Superexchange-Like Interaction of Encaged Molecular Oxygen in Nitrogen-Doped Water Cages of Clathrate Hydrates
| Autor: | Huen Lee, Yousung Jung, Joonghoe Dho, Minjun Cha, Kyuchul Shin, Jinkwon Kim, Wonhee Lee, Hyungjun Kim |
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| Rok vydání: | 2011 |
| Předmět: |
Hydrate cages
Guest molecules hydroxide Magnetism Clathrate hydrate Hydration Theoretical calculations Dioxygens Novel materials ammonia oxidative coupling Biochemistry nitrogen Spin couplings Antiferromagnetism Colloid and Surface Chemistry Super-exchange coupling Nonmagnetics Hydrates Magnetic ions spin coupling Physics::Chemical Physics Cobalt compounds Dioxygen molecules Chemistry Orbitals unclassified drug Host guest interactions Chemical physics Water cage Condensed Matter::Strongly Correlated Electrons clathrate hydrate water Inorganic chemistry Inclusion compounds Catalysis Ion Condensed Matter::Materials Science Magnetization Manganese oxide Molecule density functional theory Environmental fields Magnetic applications Nitrogen-doped General Chemistry Antiferromagnetics Molecular oxygen Superexchange magnetism Experimental approaches ion Hydrate oxygen |
| Zdroj: | Journal of the American Chemical Society. 133:20399-20404 |
| ISSN: | 1520-5126 0002-7863 |
| DOI: | 10.1021/ja2081394 |
| Popis: | Clathrate hydrates are a highly prospective material in energy and environmental fields, but the inherent nature of inclusion phenomena occurring in the stacked water cages has not been completely resolved yet. Investigating the magnetism of guest molecules is a new experimental approach in clathrate hydrate research to open the possibility of icy magnetic applications as a novel material as well as to understand the unrevealed host-guest interactions in icy inclusion compounds. In this study, we observed an indirect spin coupling between encaged dioxygen molecules via a nonmagnetic water framework through the measurement of guest magnetization. This spin coupling is reminiscent of superexchange coupling between magnetic ions through intervening oxygens in antiferromagnetic oxides, such as MnO and CoO. Theoretical calculations revealed that OH - incorporated in the framework induced the mixing of perpendicular π* orbitals of two distant dioxygens and that ammonia doping into the hydrate cage leads to a longer lifetime of that orientation. © 2011 American Chemical Society. |
| Databáze: | OpenAIRE |
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