Kocheva Anastasia N, Deriabin Konstantin V, Perevyazko Igor, Bokach Nadezhda A, Boyarskiy Vadim P, Islamova Regina M
Institute of Chemistry, St. Petersburg State University, 7/9 Universitetskaya Nab., 199034 St. Petersburg, Russia.
Department of Molecular Biophysics and Polymer Physics, St. Petersburg State University, 7/9 Universitetskaya Nab., 199034 St. Petersburg, Russia.
Polymers (Basel). 2024 Oct 14;16(20):2887. doi: 10.3390/polym16202887.
Cobaltocenium-containing (co)polysiloxanes (Cc-PDMSs) with terminal and side groups were synthesized by the reaction of catalyst-free hydroamination between ethynylcobaltocenium hexafluorophosphate and polysiloxanes comprising amino moieties as terminal and side groups. The conversion of NH groups in the polymers reaches 85%. The obtained (co)polysiloxanes "gelate" due to an increase in their molecular weight by approx. 30 times, when stored at room temperature over one week. "Gelated" Cc-PDMSs remain soluble in most polar solvents. The structure of Cc-PDMSs and the mechanism of "gelation" were established by H, C{H}, Si{H}, F{H}, P{H} nuclear magnetic resonance, infrared, ultraviolet-visible, and X-ray photoelectron spectroscopies. As determined by cyclic voltammetry, Cc-PDMSs possess redox properties (Co/Co transitions at = -1.8 and -1.3 V before and after "gelation", respectively). This synthetic approach allows to increase the molecular weights of the synthesized polysiloxanes functionalized with cobaltocenium groups easily, leading to their higher film-forming ability, which is desirable for some electronic applications. Cc-PDMSs can be utilized as redox-active polymer films in modified electrodes, electrochromic devices, redox-active coatings, and components for batteries.
通过六氟磷酸乙炔基钴茂与包含氨基作为端基和侧基的聚硅氧烷之间的无催化剂氢胺化反应，合成了具有端基和侧基的含钴茂（共）聚硅氧烷（Cc-PDMSs）。聚合物中NH基团的转化率达到85%。当在室温下储存一周以上时，所得到的（共）聚硅氧烷由于分子量增加约30倍而“凝胶化”。“凝胶化”的Cc-PDMSs在大多数极性溶剂中仍可溶解。通过氢、碳{氢}、硅{氢}、氟{氢}、磷{氢}核磁共振、红外、紫外可见和X射线光电子能谱确定了Cc-PDMSs的结构和“凝胶化”机理。通过循环伏安法测定，Cc-PDMSs具有氧化还原性质（“凝胶化”前后Co/Co转变分别在 = -1.8和-1.3 V）。这种合成方法能够轻松提高用钴茂基团官能化的合成聚硅氧烷的分子量，使其具有更高的成膜能力，这对于某些电子应用是有利的。Cc-PDMSs可用作修饰电极、电致变色器件、氧化还原活性涂层和电池组件中的氧化还原活性聚合物薄膜。
