Ionization of Decamethylmanganocene: Insights from the DFT-Assisted Laser Spectroscopy

Metallocenes represent one of the most important classes of organometallics with wide prospects for practical use in various fields of chemistry, materials science, molecular electronics, and biomedicine. Many applications of these metal complexes are based on their ability to form molecular ions. We report the first results concerning the changes in the molecular and electronic structure of decamethylmanganocene, Cp*Mn-2, upon ionization provided by the high-resolution mass-analyzed threshold ionization (MATI) spectroscopy supported by DFT calculations. The precise ionization energy of Cp*Mn-2 is determined as 5.349 +/- 0.001 eV. The DFT modeling of the MATI spectrum shows that the main structural deformations accompanying the detachment of an electron consist in the elongation of the Mn-C bonds and a change in the Me out-of-plane bending angles. Surprisingly, the DFT calculations predict that most of the reduction in electron density (ED) upon ionization is associated with the hydrogen atoms of the substituents, despite the metal character of the ionized orbital. However, the ED difference isosurfaces reveal a complex mechanism of the charge redistribution involving also the carbon atoms of the molecule.

Automated summary

Metallocenes, an important class of organometallics, show promising practical applications in various fields. In this study, we investigated the changes in the molecular and electronic structure of decamethylmanganocene upon ionization. The ionization energy was determined, and it was found that the detachment of an electron led to structural deformations and charge redistribution involving hydrogen atoms of the substituents and carbon atoms of the molecule.