TY - JOUR

T1 - Multiredox Heterobimetallic Ferrocenyl/Cobaltocenium-Containing Polysiloxanes with Sensing Activity

AU - Кочева, Анастасия Никитична

AU - Дерябин, Константин Валерьевич

AU - Зубарева, Вероника Николаевна

AU - Исламова, Регина Маратовна

PY - 2026/6/12

Y1 - 2026/6/12

N2 - The synthesis of heterobimetallic ferrocenyl/cobaltocenium-containing polymethylhydrosiloxanes with 25 mol % content of ferrocenyl and 25 mol % content of cobaltocenium side groups was optimized and conducted by different approaches of platinum-catalyzed hydrosilylation of polymethylhydrosiloxane with alkenyl/alkynyl-metallocenes: varying solvent systems and the sequence of alkenyl/alkynyl-metallocene addition, as well as mixing of presynthesized metallocene-containing polymethylhydrosiloxanes. The resulting metallocene-containing polysiloxanes were cross-linked via platinum-catalyzed Si–Si dehydrocoupling. The metallocene-containing polysiloxanes were characterized by 1H and 13C{1H} nuclear magnetic resonance, Fourier-transform infrared, ultraviolet–visible, and X-ray photoelectron spectroscopies, as well as by cyclic voltammetry, electrochemical impedance spectroscopy, and thermogravimetry. The heterobimetallic metallocene-containing polysiloxanes exhibit multiredox activity due to the presence of three well-defined and well-resolved redox peaks at E1/2 ≈ −2.3 V (Cc–/Cc), −1.3 V (Cc/Cc+), and 0.1 V (Fc/Fc+), correspondingly. The metallocene-containing polysiloxanes can serve as multisensors for detecting H2O, as evidenced by changes in the position and intensity of the Cc/Cc+ transition in the cyclic voltammogram. They can also detect glucose and dopamine, which is the characteristic of the ferrocenyl group. The presence of ferrocenyl side groups attached to the Si–O–Si backbone allows for the “self-calibration” of E1/2 for other redox peaks in the system vs. the Fc/Fc+ couple since E1/2 of this couple remains virtually unchanged with the addition of H2O. Hence, the determination of trace H2O in organic solvents by potential heterobimetallic sensors can be critical for quality control, safety, process efficiency of catalytic chemistry, and standards compliance for the petrochemical, pharmaceutical, and chemical industries.

AB - The synthesis of heterobimetallic ferrocenyl/cobaltocenium-containing polymethylhydrosiloxanes with 25 mol % content of ferrocenyl and 25 mol % content of cobaltocenium side groups was optimized and conducted by different approaches of platinum-catalyzed hydrosilylation of polymethylhydrosiloxane with alkenyl/alkynyl-metallocenes: varying solvent systems and the sequence of alkenyl/alkynyl-metallocene addition, as well as mixing of presynthesized metallocene-containing polymethylhydrosiloxanes. The resulting metallocene-containing polysiloxanes were cross-linked via platinum-catalyzed Si–Si dehydrocoupling. The metallocene-containing polysiloxanes were characterized by 1H and 13C{1H} nuclear magnetic resonance, Fourier-transform infrared, ultraviolet–visible, and X-ray photoelectron spectroscopies, as well as by cyclic voltammetry, electrochemical impedance spectroscopy, and thermogravimetry. The heterobimetallic metallocene-containing polysiloxanes exhibit multiredox activity due to the presence of three well-defined and well-resolved redox peaks at E1/2 ≈ −2.3 V (Cc–/Cc), −1.3 V (Cc/Cc+), and 0.1 V (Fc/Fc+), correspondingly. The metallocene-containing polysiloxanes can serve as multisensors for detecting H2O, as evidenced by changes in the position and intensity of the Cc/Cc+ transition in the cyclic voltammogram. They can also detect glucose and dopamine, which is the characteristic of the ferrocenyl group. The presence of ferrocenyl side groups attached to the Si–O–Si backbone allows for the “self-calibration” of E1/2 for other redox peaks in the system vs. the Fc/Fc+ couple since E1/2 of this couple remains virtually unchanged with the addition of H2O. Hence, the determination of trace H2O in organic solvents by potential heterobimetallic sensors can be critical for quality control, safety, process efficiency of catalytic chemistry, and standards compliance for the petrochemical, pharmaceutical, and chemical industries.

KW - cobaltocenium-containing polysiloxanes

KW - ferrocenyl-containing polysiloxanes

KW - multiredox properties

KW - sensor activity

KW - synthesis of polymers

UR - https://www.mendeley.com/catalogue/8a0fc40e-692e-374e-9e89-9069f7b867e9/

U2 - 10.1021/acsapm.6c01551

DO - 10.1021/acsapm.6c01551

M3 - Article

VL - 8

SP - 8899

EP - 8912

JO - ACS Applied Polymer Materials

JF - ACS Applied Polymer Materials

SN - 2637-6105

IS - 11

ER -