824
(Invited) Dynamics of Fullerenes in Solid-State Visualized with Variable Temperature Single-Crystal X-Ray Diffraction

Tuesday, 31 May 2022: 09:20
West Meeting Room 202 (Vancouver Convention Center)
F. Liu and A. A. Popov (Leibniz Institut fuer Festkorper und Werkstoffforschung)
The dynamics of fullerenes in the solid state is fundamentally interesting. Variable temperature single-crystal X-ray diffraction is a powerful tool to view the temperature-driven dynamics of fullerene molecules in the crystal lattice since the fruitful dynamics information of fullerene crystals is well located in the widely accessible liquid nitrogen cryostats temperature range (90 K - room temperature). Recently, we succeeded in the visualization of the temperature-driven circular movement of Dy2 inside a benzyl functionalized C80 cage in its solvate crystal.1 Meanwhile, we surveyed the temperature-driven dynamics of typical fullerene/nickel octaethylporphyrin (NiOEP) co-crystals, presented the rather static behaviour of porphyrin molecules, and strong libration of the fullerene cages (C60 and C80) in the temperature range of 100-280 K. While the M3N clusters (M3N = Ho2LuN, Lu3N or Sc3N) inside C80 cage show intriguing temperature-driven dynamics with subtle metal atom size/mass effects.2-3 Even more, we observed the fullerene molecule Sc3N@C70 rotation in the co-crystal with NiOEP.4 In this contribution, the details of the recently observed temperature-dependent dynamics will be discussed.

  1. Liu, F.; Velkos, G.; Krylov, D. S.; Spree, L.; Zalibera, M.; Ray, R.; Samoylova, N. A.; Chen, C.-H.; Rosenkranz, M.; Schiemenz, S.; Ziegs, F.; Nenkov, K.; Kostanyan, A.; Greber, T.; Wolter, A. U. B.; Richter, M.; Büchner, B.; Avdoshenko, S. M.; Popov, A. A., Air-stable redox-active nanomagnets with lanthanide spins radical-bridged by a metal–metal bond. Nat. Commun. 2019, 10, 571.
  2. Liu, F.; Spree, L., Molecular Spinning Top: Visualizing the Dynamics of M3N@C80 with Variable Temperature Single Crystal X-ray Diffraction. Chem. Commun. 2019, 55, 13000-13003.
  3. Hao, Y.; Wang, Y.; Spree, L.; Liu, F., Rotation of fullerene molecules in the crystal lattice of fullerene/porphyrin: C60 and Sc3N@C80. Inorg. Chem. Front. 2021, 8, 122-126.
  4. Hao, Y.; Wang, Y.; Dubrovin, V.; Avdoshenko, S. M.; Popov, A. A.; Liu, F., Caught in Phase Transition: Snapshot of the Metallofullerene Sc3N@C70 Rotation in the Crystal. J. Am. Chem. Soc. 2021, 143, 612-616.