Structural and Electrochemical Property Correlations of Metallic Nitride Endohedral Metallofullerenes
Structural and Electrochemical Property Correlations of Metallic Nitride Endohedral Metallofullerenes
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DOI：
10.1021/jp104352d
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发表时间：
2010-08-05
影响因子：
3.7
通讯作者：
Echegoyen, Luis
中科院分区：
文献类型：
--
作者：
Chaur, Manuel N.;Aparicio-Angles, Xavier;Echegoyen, Luis
研究了金属氮化物内嵌金属富勒烯（MN EMF）的结构与电化学性能的关系。这些化合物的电化学性质强烈依赖于碳笼的对称性，并且除了Sc 3 N簇外，由于HOMO和LUMO在碳笼上的局部化，这些化合物的电化学性质与金属簇的性质无关。Gd3N@C-86的X射线结构表明笼遵守孤立五边形规则，并使用具有D-3对称性的笼，与先前发表的Tb3N@C-86的数据一致，Tb3N@C-86是唯一的其他结构特征的C-86 MN EMF。不同MN EMF的电化学性质被用来探测这些化合物的结构特征。电化学用于确定M3N@C-80化合物的D-5 h和I-h异构体的相对丰度，而HPLC允许分析较大的MN EMF。计算了不同MN EMF的结合能（BE），得到了BE（簇和富勒烯笼）和相应的MN EMF丰度之间的强相关性。结果占不同的模板阶段和MN电磁场观察到的相对丰度。
Structural and electrochemical property correlations of metallic nitride endohedral metallofullerenes (MN EMFs) were studied in detail. The electrochemical properties of these compounds are strongly dependent on the symmetry of the carbon cage and, except for the Sc3N cluster, are independent of the nature of the metallic cluster due to the localization of the HOMO and LUMO on the carbon cage. The X-ray structure of Gd3N@C-86 shows that the cage obeys the isolated pentagon rule and uses a cage with D-3 symmetry, in agreement with previously published data for Tb3N@C-86, the only other structurally characterized C-86 MN EMF. The electrochemical properties of different MN EMFs are used to probe the structural features of these compounds. Electrochemistry was used to determine the relative abundances of the D-5h and I-h isomers of M3N@C-80 compounds, whereas HPLC allowed the analysis of larger MN EMFs. The binding energies (BEs) were computed for different MN EMFs, and a strong correlation between the BE (of the cluster and fullerene cage) and the corresponding abundance of the given MN EMF was obtained. The results account for the different template stages and for the relative abundances observed for MN EMFs.