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FUNCTIONALIZATION OF ENDOHEDRAL METALLOFULLERENES: INSIGHTS FROM COMPUTATIONAL STUDIES
Antonio Rodriguez Fortea¹;
¹UNIVERSITAT ROVIRA I VIRGILI, Tarragona, Spain;
PAPER: 47/Nanomaterials/Invited (Oral) OS
SCHEDULED: 11:30/Wed. 29 Nov. 2023/Dreams 3

ABSTRACT:
Since the isolation of the first endohedral metallofullerene (EMF) La@C₈₂,¹ intensive research has been devoted to this family of compounds that encapsulate metal atoms or clusters in their inner void space.² Exohedral functionalization of EMFs is a key step to obtain new materials for multiple applications. For instance, water-soluble gadofullerenes are used as powerful contrast agents in medicine.³ Derivatization has also become an essential tool to purify and separate fullerene mixtures.⁴ Cycloadditions as Bingel-Hirsch reaction, Prato reaction, Diels-Alder reaction, or carbene and benzyne additions were among the most used reactions, although multicomponent reactions have been also considered recently.⁵ Computational chemistry has helped so far not only to understand the regioselectivity of a wide variety of chemical functionalization on EMFs, but also to disclose in many cases their reaction mechanisms.⁶ We here will present an overview of our computational studies on the reactivity of EMFs and will focus on recent results on actinidofullerenes, a family recently isolated and characterized by the groups of Ning Chen in Soochow and Echegoyen at UTEP.⁷ In mono-actinidofullerenes, the actinide tends to have oxidation state +4, which involves an important metal-cage interaction with significant covalent contributions. This feature makes them different from lanthanofullerenes, where the metal is usually with oxidation state +3. Consequently, the electronic structure, properties as well as reactivity of actinidofullerenes are expected to be different compared to their lanthanide counterparts.

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