Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 143, Issue 43, Pages 18139-18149Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.1c07021
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- Deutsche Forschungsgemeinschaft [PO 1602/7-1, PO 1602/8-1, LI 3055/3-1]
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Electrophilic trifluoromethylation of lanthanide dimetallofullerenes showed high selectivity towards M-2@C-80(-) anions, yielding monoadducts as the main product. Magnetic characterization revealed that the synthesized lanthanide dimetallofullerene is a robust single-molecule magnet with broad magnetic hysteresis properties.
Lanthanide dimetallofullerenes with single-electron M-M bonds are an important class of single molecular magnets and qubit candidates, but stabilization of their unique electronic and spin structure in the form of a neutral molecule requires functionalization of the fullerene cage with a single radical group. The lack of selectivity of the currently available procedure results in a complicated and tedious separation process. Here we demonstrate that electrophilic trifluoromethylation of a mixture of metallofullerene anions with Umemoto reagent II is highly selective toward M-2@C-80(-)(M = Tb, Y) anions, yielding M-2@C-80(CF3) monoadducts as the main reaction product. Single-crystal X-ray diffraction study proved attachment of the CF3 group to the pentagon/hexagon/hexagon junction and revealed that positions of metal atoms inside the fullerene cage in the cocrystal with NiOEP are strongly related to the position of the porphyrin moieties. Magnetic characterization of Tb-2@C-80(CF3) showed that it is a robust single-molecule magnet with broad magnetic hysteresis, 100 s blocking temperature of 25 K, and the relaxation barrier of 801(4) K, corresponding to the flipping of the Tb magnetic moment in the strongly ferromagnetically coupled [Tb3+-e-Tb3+] spin system.
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