Theoretical analysis of the structure and bonding in electron-rich edge-bridged octahedral tungsten chloride clusters

The electronic structure of octahedral tungsten chlorides has been studied using density-functional theory calculations. All compounds contain isolated electron-rich W6Cl18 edge-bridged octahedral clusters. The electronic structure of these solid-state compounds is related to that of the isolated octahedral units. For all computed W6Cl18n−W6Cl18n− (n = 0, 1, 2) species, the different magnetic states are rather close in energy and the W6 core significantly distorts from the octahedral symmetry. Theoretical results are compared with available structural and magnetic data.

Graphical abstractFigure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Magnetic and non-magnetic states of octahedral electron-rich W6Cl18n−W6Cl18n− (n = 0–2) cluster species are close in energy. ► The W6 metal core significantly distorts from the octahedral symmetry. ► Periodic calculations indicate that the DOS of bulk materials derive from the MO diagram of the isolated W6Cl18 unit.