Promoting photocatalytic CO2 reduction through facile electronic modification of N-annulated perylene diimide rhenium bipyridine dyads

Abstract

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; TON_co ∼60), the use of an electron-withdrawing –CN was found to completely deactivate the catalyst (TON_co < 1) while the use of an electron-donating –NH₂ improved CO₂ photocatalysis four-fold (TON_co = 234). Despite being the strongest EWG, the –NO₂ derivative exhibited good photocatalytic CO₂ reduction abilities (TON_co = 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.