Improving Photocatalysis for the Reduction of CO₂ through Non-covalent Supramolecular Assembly

We report the enhancement of photocatalytic performance by introduction of hydrogen-bonding interactions to a Re bipyridine catalyst and Ru photosensitizer system (ReDAC/RuDAC) by the addition of amide substituents, with carbon monoxide (CO) and carbonate/bicarbonate as products. This system demonstrates a more-than-3-fold increase in turnover number (TON_CO = 100 ± 4) and quantum yield (Φ_CO = 23.3 ± 0.8%) for CO formation compared to the control system using unsubstituted Ru photosensitizer (RuBPY) and ReDAC (TON_CO = 28 ± 4 and Φ_CO = 7 ± 1%) in acetonitrile (MeCN) with 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole (BIH) as sacrificial reductant. In dimethylformamide (DMF), a solvent that disrupts hydrogen bonds, the ReDAC/RuDAC system showed a decrease in catalytic performance while the control system exhibited an increase, indicating the role of hydrogen bonding in enhancing the photocatalysis for CO₂ reduction through supramolecular assembly. The similar properties of RuDAC and RuBPY demonstrated in lifetime measurements, spectroscopic analysis, and electrochemical and spectroelectrochemical studies revealed that the enhancement in photocatalysis is due not to differences in intrinsic properties of the catalyst or photosensitizer, but to hydrogen-bonding interactions between them.