Manganese K-Edge X-Ray Absorption Spectroscopy as a Probe of the Metal–Ligand Interactions in Coordination Compounds
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Abstract
A series of manganese coordination compounds has been
investigated
by X-ray absorption spectroscopy (XAS). The K-pre-edge spectra are
interpreted with the aid of time-dependent density functional theory
(TD-DFT). This method was calibrated for the prediction of manganese
K-pre-edges with different functionals. Moreover the nature of all
observed features could be identified and classified according to
the corresponding set of acceptor orbitals, either 1s to 3d transitions
or metal-to-ligand charge transfer (MLCT) bands. The observable MLCT
bands are further divided into features that correspond to transitions
into empty π* orbitals of π-donor ligands and those of
π-acceptor ligands. The ability to computationally reproduce
the observed features at the correct relative transition energy is
strongly dependent on the nature of the transition. A detailed analysis
of the electronic structure of a series of Mn coordination compounds
reveals that the different classes of observable transitions provide
added insight into metal–ligand bonding interactions