AUTHOR=Obermeier Martin , Beckmann Fabian , Schaer Raoul S. , Wenger Oliver S. , Schwalbe Matthias 

TITLE=Sensitized Photocatalytic CO2 Reduction With Earth Abundant 3d Metal Complexes Possessing Dipicolyl-Triazacyclononane Derivatives

JOURNAL=Frontiers in Chemistry

VOLUME=9

YEAR=2021

URL=https://www.frontiersin.org/journals/chemistry/articles/10.3389/fchem.2021.751716

DOI=10.3389/fchem.2021.751716

ISSN=2296-2646

ABSTRACT=<p>Complexes based on nitrogen and sulfur containing ligands involving 3d metal centers are known for the electrocatalytic reduction of CO<sub>2.</sub> However, photocatalytical activation has rarely been investigated. We herein present results on the light-driven CO<sub>2</sub> reduction using either Ir(dFppy)<sub>3</sub> [<bold>Ir</bold>, dFppy = 2-(4,6-difluorophenyl)pyridine] or [Cu(xant)(bcp)]<sup>+</sup>, (<bold>Cu</bold>, xant = xantphos, bcp = bathocuproine) as photosensitizer in combination with TEA (triethylamine) as sacrificial electron donor. The 3d metal catalysts have either dptacn (dipicolyl-triazacyclononane, <bold>L</bold><sup><bold>N3</bold></sup>) or dpdatcn (dipicolyl-diazathiocyclononane, <bold>L</bold><sup><bold>N2S</bold></sup>) as ligand framework and Fe<sup>3+</sup>, Co<sup>3+</sup> or Ni<sup>2+</sup> 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 H<sub>2</sub> or a mixture of both. The ratio between these two products can be controlled by the right choice of reaction conditions. With using <bold>Cu</bold> as photosensitizer, we could introduce an intermolecular system that is based solely on 3d metal compounds being able to reduce CO<sub>2</sub>.</p>