Meloni Giovanni, Giustini Andrea, Park Heejune
Department of Chemistry, University of San Francisco, San Francisco, CA, United States.
Department of Physical and Chemical Sciences, Università degli Studi de L'Aquila, L'Aquila, Italy.
Front Chem. 2021 Jul 14;9:712960. doi: 10.3389/fchem.2021.712960. eCollection 2021.
With the aim of finding a suitable synthesizable superalkali species, using the B3LYP/6-31G* density functional level of theory we provide results for the interaction between the buckminsterfullerene C and the superalkali LiF. We show that this endofullerene is stable and provides a closed environment in which the superalkali can exist and interact with CO. It is worthwhile to mention that the optimized LiF structure inside C is not the most stable C isomer found for the "free" superalkali but the D geometry. The binding energy at 0 K between C and LiF (D) is computed to be 119 kJ mol. Once CO is introduced in the endofullerene, it is activated, and the angle is bent to 132. This activation does not follow the previously studied CO reduction by an electron transfer process from the superalkali, but it is rather an actual reaction where a F (from LiF) atom is bonded to the CO. From a thermodynamic analysis, both CO and the encapsulated [LiF⋅CO] are destabilized in C with solvation energies at 0 K of 147 and < -965 kJ mol, respectively.
为了找到合适的可合成超碱物种，我们使用B3LYP/6 - 31G*密度泛函理论水平，给出了巴基球C与超碱LiF之间相互作用的结果。我们表明，这种内嵌富勒烯是稳定的，并提供了一个封闭环境，超碱可以在其中存在并与CO相互作用。值得一提的是，C内部优化后的LiF结构不是“自由”超碱中最稳定的C异构体，而是D几何结构。计算得出C与LiF（D）在0 K时的结合能为119 kJ/mol。一旦将CO引入内嵌富勒烯中，它就会被激活，并且键角弯曲至132°。这种激活并非遵循先前研究的通过超碱电子转移过程进行的CO还原，而是一个实际反应，其中一个F（来自LiF）原子与CO键合。从热力学分析来看，CO和包封的[LiF⋅CO]在C中都不稳定，0 K时的溶剂化能分别为147和< -965 kJ/mol。
