Synthesis and covalent immobilization of redox-active metallopolymers for organic phase electrochemistry

Redox-active metallopolymers are promising stimuli-responsive platforms for a range of applications including sensing, energy storage, and selective separations. In particular, heterogeneously-functionalized can modulate the capture release target molecules, driven by redox electron-transfer. However, prior metallopolymer-functionalized electrodes have been fabricated non-covalent methods, tailored aqueous phase applications. As such, despite existing potential heterogeneous in organic phase, there significant constraints to stability solvents, high solubility solvents such as chloroform or tetrahydrofuran. We propose immobilization thiol-functionalized redox-active on metallic surfaces facile way enhance cyclability media, thus broaden applicability redox-metallopolymers explore anionic polymerization metal-containing monomers vinylferrocene (VFc) ferrocenyldimethylsilane (FS), their thiol end-functionalization living strategies. PFS PVFc with molar masses ranging from 1800 49900 g mol−1 2900 6300 respectively were prepared segment poly(ethylene sulfide), characterized size-exclusion chromatography, NMR spectroscopy, MALDI/ToF, thermogravimetry, elemental analysis. Both immobilized gold substrates grafting-to protocol, demonstrated redox-responsiveness electrochemical control. case PVFc, operando testing stable reversible cycling capabilities (>74% maximum current retained after 100 oxidation/reduction cycles) several chloroform, tetrahydrofuran, ethanol, methanol, acetonitrile, acetone. Immobilized was 83% cycles. envision future these covalently broad fields separations sensing storage.