Functionalized Hydrocarbon Belts: Synthesis,Structure and Properties

Hydrocarbon belts have drawn great attention because of their unique structures and tantalizing properties. Although a few belts and heteroatom-doped analogs have been synthesized, belt molecules containing non-hexagonal rings remain rare. Herein we report the construction and application of unprecedented zigzag-type hydrocarbon belts which contain functionalized eight-membered rings. The synthesis features fourfold intramolecular acylation reactions of resorcin4]arene-derived intermediates, which affords C₄-symmetric tetrabenzobelt4]arene4]cyclooctatrienones. Stereoselective ketone reduction with LiAlH₄ and nucleophilic addition with alkynyllithiums provide the corresponding tetrahydroxylated belts. The tetraol and its methyl ether are powerful and selective hosts to form 2 : 1 and 1 : 1 complexes with cesium ion, respectively, with binding constants up to (1.71±0.33)×10¹¹ M⁻² and (1.50±0.16)×10⁶ M⁻¹. In addition, enantiopure C₄-symmetric belts can emit CPL with |g_lum| being around 0.01.