10.1021/acs.joc.9b01119.s003 Yumehiro Manabe Yumehiro Manabe Mitsuharu Uesaka Mitsuharu Uesaka Tomoki Yoneda Tomoki Yoneda Yasuhide Inokuma Yasuhide Inokuma Two-Step Transformation of Aliphatic Polyketones into π‑Conjugated Polyimines American Chemical Society 2019 Two-Step Transformation ethylene-bridged oligoisopyrazoles aliphatic polyketones absorption Subsequent oxidation polyimine stereoselective oxidation Imine formation π- conjugation Aliphatic Polyketones polydisperse polymers transformation ethylene bridge metal-coordination behaviors yield 2019-06-25 00:00:00 Dataset https://acs.figshare.com/articles/dataset/Two-Step_Transformation_of_Aliphatic_Polyketones_into_Conjugated_Polyimines/8427842 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.