LAUSR

The development of CO2 conversion catalysts has become paramount in the effort to close the carbon loop. Herein, we report the synthesis, characterization, and photocatalytic CO2 reduction performance for a series of N-annulated perylene diimide (NPDI) tethered Re(bpy) supramolecular dyads [Re(bpy-C2-NPDI-R)], where R = –H, –Br, –CN, –NO2, –OPh, –NH2, or pyrrolidine (–NR2). The optoelectronic properties of these Re(bpy-C2-NPDI-R) dyads were heavily influenced by the nature of the R-group, resulting in significant differences in photocatalytic CO2 reduction performance. Although some R-groups (i.e. –Br and –OPh) did not influence the performance of CO2 photocatalysis (relative to –H; TONco ∼60), the use of an electron-withdrawing –CN was found to completely deactivate the catalyst (TONco < 1) while the use of an electron-donating –NH2 improved CO2 photocatalysis four-fold (TONco = 234). Despite being the strongest EWG, the –NO2 derivative exhibited good photocatalytic CO2 reduction abilities (TONco = 137). Using a combination of CV and UV-vis-nIR SEC, it was elucidated that the –NO2 derivative undergoes an in situ transformation to –NH2 under reducing conditions, thereby generating a more active catalyst that would account for the unexpected activity. A photocatalytic CO2 mechanism was proposed for these Re(bpy-C2-NPDI-R) dyads (based on molecular orbital descriptions), where it is rationalized that the photoexcitation pathway, as well as the electronic driving-force for NPDI2− to Re(bpy) electron-transfer both significantly influence photocatalytic CO2 reduction. These results help provide rational design principles for the future development of related supramolecular dyads.