Theoretical Insights into the Metal–Nonmetal Interaction Inside M₂O@C_2v(31922)-C₈₀ (M = Sc or Gd)

Abstract

The metal–nonmetal interaction is complicated but significant in organometallic chemistry and metallic catalysis and is susceptible to the coordination surroundings. Endohedral metallofullerene is considered to be an excellent model for studying metal–nonmetal interactions with the shielding effect of fullerenes. Herein, with the detection of ScGdO@C80 in a previous mass spectrum, we studied the effects of metal atoms (Sc and Gd) on the metal–nonmetal interactions of the thermodynamically stable molecules M2O@C 2v (31922)-C80 (M = Sc and Gd), where metal atoms M can be the same or different, using density functional theory calculations. The inner metal atom and the fullerene cage show mainly ionic interactions with some covalent character. The Sc atom with higher electronegativity plays a greater important role in the metal–nonmetal interactions than the Gd atom. This study would be useful for the further study of the metal–nonmetal interaction.

Electronic Structure, Aromaticity, and Magnetism of Minimum-Sized Regular Dodecahedral Endohedral Metallofullerenes Encapsulating Rare Earth Atoms

“…Fullerene superatoms can serve as special building blocks for constructing nanomaterials due to their ability to encapsulate atoms or molecules. − In 1985, Heath et al discovered the first stable embedded metal complex, LaC 60 , which was named metallofullerene . Since then, a rich variety of endohedral metallofullerenes (EMFs) with different cage sizes and embedded atoms have been extensively studied. − Compared to larger-sized fullerenes, small fullerenes are relatively unstable due to increased curvature, causing strain within the cage and weakening π-conjugation. − Especially for the smallest fullerene C 20 , which has all pentagonal faces, the bonds tend to be sp 3 bonds rather than the sp 2 bonds that are dominant in large fullerenes . Through metal doping, it is possible to increase the stability of smaller fullerenes and change their electronic properties. − T. Guo et al reported in 1992 that the experiment of MC 28 confirmed that the 5f feature of U in the photoemission spectra of UC 28 existing in sublimed films is consistent with the formal 4 + valence state of U.…”

Electrochemical Fabrication of 2D CuO Nanosheets on Pt Foil as a Highly Sensitive Non‐Enzymatic Glucose Sensor

“…In the last decade, noble metals in the form of Ag nanoparticles (NPs), [12–13] Au NPs, [14–16] Pt NPs, [17–19] Pd NPs, [20–21] and noble metal alloys [22–24] have been employed for the fabrication of glucose sensors because they have high conductivity and excellent catalytic activity. Nonetheless, these materials based on noble metals possess several disadvantages including poisoning of Au and Pt by the absorption of intermediates and chloride ions, which impedes electron transfer and ultimately reduces the sensitivity and selectivity of the sensors.…”