Synthesis and characterization of carbene derivatives of Th@C3v(8)-C82 and U@C2v(9)-C82: exceptional chemical properties induced by strong actinide–carbon cage interaction

Abstract

Chemical functionalization of endohedral metallofullerenes (EMFs) is essential for the application of these novel carbon materials. Actinide EMFs, a new EMF family member, have presented unique molecular and electronic structures but their chemical properties remain unexplored. Here, for the first time, we report the chemical functionalization of actinide EMFs, in which the photochemical reaction of Th@C_3v(8)-C₈₂ and U@C_2v(9)-C₈₂ with 2-adamantane-2,3′-[3H]-diazirine (AdN₂, 1) was systematically investigated. The combined HPLC and MALDI-TOF analyses show that carbene addition by photochemical reaction afforded three isomers of Th@C_3v(8)-C₈₂Ad and four isomers of U@C_2v(9)-C₈₂Ad (Ad = adamantylidene), presenting notably higher reactivity than their lanthanide analogs. Among these novel EMF derivatives, Th@C_3v(8)-C₈₂Ad(I, II, III) and U@C_2v(9)-C₈₂Ad(I, II, III) were successfully isolated and were characterized by UV-vis-NIR spectroscopy. In particular, the molecular structures of first actinide fullerene derivatives, Th@C_3v(8)-C₈₂Ad(I) and U@C_2v(9)-C₈₂Ad(I), were unambiguously determined by single crystal X-ray crystallography, both of which show a [6,6]-open cage structure. In addition, isomerization of Th@C_3v(8)-C₈₂Ad(II), Th@C_3v(8)-C₈₂Ad(III), U@C_2v(9)-C₈₂Ad(II) and U@C_2v(9)-C₈₂Ad(III) was observed at room temperature. Computational studies suggest that the attached carbon atoms on the cages of both Th@C_3v(8)-C₈₂Ad(I) and U@C_2v(9)-C₈₂Ad(I) have the largest negative charges, thus facilitating the electrophilic attack. Furthermore, it reveals that, compared to their lanthanide analogs, Th@C_3v(8)-C₈₂ and U@C_2v(9)-C₈₂ have much closer metal–cage distance, increased metal-to-cage charge transfer, and strong metal–cage interactions stemming from the significant contribution of extended Th-5f and U-5f orbitals to the occupied molecular orbitals, all of which give rise to their unusual high reactivity. This study provides first insights into the exceptional chemical properties of actinide endohedral fullerenes, which pave ways for the future functionalization and application of these novel EMF compounds.