Polycobaltoceniumylmethylene – A Water-Soluble Polyelectrolyte Prepared by Ring-Opening Transmetalation Polymerization

Abstract

The synthesis of a water-soluble polycobaltoceniumylmethylene chloride (PCM-Cl) via ring-opening transmetalation polymerization is presented. Starting from a carba[1]magnesocenophane and cobalt(II) chloride, this route gives access to a polymer with methylene-bridged cobaltocenium moieties within the polymers' main-chain. The polymer was characterized by NMR spectroscopy, elemental analysis, TGA, DSC, XRD, and CV measurements, as well as UV−vis spectroscopy. Furthermore, GPC measurements in an aqueous eluent versus pullulan standards were conducted to gain insight into the obtained molar masses and distributions. In addition, the ion-dependent solubility was demonstrated by anion exchange, tuning the hydrophobic/hydrophilic properties of this redox-responsive material.

Molecularly Selective Polymer Interfaces for Electrochemical Separations

“…To mitigate these synthesis challenges, extensive research has been dedicated to multiresponse polymers, aimed at broadening the applicability of redox-responsive polymers along with the enhancement of electrochemical stability, selectivity, and switchability of the molecules. In addition to the redox responsiveness, these polymers incorporate extra features for regulating polymer reactivity such as optical responsivity, pH sensitivity, and hydrophobicity by tailoring the non-redox-active moiety, the hydrophilicity of counterions, and polymer chain lengths (Figure b). − Use of the intrinsic properties of polymers, including thermoelectric properties and thermoresponsiveness, − could serve as additional pathways for fine-tuning selectivity and reversibility.…”

Effect of a single methyl substituent on the electronic structure of cobaltocene studied by computationally assisted MATI spectroscopy

“…Since discovery of the intriguing sandwich structure of (Cp) 2 Fe seven decades ago 1,2 metallocenes have become one of the most prominent classes of organometallics. During last years, cobaltocene and its substituted derivatives have been attracting special interest due to their relevance to modern catalytic systems, 3–5 sensors, 6–8 metallopolymers, 9–12 and molecular magnets, 13 as well as to the materials for hydrogen evolution, 14–16 batteries, 17–22 solar cells 23–25 and spintronics. 13,26,27…”