Endohedral Actinidofullerenes: Carbon-Metal Interactions and Rare Earth Metal-Metal Bonding

Identifier:  TDX:4532

Handle: https://hdl.handle.net/20.500.11797/TDX4532

Authors:  Roselló Marín, Yannick

Abstract:
This thesis focuses on the study of actinide-based endohedral metallofullerenes (EMFs), specially those containing uranium and thorium atoms encapsulated within carbon cages. The research is divided into several key areas, exploring the structural, electronic, and bonding characteristics of these complex molecules. This research thoroughly examines the interaction between the metal atom and the carbon cage in actinidofullerenes. DFT is employed to understand the stabilization mechanisms and preferred configurations. The results demonstrate that the position of the metal atom inside the fullerene cage significantly influences the electronic properties and stability of the EMFs. Further chapters explore di-actinidofullerenes, particularly those containing U−U and Ce−Ce bonds within fullerene cages. The nature of these bonds is investigated using computational techniques, revealing that strong covalent U−U bonds can form under specific conditions, challenging traditional views of actinide chemistry. Another significant contribution of this thesis is the study of clusterfullerenes, where multiple uranium atoms are encapsulated with non-metal atoms like nitrogen, forming clusters. These studies provide insights into the bonding variety and electronic structures of actinide clusters stabilized by fullerene cages. This thesis also addresses mixed di-metallofullerenes, focusing on heteronuclear bonds such as Sc−Y. These studies reveal the potential for creating new types of metal-metal bonds and enhance the understanding of interactions in mixed-metal systems. This research advances the understanding of the structural and electronic properties of actinide-based endohedral metallofullerenes. By exploring various configurations and bonding scenarios, the thesis provides a comprehensive view of the potential of these interactions.