Caught in Phase Transition: Snapshot of the Metallofullerene Sc₃N@C₇₀ Rotation in the Crystal

Abstract

The molecular structure of Sc 3 N@C 2v (7854)-C 70 was determined by single-crystal X-ray diffraction. Variabletemperature X-ray diffraction analysis unraveled the details of the phase transition caused by the temperature-driven jumplike rotation of the fullerene cage between two orientations. Whereas in the lower-temperature P2 1 /c phase the fullerene predominantly occupies one orientation, two orientations become equally occupied in the higher-temperature C2/m phase. This work provides a rare example of the well-defined order−disorder transition in metallofullerene crystals and thus gives important insight into the problem of disorder impeding metallofullerene crystallography.

Electrophilic Trifluoromethylation of Dimetallofullerene Anions en Route to Air-Stable Single-Molecule Magnets with High Blocking Temperature of Magnetization

“…80 All four NiOEP molecules in the asymmetric unit show observable translation disorder (with major/minor sites occupancies of 0.83/0.17, 0.83/0.17, 0.84/0.16, and 0.84/ 0.16 for 1, 2, 3, and 4, respectively) similar to the lowtemperature phase of the recently reported Sc 3 N@C 2v (7854)-C 70 •NiOEP crystal. 81 The fullerene at site A has fully ordered fullerene cage/CF 3 group and disordered Tb 2 dimer with 6 metal sites (occupancies 2 × 0.58, 2 × 0.22, and 2 × 0.20) as shown in Figure 3. Metal sites are distributed along the belt of hexagons of the C 80 cage (highlighted with yellow in Figure 3), which resembles the distribution of Dy sites in Dy 2 @ C 80 (CH 2 Ph).…”

Capturing the Missing Carbon Cage Isomer of C84 via Mutual Stabilization of a Triangular Monometallic Cyanide Cluster

“…Molecular structures of YCN@C 84 , DyCN@C 84 (I), DyCN@C 84 (II), and TbCN@C 84 were determined unambiguously by single-crystal X-ray diffraction based on high-quality cocrystals obtained by using different hosts (see Table S2 for detailed crystallographic data). TbCN@C 84 was cocrystallized with Ni II (OEP) (OEP = octaethylporphyrin), which is commonly used as a host in the X-ray crystallographic study of endohedral metallofullerenes, ,,− while YCN@C 84 , DyCN@C 84 (I), and DyCN@C 84 (II) cocrystallized with a decapyrrylcorannulene (DPC) host developed by us recently. − Figure a–d illustrate the relative orientations of YCN@ C 2 (13)-C 84 , DyCN@ C 2 (13)-C 84 , TbCN@ C 2 (13)-C 84 , and DyCN@ C 2 v (17)-C 84 within the corresponding YCN@ C 2 (13)-C 84 ·2DPC, DyCN@ C 2 (13)-C 84 ·2DPC, TbCN@ C 2 (13)-C 84 ·Ni II (OEP), and DyCN@ C 2 v (17)-C 84 ·2DPC cocrystals, in which only one orientation of the fullerene cage together with the major site of the MCN cluster is given for clarity. Interestingly, when the DPC host is used, two DPC molecules embrace one fullerene molecule of YCN@ C 2 (13)-C 84 /DyCN@ C 2 (13)-C 84 /DyCN@ C 2 v (17)-C 84 with a V-shape geometry, whereas the stoichiometric ratio changes to 1:1 for the Ni II (OEP) host in the case of the TbCN@ C 2 (13)-C 84 ·Ni II (OEP) cocrystal.…”

Single-Molecule Fullerenes: Current Stage and Perspective

“…Third, new principles and applications based on the properties of fullerenes should be explored. In recent years, a large number of endohedral fullerenes encapsulating magnetic atoms have been studied as single-molecule magnets. − The fullerene cage can significantly reduce the relaxation processes associated with environmental fluctuations, and the carbonaceous elemental composition can effectively preserve spin coherence due to the zero nuclear spin of 12 C, leading to the emergence of quantum states with long spin coherence. − In combination with single-molecule devices, these fullerenes hold promise for a variety of quantum spin applications, including quantum computing, , atomic clock, and quantum metrology and sensing. , The atoms/clusters encapsulated in the carbon cages are good samples to study the unusual valence states, confined interactions and motions. − The atoms/clusters encapsulated in the carbon cages are good samples to study the unusual valence states, as well as confined interactions and motions. − These will greatly expand the application prospects of fullerenes and single-molecule devices.…”