Computational Assessment of MLCT versus MC Stabilities in First-to-Third-Row d6 Pseudo-Octahedral Transition Metal Complexes.

摘要: An accurate modeling of metal-to-ligand-charge-transfer (MLCT) and metal-centered (MC) excited state energies is key to predict the photoinduced response in transition metal complexes (TMCs). Herein, importance ground reference geometries addressed for three-prototype d6 pseudo-octahedral TMCs, each displaying a different potential energy landscape MLCT versus MC relative stabilities. Several functionals are used within time-dependent density functional theory (TDDFT), as well multireference wave-function (MS-CASPT2), applied [Mn(im)(CO)3 (phen)]+ , [Ru(im)2 (bpy)2 ]2+ [Re(im)(CO)3 (im: imidazole, bpy: bypiridine, phen: phenantroline). The results revel that TDDFT robust except when using B3LYP first-row TMCs. In contrast, MS-CASPT2 calculations strongly biased those cases with competitive MLCT/MC states. reinforce reliability describe states but question validity assessing (DFT)/TDDFT performance via direct comparison performed at same DFT geometry standard strategy. © 2019 Wiley Periodicals, Inc.