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

Abstract

A discrete metallo–supramolecular assembly composed of six iron(II) cations and twelve redox–active terpyridine fragments has been developed for highly efficient visible–light–driven reduction of CO2 to CO with a TON of...

Mechanistic Insights of Photocatalytic CO2 Reduction: Experimental versus Computational Studies

“…[84][85][86] Another alternative is the use of organic pigments, such as p-terphenyl, phenazine, 9-cyanoanthracene, purpurine (PS3-PS6, Figure 3) [78,84] However, these PSs are not free of problems, such as the need for ultraviolet light to be excited, [87] since the absorption of visible light is limited to rare exceptions like PS7. [88][89][90] It is interesting to note that the use of phenazine as PS leads to the formation of formic acid as the major product instead of CO [91] which demonstrates the critical and determining role that the PS has in the catalytic reaction.…”

Noble metal-free bis-tridentate benzimidazole zinc(ii) and iron(ii) complexes for selective CO2photoreduction

“…In continuation of interest on metal complexes with tridentate ligands, 37–39 we recently found terpyridine-based iron complexes could be used for light-driven reduction of CO 2 when an organic thermally activated delayed fluorescence (TADF) compound 4CzIPN was used as the light-harvesting photosensitizer. 40–42 In similarity to 2,2′:6′,2′′-tripyridine, 2,6-bis(2-benzimidazole)pyridine has both strong σ-donor (benzimidazole unit) and π-acceptor (pyridine ring) properties, which allows them to form various metal complexes that might be also used for CO 2 photoreduction like terpyridine-based metal complexes. 43,44 Those benzimidazole-based tridentate metal complexes have been studied in numerous research fields such as sensing, 45 spin crossover, 46–48 and anticancer agents.…”

Homogeneous Systems Containing Earth‐Abundant Metal Complexes for Photoactivated CO2 Reduction: Recent Advances

“…The authors speculate that this is sufficient to enhance the nucleophilicity of the iron center and therefore facilitates the adduct formation with CO 2 . The metallo‐supramolecular assembly Fe7 contains six Fe(II) centers [32c] . The photocatalysis using Fe7 gave the best selectivity to CO (99.6 %), among the catalysts Fe5 , Fe6 and Fe7 , and an increased TON CO (14956) (Table 2, entry 17).…”