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Updated: Jun 24, 2025
Electrophoretic Crystallization of Ultrathin High-performance Metal-organic Framework Membranes
Published on: August 16, 2018
Capturing Metal Fluoride inside a Carbon Cage
Ya Zhao1, Ziqi Hu1,2, Panfeng Chuai1
1National Laboratory for Molecular Sciences, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, People's Republic of China.
Abstract:
We report here a new type of metal fluoride cluster that can be stabilized inside fullerene via in situ fluorine encapsulation followed by exohedral trifluoromethylation, giving rise to rare-earth metal fluoride clusterfullerenes (FCFs) M2F@C80(CF3) (M = Gd and Y). The molecular structure of Gd2F@C80(CF3) was unambiguously determined by single-crystal X-ray analysis to show a μ2-fluoride-bridged Gd-F-Gd cluster with short Gd-F bonds of 2.132(7) and 2.179(7) Å. The 19F NMR spectrum of the diamagnetic Y2F@C80(CF3) confirms the existence of the endohedral F atom, which exhibits a triplet with a large 19F-89Y coupling constant of 74 Hz and a high temperature sensitivity of the 19F chemical shift of 0.057 ppm/K. Theoretical studies reveal the ionic Y-F bonding nature arising from the highest electronegativity of the F element and an electronic configuration of [Y2F]5+@[C80]5- with an open-shell carbon cage, which thus necessitates the stabilization of FCFs by exohedral trifluoromethylation.
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