Sc2O@C-3v(8)-C-82: A Missing Isomer of Sc2O@C-82
Sc2O@C-3v(8)-C-82: A Missing Isomer of Sc2O@C-82
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Sc2O@C-3v(8)-C-82：Sc2O@C-82 的缺失异构体
DOI：
10.1021/acs.inorgchem.5b02901
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发表时间：
2016
影响因子：
4.6
通讯作者：
Chen Ning
中科院分区：
文献类型：
--
作者：
Tang Qiangqiang;Abella Laura;Hao Yajuan;Li Xiaohong;Wang Yingbo;Rodriguez-Fortea Antonio;Poblet Josep M.;Feng Lai;Chen Ning
通过在燃弧过程中引入CO2作为氧源，发现了Sc2O@C82的一种新异构体Sc2O@C3v（8）-C82，此前仅通过计算研究进行了研究，并通过质谱、紫外可见近红外吸收光谱、循环伏安法、45 ScNMR、密度泛函理论（DFT）计算和单晶X射线衍射进行了表征。晶体学分析明确地阐明了笼对称性归属于C3 v（8），并表明Sc2 O簇在笼内是无序的。晶体学数据的比较研究进一步揭示了Sc 1-O-Sc2角在131.0-148.9°的范围内，远大于Sc2S@C3v（8）-C82，表明笼内的双金属簇合物具有显著的柔性。电化学研究表明，Sc2O@C3v（8）-C82的电化学能隙为1.71 eV，是迄今为止报道的氧化物富勒烯（OCF）中最大的，这与其在OCF合成反应混合物中的丰富丰度密切相关.此外，电化学研究表明，双金属团簇和笼状结构对团簇富勒烯的电子结构有重要影响。计算结果表明，在较低的温度下，团簇可以发生旋转并容易地改变Sc-O-Sc角。
By introducing CO2as the oxygen source during the arcing process, a new isomer of Sc2O@C82, Sc2O@C3v(8)-C82, previously investigated only by computational studies, was discovered and characterized by mass spectrometry, UV–vis–NIR absorption spectroscopy, cyclic voltammetry,45Sc NMR, density functional theory (DFT) calculations, and single-crystal X-ray diffraction. The crystallographic analysis unambiguously elucidated that the cage symmetry was assigned toC3v(8) and suggests that Sc2O cluster is disordered inside the cage. The comparative studies of crystallographic data further reveal that the Sc1–O–Sc2 angle is in the range of 131.0–148.9°, much larger than that of the Sc2S@C3v(8)-C82, demonstrating a significant flexibility of dimetallic clusters inside the cages. The electrochemical studies show that the electrochemical gap of Sc2O@C3v(8)-C82is 1.71 eV, the largest among those of the oxide cluster fullerenes (OCFs) reported so far, well correlated with its rich abundance in the reaction mixture of OCF synthesis. Moreover, the comparative electrochemical studies suggest that both the dimetallic clusters and the cage structures have major influences on the electronic structures of the cluster fullerenes. Computational studies show that the cluster can rotate and change the Sc–O–Sc angle easily at rather low temperature.