Facile Access to Y₂C_2n (2n = 92–130) and Crystallographic Characterization of Y₂C₂@C₁(1660)-C₁₀₈: A Giant Nanocapsule with a Linear Carbide Cluster

Abstract

A series of giant metallofullerenes YC (2n = 92-130) have been successfully obtained through the treatment of the fraction enriched by 1,2-dichlorobenzene with SnCl. Subsequent chromatographic separation gives a pure sample with a composition of YC. Crystallographic results reveal that this endohedral takes the carbide form, namely YC@C(1660)-C, representing as the largest metallofullerene that has been characterized by crystallography to date. Despite the disorder of the metal cluster, the major YC adopts a previously predicted linear configuration, indicating that the compression of the internal cluster by the cage is almost negligible in this giant cage. Electrochemical studies suggest that YC@C(1660)-C is a good electron donor instead of an electron acceptor.

Trapping an unprecedented Ti3C3 unit inside the icosahedral C80 fullerene: a crystallographic survey

“…35 The B3LYP/6-31G*$SDD encapsulation-energy gain per one encapsulated atom for Ti 3 C 3 @I h -C 80 is calculated to be about 18 kcal per mol per atom which is even larger than a relative energy gain computed for the recently isolated Y 2 C 2 @C 1 (1660)-C 108 . 36 The stability calculations indeed support the nding that a novel EMF containing a unique Ti 3 C 3 cluster was experimentally obtained.…”

Crystallographic characterization of Y2C2n (2n = 82, 88–94): direct Y–Y bonding and cage-dependent cluster evolution

“…2.711Å (Table S3 †), which are similar to that observed for Y 2 C 2 @C 1 (1660)-C 108 , representing typical coordination bonds. 31 Fig . 2 presents the molecular structures of these EMFs showing the major components together with the co-crystallized Ni II (OEP) molecule.…”

“…For instance, a linear Y 2 C 2 cluster can be encapsulated into the giant C 108 cage to template the formation of Y 2 C 2 @C 1 (1660)-C 108 . 31 There is still a long way to nally clarify the mysteries in the metal-metal interactions in EMFs and new theories of coordination chemistry are expected.…”

Endohedral Metallofullerenes: New Structures and Unseen Phenomena

“…Although intensive studies on CCMFs have made significant progress in understanding the structural fundamentals, the study of M 2 C 2@ C 2 n (M=Lu, Tm, Er, Y, Tb, and Gd) with the inner cluster larger than Sc 2 C 2 but smaller than La 2 C 2 remains scarce before 2018. Then, a collection of collaborative results reported a series of CCMFs including Lu 2 C 2 @C 86–92 , Er 2 C 2 @C 80–90 , Y 2 C 2 @C 86‐92 , and even by far the largest EMFs reported, Y 2 C 2 @C 108 by single‐crystal XRD crystallography. The structures of the typical CCMFs that have been crystallographically characterized so far suggest that the ionic radius (we use the Shannon ionic radii throughout this paper) of the encapsulated metal ions is closely associated with the cage size, and increases with increasing size of the latter, that is, C 72–88 , C 80–92 , and C 90–104 for Sc 2 C 2 , Er 2 C 2 , and La 2 C 2 , respectively (Figure ).…”