Investigating Perimidine Precursors for the Synthesis of New Multiredox Polymers

Abstract We present a new simple approach for electrochemical synthesis of semi-condensed ambipolar perinone polymers with phthaloperine (p1) or phenanthroline (p2) skeleton from available and cheap perimidine precursors. Polymerization of perimidine derivatives varies in efficiency depending on the monomer, but overall is highly efficient, especially when electropolymerization is used. Electrooxidation is well controllable and provides a certain characteristic share of new bonds in the structure of perimidine polymers: semi-ladder bis-perimidine unit, ladder bis-perimidine unit, and protonated bis-perimidine unit. Polymer p2 obtained with higher efficiency was put through broader analysis (UV-Vis, IR, ESR and quantum-chemical calculations). As indicated, donor-acceptor structure and specific intermolecular interactions of p2 assure its electrical conductivity and complex redox activity. Although protonated bonds break π-conjugation in the structure of the macromolecule, there is also a diradical state that favors intermolecular interactions and intermolecular π-conjugation channels within bis-perimidine segments. It has been proven that there is a diradical state which appears as an intermediate state between the oxidized and reduced states of the protonated polymer unit. This work positions perimidine polymers as a versatile ambipolar multiredox p- and n-type conductor, indicating a potential for expanding perinone-based perylene-diperimidine polymers for innovative electronics and (bio)sensors.