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Abstract

A helical step‐ladder polyarylene incorporating chiral (R)‐2,2′‐dioctoxy‐1,1′‐binaphthyl units was synthesized for the first time. The first step involved the preparation of a precursor poly(arylene ketone) via a palladium‐mediated Suzuki‐type cross‐coupling reaction with the aid of microwave heating. Two polymer‐analog reaction steps, the reduction of the keto groups to tertiary alcohol functionalities and subsequent intramolecular Friedel–Crafts cyclization, gave a step‐ladder polymer (6) in good yields with reasonable mean average molecular weights greater than 13,000. The regioselective cyclization pattern in the α position of the naphthalene core was confirmed by a comparison of the NMR data of the polymer with those of the corresponding model ladder oligomers, 12 and 13, and also a single‐crystal structure of 13. The optical spectra of the oligomers and polymers indicated that there was little electronic interaction across the binaphthyl units. The circular dichroism spectrum of 6 exhibited a strong bisignate Cotton effect in the π–π* absorption region of the planar chromophores, which reflected the strong exciton coupling within the helical polymer chain.