Autor: |
Terasaka K; Department of Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan., Kamoshida T; Department of Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan., Ichikawa T; Department of Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan., Yokoyama T; Department of Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan., Shibuta M; Keio Institute of Pure and Applied Sciences (KiPAS), Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan., Hatanaka M; Department of Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan., Nakajima A; Department of Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan.; Keio Institute of Pure and Applied Sciences (KiPAS), Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan. |
Abstrakt: |
Transition metal atom (M)-encapsulating silicon cage nanoclusters (M@Si 16 ) 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@Si 16 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@Si 16 , comprising a central atom from group 6 (M VI = Cr, Mo, and W) were deposited on C 60 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@Si 16 , the extent of charge transfer to the C 60 substrate is approximately doubled, while the oxidative reactivity is subdued for M VI @Si 16 on C 60 , especially for W@Si 16 . The results show that a divalent state of M VI @Si 16 2+ appears on the C 60 substrate, which is consistently calculated to be a symmetrical cage structure of W@Si 16 2+ in C 3 v , revealing insights into the "periodic law" of M@Si 16 superatoms pertaining to the characteristics of alkaline earth metals. |