Alkaline Earth Metal Superatom of W@Si16: Characterization of Group 6 Metal Encapsulating Si16 Cage on Organic Substrates

Transition metal atom (M)-encapsulating silicon cage nanoclusters (M@Si16) exhibit a superatomic nature, depending on the central M atom owing to the number of valence electrons and charge state on organic substrates. Since M@Si16 superatom featuring group 4 and 5 transition metal atoms exhibit rare-gas-like and alkali-like characteristics, respectively, group 6 transition metal atoms are expected to show alkaline earth-like behavior. In this study, M@Si16, comprising a central atom from group 6 (MVI = Cr, Mo, and W) were deposited on C60 substrates, and their electronic and chemical stabilities were investigated in terms of their charge state and chemical reactivity against oxygen exposures. In comparison to alkali-like Ta@Si16, the extent of charge transfer to the C60 substrate is approximately doubled, while the oxidative reactivity is subdued for MVI@Si16 on C60, especially for W@Si16. The results show that a divalent state of MVI@Si16 2+ appears on the C60 substrate, which is consistently calculated to be a symmetrical cage structure of W@Si16 2+ in C 3v , revealing insights into the “periodic law” of M@Si16 superatoms pertaining to the characteristics of alkaline earth metals.