Photocatalytic Conversion of CO₂ to CO using Rhenium Bipyridine Platforms Containing Ancillary Phenyl or BODIPY...

Harnessing of solar energy to drive the reduction of carbon dioxide to fuels requires the development of efficient catalysts that absorb sunlight. In this work, we detail the synthesis, electrochemistry and photophysical properties of a set of homologous fac-Re^I(CO)₃ complexes containing either an ancillary phenyl (8) or BODIPY (12) substituent. These studies demonstrate that both the electronic properties of the rhenium center and BODIPY chromophore are maintained for these complexes. Photolysis studies demonstrate that both assemblies 8 and 12 are competent catalysts for the photochemical reduction of CO₂ to CO in DMF using triethanolamine (TEOA) as a sacrificial reductant. Both compounds 8 and 12 display TOFs for photocatalytic CO production upon irradiation with light (λ_ex ≥ 400 nm) of ~5 hr^-1 with TON values of approximately 20. Although structural and photophysical measurements demonstrate that electronic coupling between the BODIPY and fac-Re^I(CO)₃ units is limited for complex 12, this work clearly shows that the photoactive BODIPY moiety is tolerated during catalysis and does not interfere with the observed photochemistry. When taken together, these results provide a clear roadmap for the development of advanced rhenium bipyridine complexes bearing ancillary BODIPY groups for the efficient photocatalytic reduction of CO₂ using visible light.