Liu Yang, Li Wangchang, Li Peiying, Guo Yanmin, Cui Peng, Zhang Zhuxia
College of Materials Science and Engineering, Key Laboratory of Interface Science and Engineering in Advanced Materials, Taiyuan University of Technology Taiyuan 030024 China.
The Novel Computer Architecture Laboratory, School of Information, Guizhou University of Finance and Economics Guiyang 550025 China
RSC Adv. 2023 Feb 3;13(7):4553-4563. doi: 10.1039/d2ra08153a. eCollection 2023 Jan 31.
The encapsulation of fullerenes by carbon nanorings has gained increasing attention because of the unique molecular structure and special properties of the formed complexes. The host-guest interactions between the fullerenes and the carbon nanorings can influence the metal ion orientation and the molecular electronic structure. In this study, we hooped a series of carbide cluster metallofullerenes, namely ScC@C(5)-C, ScC@C(8)-C, and ScC@D(23)-C, with molecular carbon nanorings of [12]cycloparaphenylene ([12]CPP) and perfluoro[12]cycloparaphenylene (PF[12]CPP). The formed complexes were computationally studied dispersion-corrected density functional theory calculations. The results showed that the deformation rate of PF[12]CPP after the formation of the fullerene-containing complexes was significantly smaller than that of [12]CPP. The binding energy and thermodynamic information showed that PF[12]CPP was more suitable for fullerene encapsulation. Moreover, charge population analysis showed that PF[12]CPP transferred more electrons to ScC@C ( = 40, 41, and 42) compared with [12]CPP. Energy decomposition and real-space function analyses of host-guest interactions revealed the characteristics and nature of the noncovalent interactions in the supramolecules. These results provide theoretical support for the study of host-guest systems based on metallofullerenes.
由于所形成配合物独特的分子结构和特殊性质，富勒烯被碳纳米环包封已受到越来越多的关注。富勒烯与碳纳米环之间的主客体相互作用会影响金属离子的取向和分子电子结构。在本研究中，我们用[12]对环芳撑（[12]CPP）和全氟[12]对环芳撑（PF[12]CPP）的分子碳纳米环环箍了一系列碳化物簇金属富勒烯，即ScC@C(5)-C、ScC@C(8)-C和ScC@D(23)-C。通过色散校正密度泛函理论计算对所形成的配合物进行了理论研究。结果表明，含富勒烯配合物形成后PF[12]CPP的形变率明显小于[12]CPP。结合能和热力学信息表明PF[12]CPP更适合包封富勒烯。此外，电荷布居分析表明，与[12]CPP相比，PF[12]CPP向ScC@C（n = 40、41和42）转移了更多电子。主客体相互作用的能量分解和实空间函数分析揭示了超分子中非共价相互作用的特征和本质。这些结果为基于金属富勒烯的主客体体系研究提供了理论支持。
