TY - JOUR

T1 - When a Side Reaction Is a Benefit: A Catalyst-Free Route to Obtain High-Molecular Cobaltocenium-Functionalized Polysiloxanes by Hydroamination

AU - Кочева, Анастасия Никитична

AU - Дерябин, Константин Валерьевич

AU - Перевязко, Игорь Юрьевич

AU - Бокач, Надежда Арсеньевна

AU - Боярский, Вадим Павлович

AU - Исламова, Регина Маратовна

PY - 2024/10/14

Y1 - 2024/10/14

N2 - 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 2 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 (Co II/Co III transitions at E 1/2 = -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.

AB - 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 2 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 (Co II/Co III transitions at E 1/2 = -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.

KW - cobaltocenium

KW - hydroamination

KW - molecular weight

KW - polysiloxanes

KW - redox properties

UR - https://www.mdpi.com/2073-4360/16/20/2887

UR - https://www.mendeley.com/catalogue/efd89a34-38cc-3b7a-a83b-e8aab4f461b8/

U2 - 10.3390/polym16202887

DO - 10.3390/polym16202887

M3 - Article

C2 - 39458715

VL - 16

JO - Polymers

JF - Polymers

SN - 2073-4360

IS - 20

M1 - 2887

ER -