Deciphering the excited-state landscape of Cr(iii) tris(diimines) using [Cr(phen)₃]3+

Earth-abundant Cr(iii) polypyridines chromophores feature long-lived doublet ligand-field excited states. The thermally equilibrated ²T₁/²E ligand-field excited state manifold produces broad, structured UV-Vis-NIR absorption bands. Although ubiquitous across pseudo-octahedral Cr(iii) diimine complexes, the dynamics and individual electronic transitions underlying these spectra have remained elusive. Here, we combine time-resolved spectroscopy and multiconfigurational calculations to assign ground- and excited-state absorption spectra of Cr(iii) tris(1,10-phenanthroline), [Cr(phen)₃]³⁺, as a prototypical example for this class of complexes. Excited-state kinetics reveal a rapid biexponential decay of the initially prepared intraligand/ligand-to-metal charge transfer [⁴(¹IL)/⁴LMCT] excited state into the lowest ²T₁/²E state within 10 picoseconds, assigned to intersystem crossing and vibrational relaxation. Calculations identify broad excited-state absorption features associated with metal-centered ligand-field states (²MC) mixed with intraligand (²IL) transitions within the doublet manifold. These results provide detailed spectral assignments and highlight the need to include multiconfigurational ligand-based orbitals when modeling the spectral properties of Cr(iii) coordination complexes.