Metal Sulfide in a C82 Fullerene Cage: A New Form of Endohedral Clusterfullerenes
Metal Sulfide in a C82 Fullerene Cage: A New Form of Endohedral Clusterfullerenes
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DOI：
10.1021/ja909580j
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发表时间：
2010-04-21
影响因子：
15
通讯作者：
Popov, Alexey A.
中科院分区：
文献类型：
--
作者：
Dunsch, Lothar;Yang, Shangfeng;Popov, Alexey A.
一种新型的含硫富勒烯团簇扩展了内嵌富勒烯的行列：金属硫化物（M2 S）首次稳定在富勒烯笼中。新的含硫富勒烯簇合物M2S@C-82-C-3v（8）已被分离用于多种金属（M = Sc，Y，Dy和Lu）。UV-vis-NIR，电化学和FTIR光谱表征和扩展的DFT计算指出，M2S@C-82笼异构体和电子结构与碳化物簇富勒烯M2C2@C-2n的结构非常相似。通过分子轨道分析、分子中原子量子理论（QTAIM）和电子局域函数（ELF）方法对M2S@C-82中的成键进行了详细的研究。金属硫化物簇合物形式上将四个电子转移到碳笼上，并形成具有高度共价性的金属-硫和金属-碳笼键。分子动力学模拟结果表明，Sc 2S团簇围绕碳笼的C-3轴几乎自由旋转，形成单线的Sc-45 NMR谱。
The row of endohedral fullerenes is extended by a new type of sulfur-containing clusterfullerenes: the metal sulfide (M2S) has been stabilized within a fullerene cage for the first time. The new sulfur-containing clusterfullerenes M2S@C-82-C-3v(8) have been isolated for a variety of metals (M = Sc, Y, Dy, and Lu). The UV-vis-NIR, electrochemical, and FTIR spectroscopic characterization and extended DFT calculations point to a close similarity of the M2S@C-82 cage isomeric and electronic structure to that of the carbide clusterfullerenes M2C2@C-2n. The bonding in M2S@C-82 is studied in detail by molecular orbital analysis as well as with the use of quantum theory of atom-in-molecules (QTAIM) and electron localization function (ELF) approaches. The metal sulfide cluster formally transfers four electrons to the carbon cage, and metal-sulfur and metal-carbon cage bonds with a high degree of covalency are formed. Molecular dynamics simulations show that Sc2S cluster exhibits an almost free rotation around the C-3 axis of the carbon cage, resulting thus in a single line Sc-45 NMR spectrum.