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- ItemMixed dysprosium-lanthanide nitride clusterfullerenes DyM2N@C80-: I h and Dy2MN@C80- i h (M = Gd, Er, Tm, and Lu): Synthesis, molecular structure, and quantum motion of the endohedral nitrogen atom(Cambridge : RSC Publ., 2019) Schlesier, C.; Liu, F.; Dubrovin, V.; Spree, L.; Büchner, B.; Avdoshenko, S.M.; Popov, A.A.Systematic exploration of the synthesis of mixed-metal Dy-M nitride clusterfullerenes (NCFs, M = Gd, Er, Tm, Lu) is performed, and the impact of the second metal on the relative yield is evaluated. We demonstrate that the ionic radius of the metal appears to be the main factor allowing explanation of the relative yields in Dy-M mixed-metal systems with M = Sc, Lu, Er, and Gd. At the same time, Dy-Tm NCFs show anomalously low yields, which is not consistent with the relatively small ionic radius of Tm3+ but can be explained by the high third ionization potential of Tm. Complete separation of Dy-Gd and Dy-Er, as well as partial separation of Dy-Lu M3N@C80 nitride clusterfullerenes, is accomplished by recycling HPLC. The molecular structures of DyGd2N@C80 and DyEr2N@C80 are analyzed by means of single-crystal X-ray diffraction. A remarkable ordering of mixed-metal nitride clusters is found despite similar size and electronic properties of the metals. Possible pyramidalization of the nitride clusters in these and other nitride clusterfullerenes is critically analyzed with the help of DFT calculations and reconstruction of the nitrogen inversion barrier in M3N@C80 molecules is performed. Although a double-well potential with a pyramidal cluster structure is found to be common for most of them, the small size of the inversion barrier often leads to an apparent planar structure of the cluster. This situation is found for those M3N@C80 molecules in which the energy of the lowest vibrational level exceeds that of the inversion barrier, including Dy3N@C80 and DyEr2N@C80. The genuine pyramidal structure can be observed by X-ray diffraction only when the lowest vibrational level is below the inversion barrier, such as those found in Gd3N@C80 and DyGd2N@C80. The quantum nature of molecular vibrations becomes especially apparent when the size of the inversion barrier is comparable to the energy of the lowest vibrational levels.
- ItemSingle Molecule Magnetism with Strong Magnetic Anisotropy and Enhanced Dy∙∙∙Dy Coupling in Three Isomers of Dy-Oxide Clusterfullerene Dy2O@C82(Chichester : John Wiley and Sons Ltd, 2019) Yang, W.; Velkos, G.; Liu, F.; Sudarkova, S.M.; Wang, Y.; Zhuang, J.; Zhang, H.; Li, X.; Zhang, X.; Büchner, B.; Avdoshenko, S.M.; Popov, A.A.; Chen, N.A new class of single-molecule magnets (SMMs) based on Dy-oxide clusterfullerenes is synthesized. Three isomers of Dy2O@C82 with Cs(6), C3v(8), and C2v(9) cage symmetries are characterized by single-crystal X-ray diffraction, which shows that the endohedral Dy−(µ2-O)−Dy cluster has bent shape with very short Dy−O bonds. Dy2O@C82 isomers show SMM behavior with broad magnetic hysteresis, but the temperature and magnetization relaxation depend strongly on the fullerene cage. The short Dy−O distances and the large negative charge of the oxide ion in Dy2O@C82 result in the very strong magnetic anisotropy of Dy ions. Their magnetic moments are aligned along the Dy−O bonds and are antiferromagnetically (AFM) coupled. At low temperatures, relaxation of magnetization in Dy2O@C82 proceeds via the ferromagnetically (FM)-coupled excited state, giving Arrhenius behavior with the effective barriers equal to the AFM-FM energy difference. The AFM-FM energy differences of 5.4–12.9 cm−1 in Dy2O@C82 are considerably larger than in SMMs with {Dy2O2} bridges, and the Dy∙∙∙Dy exchange coupling in Dy2O@C82 is the strongest among all dinuclear Dy SMMs with diamagnetic bridges. Dy-oxide clusterfullerenes provide a playground for the further tuning of molecular magnetism via variation of the size and shape of the fullerene cage.
- ItemSpin-glass state and reversed magnetic anisotropy induced by Cr doping in the Kitaev magnet α-RuCl3(College Park, MD : American Physical Society, 2019) Bastien, G.; Roslova, M.; Haghighi, M.H.; Mehlawat, K.; Hunger, J.; Isaeva, A.; Doert, T.; Vojta, M.; Büchner, B.; Wolter, A.U.B.Magnetic properties of the substitution series Ru1-xCrxCl3 were investigated to determine the evolution from the anisotropic Kitaev magnet α-RuCl3 with Jeff=1/2 magnetic Ru3+ ions to the isotropic Heisenberg magnet CrCl3 with S=3/2 magnetic Cr3+ ions. Magnetization measurements on single crystals revealed a reversal of the magnetic anisotropy under doping, which we argue to arise from the competition between anisotropic Kitaev and off-diagonal interactions on the Ru-Ru links and approximately isotropic Cr-Ru and isotropic Cr-Cr interactions. In addition, combined magnetization, ac susceptibility, and specific-heat measurements clearly show the destabilization of the long-range magnetic order of α-RuCl3 in favor of a spin-glass state of Ru1-xCrxCl3 for a low doping of x≤0.1. The corresponding freezing temperature as a function of Cr content shows a broad maximum around x ≤ 0.45.
- ItemShape-adaptive single-molecule magnetism and hysteresis up to 14 K in oxide clusterfullerenes Dy2O@C72 and Dy2O@C74 with fused pentagon pairs and flexible Dy-(μ2-O)-Dy angle(Cambridge : Royal Society of Chemistry, 2020) Velkos, G.; Yang, W.; Yao, Y.-R.; Sudarkova, S.M.; Liu, X.; Büchner, B.; Avdoshenko, S.M.; Chen, N.; Popov, A.A.Dysprosium oxide clusterfullerenes Dy2O@Cs(10528)-C72 and Dy2O@C2(13333)-C74 are synthesized and characterized by single-crystal X-ray diffraction. Carbon cages of both molecules feature two adjacent pentagon pairs. These pentalene units determine positions of endohedral Dy ions hence the shape of the Dy2O cluster, which is bent in Dy2O@C72 but linear in Dy2O@C74. Both compounds show slow relaxation of magnetization and magnetic hysteresis. Nearly complete cancelation of ferromagnetic dipolar and antiferromagnetic exchange Dy⋯Dy interactions leads to unusual magnetic properties. Dy2O@C74 exhibits zero-field quantum tunneling of magnetization and magnetic hysteresis up to 14 K, the highest temperature among Dy-clusterfullerenes.