Electropolymerization and characterization of a new ambipolar perimidine polymer with a perylene core

Abstract

We successfully synthesized a stable electroactive perinone polymer by electropolymerization from the mixture of syn- and anti- isomers (ratio 1:1) of 3,4:9,10-bis(1,8-naphthapyrimidine)-1,6,7,12-tetrakis(1,1,3,3-tetramethylobutylphenoxy)perylene (NPP). The polymer p(NPP) exhibited distinct redox process, with reduction at -1.20 V and oxidation at 0.60 V (vs. ferrocene/ferrocenium couple). Spectroscopic and computational analyses confirmed structural similarity of the polymer to its monomeric form, revealing a perimidine unit involved in electrocoupling. Our thorough investigations elucidated the redox reactions electrochemical mechanism within the polymer film, identifying predominantly deprotonated bis-perimidine segments contributing to oxidation peaks at 0.60 V and 0.68 V. Additionally, the perylenediamide core exhibits the reversible, multi-stage reduction process. Impedance analysis highlighted efficient n-doping-induced conductivity, suggesting application in organic optoelectronic devices. This work positions p(NPP) as a versatile ambipolar multiredox p- and n-type conductor, indicating a potential for expanding perinone-based perylene-diperimidine polymers for innovative electronics.