Liu Zeyu, Lu Tian
School of Environmental and Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang, 212100, People's Republic of China.
Beijing Kein Research Center for Natural Sciences, Beijing, 100022, People's Republic of China.
Chemistry. 2024 Oct 1;30(55):e202402227. doi: 10.1002/chem.202402227. Epub 2024 Sep 13.
This work conducts a comprehensive theoretical study on the non-covalent complexation between cyclocarbons and C fullerene for the first time. The binding energy between cyclocarbons and C fullerene is significantly stronger than that between two C or two C fullerenes, indicating a particularly strong affinity. The cyclocarbons and C fullerene can spontaneously assemble into complexes in the gas phase at room temperature, and the hydrophobic effect caused by the solvent environment can promote this binding. The binding strength with C fullerene increases almost linearly with the increase of cyclocarbon size, and the C@C dimer exhibits a perfect nano-Saturn structure. As the ring size increases, the angle between the two cyclocarbons of the 2 : 1 trimers formed by cyclocarbons and C fullerene gradually decreases. In C@2 C trimer, the fullerene is symmetrically surrounded by two cyclocarbons. The results on the trimers formed by cyclocarbon and C fullerenes in a 1 : 2 ratio showed when the cyclocarbon sandwiched between two fullerenes is not quite large, the trimers exhibit an ideal dumbbell-like structure, and the presence of the first fullerene has a significant synergistic effect on the binding of the second one. The cyclocarbon greatly promotes the dimerization of fullerenes, which acted as a "molecular glue".
这项工作首次对环碳与C富勒烯之间的非共价络合进行了全面的理论研究。环碳与C富勒烯之间的结合能明显强于两个C或两个C富勒烯之间的结合能，表明具有特别强的亲和力。环碳和C富勒烯在室温下可在气相中自发组装成络合物，溶剂环境引起的疏水作用可促进这种结合。与C富勒烯的结合强度几乎随环碳尺寸的增加呈线性增加，C@C二聚体呈现出完美的纳米土星结构。随着环尺寸的增加，由环碳和C富勒烯形成的2 : 1三聚体的两个环碳之间的夹角逐渐减小。在C@2 C三聚体中，富勒烯被两个环碳对称包围。关于由环碳和C富勒烯以1 : 2比例形成的三聚体的结果表明，当夹在两个富勒烯之间的环碳不太小时，三聚体呈现出理想的哑铃状结构，第一个富勒烯的存在对第二个富勒烯的结合有显著的协同作用。环碳极大地促进了富勒烯的二聚化，其起到了“分子胶水”的作用。
