Del Castillo Roxana M, Miralrio Alan, Rios Citlalli, Salcedo Roberto
Departamento de Física, Facultad de Ciencias, Universidad Nacional Autónoma de México, Circuito Exterior s/n, Ciudad Universitaria, Coyoacán, 04510, Ciudad de México, Mexico.
Departamento de Ciencias, Tecnologico de Monterrey, Campus Toluca, Eduardo Monroy Cardenas 2000, San Antonio Buenavista, 50110, Toluca, Mexico.
J Mol Model. 2019 Jul 23;25(8):239. doi: 10.1007/s00894-019-4118-0.
New organometallic complexes of carbon nanotori were designed and theoretically described by means of density functional theory. After a systematic structural search, it was found that energetically favorable complexes were formed by the metal atoms Cr and Ni, both located at the center of a nanotorus with diameter around 5 Å and 120 carbon atoms. The nature of the metal-nanotorus interaction shows a partial polar-covalent character, different from those found in other well-known organometallic compounds. Interactions were studied through molecular orbitals and thermodynamic stability. Ten bonds are set up between the metal atom and nanotorus, confirmed by electron density topology analysis, showing ten bond critical points among the metal atoms and the surrounding carbon atoms. The response of the induced electron current caused by a magnetic field perpendicular to the nanotorus was analyzed to explain the electron delocalization and aromaticity of the complexes. Only in the case of the chromium complex, the electron density is fully delocalized on the whole complex. According to a geometry-based index of aromaticity, interaction with the metal atom only changes the aromatic character of the carbon rings slightly. Also, induced currents were used to elucidate the presence of a ferrotoroidal behavior. The isolated nanotorus and its compound with a single Ni atom have well-defined ferrotoroidal behavior because they present broken symmetries and could help to design a topological insulator. Meanwhile, the nanotorus with a Cr atom at the center lacks ferrotoroidal behavior as a consequence of the absence of magnetic vortices. Graphical abstract Organometallic complex of carbon nanotorus with chromium and induced currents on it by applying an external magnetic field.
通过密度泛函理论设计并从理论上描述了新型碳纳米环金属有机配合物。经过系统的结构搜索,发现由金属原子铬(Cr)和镍(Ni)形成的配合物在能量上是有利的,这两种金属原子都位于直径约为5埃且含有120个碳原子的纳米环中心。金属 - 纳米环相互作用的性质表现出部分极性共价特征,这与其他知名金属有机化合物中的相互作用不同。通过分子轨道和热力学稳定性研究了相互作用。金属原子与纳米环之间形成了十个键,电子密度拓扑分析证实了这一点,表明在金属原子与周围碳原子之间存在十个键临界点。分析了垂直于纳米环的磁场引起的感应电子电流的响应,以解释配合物的电子离域和芳香性。仅在铬配合物的情况下,电子密度在整个配合物上完全离域。根据基于几何的芳香性指数,与金属原子的相互作用仅略微改变了碳环的芳香特性。此外,感应电流被用于阐明铁环面行为的存在。孤立的纳米环及其与单个镍原子的化合物具有明确的铁环面行为,因为它们呈现出对称性破缺,并且有助于设计拓扑绝缘体。同时,中心有一个铬原子的纳米环由于没有磁涡旋而缺乏铁环面行为。图形摘要:碳纳米环与铬的金属有机配合物以及施加外部磁场时其上的感应电流。