Self-cross-linkable ferrocenyl-containing polysiloxanes as flexible electrochromic materials

Deriabin, Konstantin V.; Vereshchagin, Anatoliy A.; Kirichenko, Sergey O.; Rashevskii, Artem A.; Levin, Oleg V.; Islamova, Regina M.

doi:10.1016/j.mtchem.2023.101399

Cited by 4 publications

(12 citation statements)

References 43 publications

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“…Polymer density. The polymer density was determined via the pycnometric method using distilled H 2 O [57]. The density of a silicone rubber (ρ p ) was calculated by Equation (2):…”

Section: Swelling Propertiesmentioning

confidence: 99%

“…Cross-linking degree. Swelling measurements were conducted to estimate the crosslinking degree of silicone rubbers [57]. Toluene (125 mL) was added to a flask attached to a Soxhlet extractor and reflux condenser, and the cylindrical polymer samples with a diameter of 10 mm and a thickness of 1-2 mm (at least 4 samples for each series of silicone rubbers) were put into the thimble inside the extractor.…”

Section: Swelling Propertiesmentioning

confidence: 99%

“…make a polymer composite toxic and decrease its tensile properties [36]. Therefore, to impart antistatic and redox-active properties, the most effective approach is to functionalize the polysiloxane backbone with redox-active substituents [9,[54][55][56][57]. The ferrocenyl group is chemically sustainable in the air at room temperature (RT, 25 • C), with an easy and stable one-electron redox transition, making it one of the most suitable side substituents to obtain antistatic protective coatings [58,59].…”

Section: Introductionmentioning

confidence: 99%

“…Previously, we had already obtained ferrocenyl-containing silicone materials that did not have self-healing ability [9]. Thus, antistatic coatings [54], redox-active layers for flexible optoelectronic devices [55], prototypes of neuronal implants [56], and stretchable electrochromic materials [57] were prepared on their basis. The discovery of siloxane equilibrium [60][61][62][63][64][65] is the key to synthesizing self-healing silicone rubbers (by ring-opening anionic polymerization, ROAP), which provides new opportunities for the creation of multifunctional materials exhibiting a triple function: (i) flexibility and stretchability, (ii) antistatic properties and redox activity, and (iii) a self-healing ability.…”

Section: Introductionmentioning

confidence: 99%

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Self-Healing Redox-Active Coatings Based on Ferrocenyl-Containing Polysiloxanes

et al. 2023

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The known ferrocenyl-containing silicone materials have redox activity and electrical conductivity at the level of antistatic materials, but they are incapable of self-healing due to their irreversible cross-linking, which significantly reduces their application area. The development of novel self-healing ferrocenyl-containing silicone rubbers (FSRs) is a promising area of research that extends the possibilities of their application as protective coatings. In this work, a new method was developed to synthesize FSRs with different ferrocenyl unit content (25 and 50 mol.%) by anionic copolymerization of cyclic octamethylcyclotetrasiloxane (D4), cyclic tetraferrocenyl-substituted 1,3,5,7-tetramethyltetrasiloxane (Fc4D4), and bicyclic cross-linking agent (bis-D4). The optimal concentrations of the cross-linking agent and ferrocenyl-substituted unit content for FSRs are 5 wt.% and 25 mol.%, respectively. The FSRs exhibit tensile strength and elongation at break up to 0.1 MPa and 215%. The FSRs possess both self-healing at room and/or elevated temperatures (100 °C) and redox activity (Fc/Fc+ transformations at E0 = 0.43 V) and conductivity at the antistatic level (ca. 10−10–10−11 S·cm−1). The thermal properties of the FSRs were studied. The proposed approach is relevant for the creation of new functional silicone materials as flexible, self-healing, and antistatic protective coatings.

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“…Polymer density. The polymer density was determined via the pycnometric method using distilled H 2 O [57]. The density of a silicone rubber (ρ p ) was calculated by Equation (2):…”

Section: Swelling Propertiesmentioning

confidence: 99%

Section: Swelling Propertiesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Self-Healing Redox-Active Coatings Based on Ferrocenyl-Containing Polysiloxanes

et al. 2023

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“…Ferrocene, since its discovery in 1951 , and revealing the sandwich structure and aromaticity in 1952, , received much attention due to its properties gaining wide application in the field of catalysis, energy storage, sensing, coating’s production, , and medicine. − In 1963, 11 years after describing the aromaticity of ferrocene, modification of ferrocene via ligand exchange reaction (LER) was reported …”

Section: Introductionmentioning

confidence: 99%

Ligand Exchange Reaction between Ferrocene and Multiwalled Carbon Nanotubes: A Contemporary Approach

Golovenko,

Pankin,

Deriabin

et al. 2024

Langmuir

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Ligand exchange reaction (LER) between carbon nanoparticles and ferrocene (Cp 2 Fe) was conducted several times, but there was no convincing evidence of half-sandwich CpFe + coordination to multiwalled carbon nanotubes (MWCNT). In this study, MWCNT is modified by LER with ferrocene using AlCl 3 /Al as a catalytic system. The modified MWCNT (Fc-MWCNT) are investigated for better understanding of the processes taking place on the surface of MWCNT using different spectroscopic and electrochemical methods. The formation of the Fe−C covalent bond between CpFe + and MWCNT is confirmed by changes in the Raman spectrum of Fc-MWCNT compared to pristine MWCNT. The densest structure of Fc-MWCNT is investigated by transmission electronic microscopy. According to density-functional theory calculations of the model interaction between Fe and coronene, the Fe−C bond length is 2.1687−2.1855 Å. X-ray photoelectron spectroscopy also confirms the coordination of the Fe atom to MWCNT by analysis of oxidation states of Fe 2p and deconvolution of C 1s. Utilization of cyclic voltammetry corroborated MWCNT modification via LER. These data are important for both theoretical and practical applications due to increased interest in LER-modified compounds in different areas including thermoelectric devices, sensors, and its potential application in the field of molecular machine construction.

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Cobaltocenium-Containing Polysiloxanes: Catalytic Synthesis, Structure, and Properties

Kocheva,

Deriabin,

Volkov

et al. 2024

ACS Appl. Polym. Mater.

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Two different catalytic approaches to synthesize non-cross-linked and cross-linked cobaltocenium-containing polysiloxanes (Cc-polysiloxanes) were proposed and represent coppercatalyzed azide−alkyne cycloaddition (CuAAC) and platinumcatalyzed hydrosilylation reactions. CuAAC of ethynylcobaltocenium hexafluorophosphate with azide-substituted oligo/polysiloxanes leads to obtain Cc-oligo/polysiloxanes with the highest Ccsubstituted unit content up to 91 mol % compared to the hydrosilylation reaction with polymethylhydrosiloxane (53 mol %). The structure of the obtained Cc-oligo/polysiloxanes was confirmed by 1 H, 13 C{ 1 H}, 29 Si{ 1 H} NMR, and UV−vis spectroscopies. The non-cross-linked Cc-oligo/polysiloxanes are predominantly soluble in polar solvents (acetone, CH 3 OH, CH 3 CN, and H 2 O) due to hydrophilic cobaltocenium cationic moieties attached to the polysiloxane chain, making them different from typical polydimethylsiloxane and ferrocenyl-containing polysiloxanes. All the obtained Cc-oligo/polysiloxanes exhibit redox properties. Cyclic voltammograms of the Cc-oligo/polysiloxanes contain two pairs of redox peaks corresponding to Co II /Co III (E 1/2 ≈ −1.4 V) and Co I /Co II (E 1/2 ≈ −2.3 V). The cross-linked Cc-polysiloxanes are thermally stable to approx. 230 °C both in the air and argon.

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Self-cross-linkable ferrocenyl-containing polysiloxanes as flexible electrochromic materials

Cited by 4 publications

References 43 publications

Self-Healing Redox-Active Coatings Based on Ferrocenyl-Containing Polysiloxanes

Self-Healing Redox-Active Coatings Based on Ferrocenyl-Containing Polysiloxanes

Ligand Exchange Reaction between Ferrocene and Multiwalled Carbon Nanotubes: A Contemporary Approach

Cobaltocenium-Containing Polysiloxanes: Catalytic Synthesis, Structure, and Properties

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