes; indenofluorenes.