Investigation of electronic structure of tri- and tetranuclear molybdenum clusters by X-ray photoelectron and emission spectroscopies and quantum chemical methods

• Published in: Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy Molecular and biomolecular spectroscopy, 2018-02, Vol.190, p.347-352
• Main Authors: Kryuchkova, Natalya A., Syrokvashin, Mikhail M., Gushchin, Artem L., Korotaev, Evgeniy V., Kalinkin, Alexander V., Laricheva, Yuliya A., Sokolov, Maxim N.
• Format: Article
• Language: English
• Subjects: Bipyridine; DFT method; Molybdenum; Quantum chemical calculations; Sulfide cluster; Thiourea; X-ray emission spectroscopy; X-ray photoelectron spectroscopy
• ISSN: 1386-1425
• DOI: 10.1016/j.saa.2017.09.043

Charge state studies of compounds [Mo3S4(tu)8(H2O)]Cl4·4H2O (1), [Mo3S4Cl3(dbbpy)3]Cl·5H2O (2), [Mo3S4(CuCl)Cl3(dbbpy)3][CuCl2] (3), containing {Mo3S4}4+ and {Mo3CuS4}5+ cluster cores bearing terminal thiourea (tu) or 4,4′-di-tert-butyl-2,2′-bipyridine (dbbpy) ligands, have been performed by X-ray photoelectron and X-ray emission spectroscopies combined with quantum chemical calculations. The best agreement between theory and experiments has been obtained using the B3LYP method. According to the experimental and calculated data, the Mo atoms are in the oxidation state 4+ for all compounds. The energies and shapes of the Cu2p lines indicate formal oxidation states of Cu as 1+. The coordination of Сu(I) to the cluster {Mo3S4} in 3 does not lead to significant changes in the charge state of the molybdenum atoms and the {Mo3S4} unit can be considered as a tridentate metallothia crown ether. XPS, XES and DFT investigation of electronic structure of tri- (left) and tetranuclear (right) molybdenum clusters decorated with bipyridine ligands has been performed. [Display omitted] •The charge states of tri- and tetranuclear molybdenum clusters are investigated by the XPS, XES and DFT calculations.