Theoretical and Computational Chemistry

The Effect of N-Heterocyclic Carbene Units on the Absorption Spectra of Fe(II) Complexes: A Challenge for Theory



The absorption spectra of five Fe(II) homoleptic and heteroleptic complexes containing strong sigma-donating N-heterocyclic carbene (NHC) and polypyridyl ligands have been theoretically characterized using a tuned range-separation functional.
From a benchmark comparison of the obtained results against other functionals and a multiconfigurational reference, it is concluded that none of the methods is completely satisfactory to describe the absorption spectra.
Using a compromised choice of 20\% exact exchange, the electronic excited states underlying the absorption spectra are analyzed.
The low-lying energy band of all the compounds shows predominant metal-to-ligand charge transfer (MLCT) character while the triplet excited states have metal-centered (MC) nature, which becomes more pronounced with increasing the number of NHC-donor groups. Excited MC states with partial charge transfer to the NHC-donor groups are higher in energy than comparable states without these contributions. The presence of the low-lying MC states prevents the formation of long-lived MLCT states.


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