N-heterocyclic carbene (NHC)-protected gold nanoclusters display high stability and high photoluminescence, making them well-suited for fluorescence imaging and photodynamic therapeutic applications. We report herein the synthesis of two bisNHC-protected Au13 nanoclusters with π-extended aromatic systems. Depending on the position of the π-extended aromatic system, changes to the structure of the ligand shell in the cluster are observed, with the ability to correlate increases in rigidity with increases in fluorescence quantum yield. Density functional theory analysis reveals that both synthesized Au13 nanoclusters are 8-electron superatoms but have distinct differences in the characteristics of the lowest unoccupied single-electron states. Qualitatively, this implies different mechanisms for excitations and their decay over the fundamental energy gap. Stability and photophysical studies were carried out to provide the emission lifetime and optical purity of the two clusters. Active intracellular uptake of the nanoclusters was confirmed in vitro using confocal microscopy in human epithelial carcinoma cells. Reactive oxygen species production was measured at 7% efficiency. The high cluster stability, photoluminescence quantum yields, and efficient cellular uptake in cancer cells suggest potential for these nanoclusters as highly efficient and tunable nanomedical platforms.