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.

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► 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.