The synthesis and complete photophysical characterization of rigidified neutral hemicage iridium complexes are presented. The hemicage ligands were obtained via a modular synthesis, which will facilitate the expansion of future hemicage syntheses. Slight variations in structure between the two iridium hemicage podates reveal subtle differences in photophysical behavior, which will aid in the design of functional materials. A parallel computational investigation corroborates the experimental findings. The insight gleaned from this study will have an impact for the design of iridium-based luminophores for OLED-type applications.