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Two-Step Transformation of Aliphatic Polyketones into π‑Conjugated Polyimines

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posted on 25.06.2019, 00:00 by Yumehiro Manabe, Mitsuharu Uesaka, Tomoki Yoneda, Yasuhide Inokuma
The chemo- and stereo-selective two-step transformation of aliphatic polyketones composed of 3,3-dimethylpentane-2,4-dione units was achieved to generate π-conjugated polyimines. Upon treatment with hydrazine, discrete oligoketones with 4–8 carbonyl groups afforded ethylene-bridged oligoisopyrazoles in 80–89% yields. These oligoisopyrazoles underwent stereoselective oxidation at the ethylene bridge to give fully π-conjugated oligo­(isopyrazole-3,5-diyl-trans-vinylene)­s in 73–87% yields. Oxidation of the oligoimines drastically changed their absorption and metal-coordination behaviors. Finally, this two-step transformation was applied to polydisperse polymers. Imine formation proceeded almost quantitatively, even for longer polyketones, including docosamer. Subsequent oxidation of the polyimines furnished a virtually insoluble material that showed broad and red-shifted solid-state absorption over the whole visible region resulting from extended π-conjugation.