Sensitized Photocatalytic CO₂ Reduction With Earth Abundant 3d Metal Complexes Possessing Dipicolyl-Triazacyclononane...

Complexes based on nitrogen and sulfur containing ligands involving 3d metal centers are known for the electrocatalytic reduction of CO_2. However, photocatalytical activation has rarely been investigated. We herein present results on the light-driven CO₂ reduction using either Ir(dFppy)₃ [Ir, dFppy = 2-(4,6-difluorophenyl)pyridine] or [Cu(xant)(bcp)]⁺, (Cu, xant = xantphos, bcp = bathocuproine) as photosensitizer in combination with TEA (triethylamine) as sacrificial electron donor. The 3d metal catalysts have either dptacn (dipicolyl-triazacyclononane, L ) or dpdatcn (dipicolyl-diazathiocyclononane, L ) as ligand framework and Fe³⁺, Co³⁺ or Ni²⁺ as central metal ion. It turned out that the choice of ligand, metal center and solvent composition influences the selectivity for product formation, which means that the gaseous reduction products can be solely CO or H₂ or a mixture of both. The ratio between these two products can be controlled by the right choice of reaction conditions. With using Cu as photosensitizer, we could introduce an intermolecular system that is based solely on 3d metal compounds being able to reduce CO₂.