Stabilizing cations in the backbones of conjugated polymers

摘要: We synthesized a cross-conjugated polymer containing ketones in the backbone and converted it to linearly conjugated, cationic polyarylmethine via process we call “spinless doping” create new class of materials, conjugated polyions. This involves activating with Lewis acid converting them trivalent cations nucleophilic addition electron-rich aryl moieties. Spinless doping lowers optical band gap from 3.26 1.55 eV while leaving intrinsic semiconductor properties intact. Electrochemical reduction (traditional doping) further decreases predicted 1.18 introduces radicals form positive polarons; here, n-doping produces p-doped its metallic state. Treatment nucleophile (NaOMe) converts neutral, non-conjugated state, allowing be tuned chemically, post-polymerization. The synthesis these materials is carried out entirely without use Sn or Pd relies on scalable Friedel–Crafts chemistry.