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• W2016119440 abstract "Continuous wave and pulsed electron paramagnetic resonance studies were performed on the superoxide ion, O 2 - , encaged in the nanoporous crystal 12CaO.7Al 2 O 3 (C12A7). Hyperfine splitting due to 1 7 O in O 2 - was observed in C12A7 heated in 40% 1 7 O-enriched O 2 gas at 550 °C, providing solid evidence that encaged O 2 derives from gaseous O 2 in the atmosphere via reactions with free oxygen ions in the cage. Angular variations of g values, 1 7 O hyperfine splitting in the single crystal at 20 K, and 2 7 Al electron spin-echo envelope modulation pattern for the powder at 4 K clarified that an O 2 - is encaged in a subnanometer-sized cage of C12A7 and adsorbed on a Ca 2 + ion forming a part of the cage wall. Further, two oxygen atoms in the O 2 - ion are equivalent in the cage, indicating that the O 2 - ion takes a side-on configuration. Then, the O-O bond is perpendicular to the 2-fold rotation axis (C 2 ∥ (100)) across the center of the cage and directed to two oxygen ions forming the cage wall. Variation in the g values with temperature indicates that the O 2 - may be regarded as solidlike below ∼20 K and above this temperature the rocking motion of the O-O bond about the C 2 axis is activated with an increase in temperature, but the anisotropy in the motion remains even at 400 K. This result may be explained by a view that Coulombic interaction of the Ca 2 + with the fully occupied π orbital in the O 2 - is stronger than that with the semioccupied π orbital, controlling the dynamics." @default.
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• W2016119440 date "2004-11-09" @default.
• W2016119440 modified "2023-09-26" @default.
• W2016119440 title "Superoxide Ion Encaged in Nanoporous Crystal 12CaO·7Al2O3 Studied by Continuous Wave and Pulsed Electron Paramagnetic Resonance" @default.
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• W2016119440 doi "https://doi.org/10.1021/jp046963s" @default.
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