Strain-Driven Endohedral Redox Couple CeIV/CeIII in Nitride Clusterfullerenes CeM2N@C80 (M = Sc, Y, Lu)
Strain-Driven Endohedral Redox Couple CeIV/CeIII in Nitride Clusterfullerenes CeM2N@C80 (M = Sc, Y, Lu)
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DOI：
10.1021/jz4009773
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发表时间：
2013-07
影响因子：
5.7
通讯作者：
Yang Zhang;S. Schiemenz;A. Popov;L. Dunsch
中科院分区：
文献类型：
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作者：
Yang Zhang;S. Schiemenz;A. Popov;L. Dunsch
电化学和核磁共振研究表明，CeIII在氮化物簇合物CeM2N@C80(M=Sc，Y，Lu)中发生了面内氧化。CeIV/CeIII的氧化还原电势随第二团簇金属的离子半径而有系统地变化。密度泛函理论计算表明，这种金属依赖性是由于形成离子半径较小的CeIV时的应变释放所致。特别是，在[CeM2N@C80]+阳离子中，[CeM2N@C80]+中的锥形CeY2N团簇在氧化后变为平面。
Electrochemical and NMR spectroscopic studies prove the endohedral oxidation of CeIII in nitride clusterfullerenes CeM2N@C80 (M = Sc, Y, Lu). The redox potential of the endohedral CeIV/CeIII couple systematically varies with the ionic radius of the second cluster metal. DFT computations show that this metal dependence is caused by the release of strain when CeIV with a small ionic radius is formed. In particular, after endohedral oxidation the pyramidal CeY2N cluster becomes planar in the [CeM2N@C80]+ cation.