Phosphorescent Properties of Heteroleptic Ir(III) Complexes: Uncovering Their Emissive Species.

In this contribution, we assess the computational machinery to calculate the phosphorescence properties of a large pool of heteroleptic [Ir(C^N)(N^N)] complexes (where N^N is an ancillary ligand and C^N is a cyclometalating ligand) including their phosphorescent rates and their emission spectra. Efficient computational protocols are next proposed. Specifically, different flavors of DFT functionals were benchmarked against DLPNO-CCSD(T) for the phosphorescence energies. The transition density matrix and decomposition analysis of the emitting triplet excited state enable us to categorize the studied complexes into different cases, from predominant triplet ligand-centered (LC) character to predominant charge-transfer (CT) character, either of metal-to-ligand charge transfer (MLCT), ligand-to-ligand charge transfer (LLCT), or a combination of the two. We have also calculated the vibronically resolved phosphorescent spectra and rates. Ir(III) complexes with predominant CT character are characterized by less vibronically resolved bands as compared to those with predominant LC character. Furthermore, some of the complexes are characterized by close-lying triplet excited states so that the calculation of their phosphorescence properties poses additional challenges. In these scenarios, it is necessary to perform geometry optimizations of higher-lying triplet excited states (i.e., T). We demonstrate that in the latter scenarios all of the close-lying triplet species must be considered to recover the shape of the experimental emission spectra. The global analysis of computed emission energies, shape of the computed emission spectra, computed rates, etc. enable us to unambiguously pinpoint for the first time the triplet states involved in the emission process and to provide a general classification of Ir(III) complexes with regard to their phosphorescence properties.