Interplay of stereo-electronic, vibronic and environmental effects in tuning the chiroptical properties of an Ir(III) cyclometalated N-heterocyclic carbene

Chiroptical spectra are among the most suitable techniques for investigating the ground and excited electronic states of chiral systems, but their interpretation is not straightforward and strongly benefits from quantum chemical simulations, provided that the employed computational model is sufficiently accurate and deals properly with stereo-electronic, vibrational averaging and environmental effects. Since the synergy among all these effects is only rarely accounted for, especially for large and flexible organometallic systems, the main aim of this contribution is to illustrate the latest developments of computational approaches rooted into the density functional theory for describing stereo-electronic effects and complemented by effective techniques to deal with vibrational modulation effects and solvatochromic shifts. In this connection, chiral iridium complexes offer an especially suitable case study in view of their bright phosphorescence, which is particularly significant for building effective light emitting diodes (OLEDs) and biomarkers and can be finely tuned by the nature of the metal ligands. For instance, a recently synthesized family of cycloiridiated complexes, KC and KD, bearing a pentahelicenic N-heterocyclic carbene (KB), has shown an enhanced long-lasting, bright phosphorescence. Deeper insights into the still unclear nature and origin of the enhancement could be gained by the interpretation of the chiroptical spectra, which is quite challenging in view of the presence of two sources of chirality, the chiral center on Ir and the chiral axis related to the helicene ligand, in addition to the relativistic effects related to the presence of the Ir center. At the same time, the large dimensions of KC and KD hamper the use of the most sophisticated (but prohibitively expensive) computational models, so that more approximate approaches must be validated on a suitable model compound. To this end, after optimizing the computational scheme on a model system devoid of the helicene moiety (KA), we have performed a comprehensive investigation of the KC and KD spectra, whose interpretation is further aided by novel graphical tools. The discussion and analysis of the results will not be focused on the theoretical background, but, rather, on practical details (specific functional, basis set, vibronic model, solvent regime) with the aim of providing general guidelines for the use of last-generation computational spectroscopy tools also by non-specialists.