When a Side Reaction Is a Benefit: A Catalyst-Free Route to Obtain High-Molecular Cobaltocenium-Functionalized Polysiloxanes by Hydroamination
Year: 2024
Type: article
Abstract: 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 NH2 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 1H, 13C{1H}, 29Si{1H}, 19F{1H}, 31P{1H} nuclear magnetic resonance, infrared, ultraviolet–visible, and X-ray photoelectron spectroscopies. As determined by cyclic voltammetry, Cc-PDMSs possess redox properties (CoII/CoIII transitions at E1/2 = −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.
Source: Polymers
Institution: St Petersburg University
Language: English
Subfield: Materials Chemistry
Field: Materials Science
Domain: Physical Sciences
Open Access status: gold
Estimated APC paid: $3,069
Awards: G2708844083, G6444257319
OpenAlex ID: W4403380326