Ahmetali Erem, Kocaarslan Azra, Bräse Stefan, Théato Patrick, Kasım Şener M
Institute of Organic Chemistry (IOC), Karlsruhe Institute of Technology (KIT), Kaiserstraße 12, 76131, Karlsruhe, Germany.
Department of Chemistry, Yıldız Technical University, Istanbul, 34210, Turkey.
Macromol Rapid Commun. 2025 Jan;46(1):e2400601. doi: 10.1002/marc.202400601. Epub 2024 Sep 28.
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.
氮氧化物介导的聚合反应（NMP）和氮氧化物交换反应（NER）是非常有效的方法，只需要合适的烷氧基胺衍生物，并能以可控的方式生成不同的聚合物结构。本文通过NMP和NER展示了含TEMPO取代对称锌酞菁（ZnPc）的星形聚合物的合成。此外，在TEMPO取代的不对称ZnPc的单臂上进行线性聚合物的形成，以阐明星形聚合物的性质。所有线性和星形聚合物都通过傅里叶变换红外光谱（FT-IR）、紫外可见光谱（UV-vis）、荧光光谱、凝胶渗透色谱（GPC）、核磁共振（NMR）和电子顺磁共振（EPR）技术进行表征。结果表明，所提出的反应能够形成可控的星形聚合物。由于臂长不同，臂数增加（从单臂到四臂）会导致不同的分散度值（Đ）（1.2 - 3），特别是在NMP中。然而，通过NER克服了这一困难，成功合成了相对低分子量（30K > 10K）和低分散度（1.2 - 1.9）的星形聚合物。结果清楚地表明，虽然苯乙烯和4-乙烯基苄基氯单体被平等地引入到结构中，但含酞菁的星形聚合物可以以可控的方式合成，并且它们的季铵化衍生物有潜力作为光动力疗法中的光活性剂发挥作用。
