Electronic Properties and 13C NMR Structural Study of Y3N@C88

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• 作者：Wujun Fu ; Jianyuan Zhang ; Hunter Champion ; Tim Fuhrer ; Hugo Azuremendi ; Tianming Zuo ; Jianfei Zhang ; Kim Harich ; Harry C. Dorn
• 刊名：Inorganic Chemistry
• 出版年：2011
• 出版时间：May 16, 2011
• 年：2011
• 卷：50
• 期：10
• 页码：4256-4259
• 全文大小：768K
• 年卷期：v.50,no.10(May 16, 2011)
• ISSN：1520-510X

文摘

In this paper, we report the synthesis, purification, ¹³C NMR, and other characterization studies of Y₃N@C₈₈. The ¹³C NMR, UV鈭抳is, and chromatographic data suggest an Y₃N@C₈₈ having an IPR-allowed cage with D₂(35)-C₈₈ symmetry. In earlier density functional theory (DFT) computational and X-ray crystallographic studies, it was reported that lanthanide (A₃N)⁶⁺ clusters are stabilized in D₂(35)-C₈₈ symmetry cages and have reduced HOMO鈭扡UMO gaps relative to other trimetallic nitride endohedral metallofullerene cage systems, for example, A₃N@C₈₀. In this paper, we report that the nonlanthanide (Y₃N)⁶⁺ cluster in the D₂(35)-C₈₈ cage exhibits a HOMO鈭扡UMO gap consistent with other lanthanide A₃N@C₈₈ molecules based on electrochemical measurements and DFT computational studies. These results suggest that the reduced HOMO鈭扡UMO gap of A₃N@C₈₈ systems is a property dominated by the D₂(35)-C₈₈ carbon cage and not f-orbital lanthanide electronic metal cluster (A₃N)⁶⁺ orbital participation.