Electronic Structure of Ytterbium(III) Solvates-a Combined Spectroscopic and Theoretical Study.

The wide range of optical and magnetic properties of lanthanide(III) ions is associated with their intricate electronic structures which, in contrast to lighter elements, is characterized by strong relativistic effects and spin-orbit coupling. Nevertheless, computational methods are now capable of describing the ladder of electronic energy levels of the simpler trivalent lanthanide ions, as well as the lowest energy term of most of the series. The electronic energy levels result from electron configurations that are first split by spin-orbit coupling into groups of energy levels denoted by the corresponding Russell-Saunders terms. Each of these groups are then split by the ligand field into the actual electronic energy levels known as microstates or sometimes mJ levels. The ligand-field splitting directly informs on the coordination geometry and is a valuable tool for determining the structure and thus correlating the structure and properties of metal complexes in solution. The issue with lanthanide complexes is that the determination of complex structures from ligand-field splitting remains a very challenging task. In this paper, the optical spectra-absorption, luminescence excitation, and luminescence emission-of ytterbium(III) solvates were recorded in water, methanol, dimethyl sulfoxide (DMSO), and N,N-dimethylformamide (DMF). The electronic energy levels, that is, the microstates, were resolved experimentally. Subsequently, density functional theory calculations were used to model the structures of the solvates, and ab initio relativistic complete active space self-consistent field calculations (CASSCF) were employed to obtain the microstates of the possible structures of each solvate. By comparing the experimental and theoretical data, it was possible to determine both the coordination number and solution structure of each solvate. In water, methanol, and N,N-dimethylformamide, the solvates were found to be eight-coordinated and have a square antiprismatic coordination geometry. In DMSO, the speciation was found to be more complicated. The robust methodology developed for comparing experimental spectra and computational results allows the solution structures of homoleptic lanthanide complexes to be determined.