The ability of a compound to broadly absorb light across the incident solar spectrum is an important design target in the development of molecular photosensitizers. The ‘HOMO inversion’ model predicts that for [(tpy)2Fe]2+ (tpy = 2,2′:6′,2″-terpyridine) compounds, adjusting the character of the highest occupied molecular orbital (HOMO) from metal-centered to ligand-centered can drastically improve photophysical properties by broadening absorption in the visible and increasing molar extinction coefficients. In an effort to experimentally realize strong, panchromatic absorption, a tridentate N^N–^N diarylamido ligand bearing flanking benzannulated N-heterocyclic donors (tBuL) was used to prepare deeply colored, pseudo-octahedral coordination complexes of a range of first-row transition and main-group metals [(tBuL)2M0/+; M = Fe, Co, Ni, Zn, Ga]. While the Fe(II) congener exhibits the sought-after broad absorption, isostructural and isoelectronic complexes of other first-row transition and main-group metals show vastly different absorption and redox properties. Density functional theory (DFT) calculations point toward the relative energies of the metal d orbitals and ligand orbitals as the source of major changes in electronic structure, confirming aspects and limitations of the predictive 'HOMO inversion' model in experimentally realized systems with implications for the design of abundant transition-metal sensitizers with broad, panchromatic absorptive properties.