Coordination-driven discrete metallo-supramolecular assembly for rapid and selective photochemical CO2 reduction in aqueous solution

A discrete metallo-supramolecular assembly composed of six iron(ii) cations and twelve redox-active terpyridine fragments has been developed for the highly efficient visible-light-driven reduction of CO2 to CO with a TON of 14 956 and 99.6% selectivity in the presence of an organic thermally activated delayed fluorescence (TADF) photosensitizer 4CzIPN in aqueous solution. The photochemical system proceeds rapidly with a turnover frequency (TOF) of 276 min(-1). It is demonstrated that the redox-active terpyridine fragments in the assembly are reduced by the photosensitizer which could further act as an electron reservoir for CO2 reduction, resulting in the highly efficient reduction of CO2. This work shows that discrete metallo-supramolecular assemblies could be used for robust photochemical CO2 reduction.