LAUSR

Abstract Nitroxide‐mediated polymerization (NMP) and nitroxide exchange reaction (NER) are very efficient methodologies that require only suitable alkoxyamine derivatives and create different polymeric architectures in a controlled manner. Herein, the synthesis of star polymers containing TEMPO‐substituted symmetric zinc phthalocyanine (ZnPc) is presented via NMP and NER. Moreover, linear polymer formation is conducted in a single arm on TEMPO‐substituted asymmetric ZnPc to elucidate the properties of star polymers. All linear and star polymers are characterized by FT‐IR, UV–vis, fluorescence, GPC, NMR, and EPR techniques. The results show that the proposed reactions are capable of forming controlled star‐shaped polymers. The increasing arm number (from a single to four arms) results in variable dispersity values (Đ) (1.2–3) due to different arm lengths, especially in NMP. However, this difficulty has been overcome via NER, and star polymers have been successfully synthesized with relatively low molecular weight (30 K > 10 K) and low dispersity (1.2–1.9). The results clearly indicate that while styrene and 4‐vinyl benzyl chloride monomers are introduced to the structure equally, star polymers with phthalocyanine can be synthesized in a controlled manner, and their quarternized derivatives have the potential to be effective as photoactive agents in photodynamic therapy.