LAUSR

Two novel cyclometalated ruthenium complexes, RC‐4 and RC‐5, featuring 1‐phenylisoquinoline and phenyl quinazoline as ancillary ligands, respectively, were synthesized to investigate their viability with the environmentally friendly copper (Cu) redox mediator, [Cu(bpye)2]2+/+. The modification of the ligand environment resulted in variations in the energetics, photophysical properties, and photovoltaic performance of RC‐4 and RC‐5 sensitizers. Despite RC‐5 sensitizer possessing a more positive ground state potential of 1.19 V versus the NHE, the RC‐4 sensitizer, with a lower HOMO level of 0.72 V versus NHE, exhibited superior photovoltaic performance along with the Cu electrolyte, attributed to its enhanced light harvesting ability, improved lifetime and reduced back electron transfer, contributing to higher Jsc, Voc, and PCE.