Synthesis and characterization of metal–rich phosphonium polyelectrolytes and their use as precursors to nanomaterials

Abstract

Upon efficient quaternization and salt metathesis of stable triethyl ferrocene/ruthenocene phosphines, styrene-based phosphonium triflate monomers with four different stoichiometric ratios of Fe/Ru were synthesized. Free-radical polymerization of the monomers afforded four polyelectrolytes (M_n: 38 650–69 100 g mol⁻¹, Đ: 3.16–4.10) that retained many of the spectroscopic and electrochemical properties of the ferrocene/ruthenocene units. TGA studies demonstrated the thermal stability (onset of decomposition: ∼310 °C) and high char yields (33–54% at 1000 °C) of the polyelectrolytes. Pyrolysis in N₂/H₂ (95/5) (film thickness of ∼6 μm, 1000 °C, 3 h) yielded crystalline, mixed-phase nanomaterials containing iron, ruthenium, and phosphorus with compositions influenced by the structure of the parent polyelectrolytes.