Superexchange-Like Interaction of Encaged Molecular Oxygen in Nitrogen-Doped Water Cages of Clathrate Hydrates

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• 作者：Kyuchul Shin ; Minjun Cha ; Wonhee Lee ; Hyungjun Kim ; Yousung Jung ; Joonghoe Dho ; Jinkwon Kim ; Huen Lee
• 刊名：Journal of the American Chemical Society
• 出版年：2011
• 出版时间：December 21, 2011
• 年：2011
• 卷：133
• 期：50
• 页码：20399-20404
• 全文大小：881K
• 年卷期：v.133,no.50(December 21, 2011)
• ISSN：1520-5126

文摘

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鈥揼uest 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^{鈥?/sup> incorporated in the framework induced the mixing of perpendicular 蟺* orbitals of two distant dioxygens and that ammonia doping into the hydrate cage leads to a longer lifetime of that orientation.}