Coordination-driven assembly of a ferrocene-functionalized lead iodide framework with enhanced stability and charge transfer for photocatalytic CO2-to-CH3OH conversion†

Abstract

Hybrid lead halides are promising photocatalysts due to their high structural tunability and excellent photophysical properties, but their ionic structures suffer from instability in polar environments and suppressed charge transfer between lead halide units and organic components. Herein, we successfully incorporated a ferrocene-based light-harvesting antenna into a lead iodide framework by coordination-driven assembly. The π-conjugated Pb²⁺-carboxylate linkage affords synergistic interactions between [Pb₂I₂]²⁺ chains and ferrocene linkers, achieving broad visible absorption up to 612.7 nm and efficient ligand-to-metal charge transfer for spatial charge separation. This ultrastable framework combines strong visible-light absorption of ferrocene centers with excellent charge transport of lead halide units, achieving 6e⁻ CO₂ photoreduction to CH₃OH coupled with ethanol oxidation. Mechanistic studies reveal that ferrocene photoexcitation followed by linker-to-metal charge transfer significantly enhances carrier accumulation, accelerating CH₃O* intermediate formation as indicated by in situ spectroscopy and theoretical calculations.