On November 17th, the top international journal Science published the latest research results of Nankai University online. The research topic is "An all metal fullerene: [K@Au12Sb20]5-", which reports on the synthesis and bonding mechanism of all metal fullerene [K@Au12Sb20]5- (Figure 1-2), showcasing a novel compound synthesis technique and the application of precise control of metal bonds in structural chemistry, providing a new research approach for the creation of new materials. This breakthrough achievement highlights the important position of Nankai University in the fields of synthetic chemistry and coordination chemistry of main group metal elements.
Figure 1: Schematic diagram of the cluster structure of all metal fullerene [K@Au12Sb20]5-; Potassium atoms are purple, gold atoms are yellow and antimony atoms are blue
Since 2000, the Nobel Prize in Chemistry has been awarded to scientists in the field of synthetic chemistry for seven times. And this year it has been awarded to three scientists who have made original contributions to the discovery and synthesis of quantum dots. In 1985, Smalley et al. first discovered a football shaped carbon cluster C60 composed of 60 carbon atoms, also known as fullerene. It was precisely because of this significant scientific discovery that they were awarded the Nobel Prize in Chemistry in 1996.
Due to its unique highly symmetrical structure, unique physical properties and diverse chemical reaction characteristics, fullerene has attracted much attention since its discovery, prompting people to continuously explore its applications in different fields. The bonding properties of fullerene have gradually been extended to the field of inorganic synthetic chemistry. Theoretically, it is predicted that inorganic fullerene will exhibit unusual stability and reactivity, which has aroused great interest among scientists. However, its synthesis still faces enormous challenges.
Prof. Zhongming Sun 's research group from the School of Materials Science and Engineering, Nankai University has successfully prepared all metal fullerene [K@Au12Sb20]5- by developing a new synthesis method that combines high-temperature solid-state synthesis with metal organic chemistry.
This compound exhibits a structure close to the Archimedean dodecahedron, with each side consisting of an antimony pentagonal plane containing a gold atom. The inner diameter is approximately 0.90 nanometers, slightly larger than the diameter of C60 molecules (0.71 nanometers). In this relatively large cluster cavity, only one potassium ion is embedded, and the cluster as a whole does not require the protection of organic ligands. Its structure still has good chemical stability, making it the pure inorganic compound with the closest coordination environment to fullerene to date.
Figure 2: Bonding modes and molecular orbitals of [K@Au12Sb20]5-clusters
The stability of this exposed heavy metal spherical cluster was achieved, partly due to the central potassium ion serving as a template support and partly due to the unique heterometallic bond between gold and antimony playing a crucial role in maintaining the overall structural integrity (Figure 2).
Figure 3: Electronic structure analysis of [K@Au12Sb20]5-
Theoretical calculation results show that one of the most prominent features of the molecule is its three-dimensional spherical aromatic electronic structure, which leads to the formation of a delocalized π electron cloud on the surface of the cluster, endowing all metal fullerene compounds with unique physical and chemical properties (Figure 3). This discovery is expected to play an important role in fields such as optoelectronic materials or room temperature catalysis, and has broad application potential.
When reporting on this research work, American Chemical and Engineering News suggested that this inorganic fullerene may help chemists design and synthesize other precision structured nanostructures. Prof. Andreas Schnepf, a chemist from the Universitaet Tuebingen in Germany, stated that this molecule exhibits remarkable bonding properties and he believes that these clusters may exhibit interesting reactivity and potential applications in solution.
Yuhe Xu, a doctoral student from the School of Materials Science and Engineering, Nankai University is the first author of this paper and Prof. Zhongming Sun is the corresponding author. This work received important support in theoretical calculations from Dr. Wenjuan Tian from Shanxi University, Prof. Muñoz-Castro from the University of San Sebastian in Chile and Profe. Frenking from the University of Marburg in Germany. Other relevant data analysis was supported by Prof. Xuebin Wang, Associate Prof. Jun Xu, and Dr. Ning Li.
This study has also been supported by relevant projects from the National Natural Science Foundation of China, he Bureau of Science and Technology of Tianjin and Nankai University.
Prof. Zhongming Sun 's research group has long been committed to the field of synthetic chemistry and coordination chemistry of main group metal elements. The publication of the research results on the synthesis and bonding mechanism of all metal fullerene [K@Au12Sb20]5- marks an important progress and breakthrough in the related research field of Nankai University.
Relevant achievements were published in SCIENCE, 2023, DOI: 10.1126/science.adj6491.
https://www.science.org/doi/10.1126/science.adj6491
