Phthalocyanine-cored conductive polymer design: effect of substitution pattern and chalcogen nature on optical and electrical properties of Zn(II)-phthalocyanine–cored polycarbazoles

Abstract

Phthalocyanines are one of the important candidates of tetrapyrrolic macrocycles having a π-conjugated system, and conductive polymers (CPs) have recently attracted an increasing interest as designing of new molecular materials. A smart combination of these two unique structures can produce materials with the desired properties to design various organic-molecular devices. However, fundamental principles of the design engineering for synthesis of phthalocyanine-cored CP with unique optoelectronic properties has not been investigated yet. For this purpose, tetrasubstituted peripheral or non-peripheral Zn(II)-phthalocyanine containing thioalkyl- or alkoxy-group–linked carbazoles have been synthesized. Electropolymerization of the materials under potentiodynamic conditions yielded a series of analogous donor−acceptor CPs in which the only difference was the nature of the chalcogen (O or S) and substitution pattern (peripheral or non-peripheral) on the phthalocyanine core. This was shown to have a significant impact on the optical and electrochemical properties of the CPs because of the difference in electronegativity of chalcogen and inductive effect of the substitution pattern. Here, a comprehensive investigation of the design of phthalocyanine-cored CP has been concluded to reveal structure–property relationship.