A central challenge in the realization of effective systems for artificial photosynthesis lies in the ability to transition from mechanisms that stabilize charge separation from initial transient excited states to those that enable multi-electron, proton-coupled charge accumulation which is needed to drive water-splitting coupled to fuels catalysis. Further, understanding where photogenerated electronic excited states localize and how long they persist is of fundamental, critical importance for effective solar energy conversion. The asymmetric and stable coordination environment of heteroleptic Cu(I)bis(phenanthroline) complexes (CuHETPHEN) complexes presents a special opportunity to understand how we can utilize earth-abundant first row transition metal complexes as photosensitizers and leverage their excited state dynamics to stabilize charge-separated states. This talk will focus on our group’s recent work using CuHETPHEN complexes as a platform to investigate directional charge transfer, microenvironment effects on excited state dynamics, weak but specific and fluxional intermolecular assembly to achieve long-lived charge separation, and coordinating ligand designs that promote charge accumulation that is stabilized by proton-coupled electron transfer. This work will be used to design pathways for connecting Cu(I)-based photosensitizers to catalysts or electrodes, and integration into systems for light-driven catalysis.