NC unit trapped by fullerenes: a density functional theory study on Sc3NC@C2n (2n=68, 78 and 80)
NC unit trapped by fullerenes: a density functional theory study on Sc3NC@C2n (2n=68, 78 and 80)
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DOI：
10.1039/b923106d
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发表时间：
2010-01-01
影响因子：
3.3
通讯作者：
Chen, Zhongfang
中科院分区：
文献类型：
--
作者：
Jin, Peng;Zhou, Zhen;Chen, Zhongfang
捕获团簇尺寸大于4的面体内金属富勒烯(EMF)是相当稀少的。在最近一次实验观察的启发下，我们通过密度泛函计算，探索了将一个不寻常的Sc3NC单元封装在三个有代表性的富勒烯笼子中的可能性，即C-68，C-78和C-80。研究了相应的电动势Sc3NC@C-2n(2n=68、78和80)的几何构型、电子和电化学性质。这些新颖的电动势都具有非常有利的结合能，这意味着有相当大的可能性可以在实验上实现。最近在质谱学中观察到的m/z=1121峰被表征为Sc3NC@C-80。值得注意的是，Sc3NC@C-78的能量最低的异构体有一个非IPR的C-78外笼，在一个小到C-68的富勒烯中容纳五个原子的可能性也很有趣。此外，在分子研究中用原子的量子理论揭示了簇内和金属-笼状共价相互作用。还计算了红外吸收光谱和C-13核磁共振光谱，以辅助今后的实验表征。
Endohedral metallofullerenes (EMFs) with a trapped cluster size larger than four are rather scarce. Inspired by a recent experimental observation, we explored the possibility of encapsulating an unusual Sc3NC unit in three representative fullerene cages, namely, C-68, C-78 and C-80, by means of density functional computations. The geometries, electronic and electrochemical redox properties of the corresponding EMFs, Sc3NC@C-2n (2n = 68, 78 and 80), were investigated. These novel EMFs all have very favorable binding energies, implying a considerable possibility for experimental realization. The recently observed m/z = 1121 peak in the mass spectroscopy was characterized as Sc3NC@C-80. Notably the lowest-energy isomer of Sc3NC@C-78 has a non-IPR C-78 outer cage, the possibility to accommodate five atoms inside a fullerene as small as C-68 is also intriguing. Moreover, the intracluster and metal-cage covalent interactions were revealed by a quantum theory of atoms in molecules study. Infrared absorption spectra and C-13 nuclear magnetic resonance spectra were also computed to assist future experimental characterization.