The magnetic properties of nitride clusterfullerenes GdxSc3-xN@C80 (x = 1-3) are studied as a function of the number of Gd atoms in the cluster. The intracluster interaction of the Gd ions in Gd2ScN@C80 and Gd3N@C80 is ferromagnetic with exchange constants of -1.2 K ± 0.1 K and -0.6 K ± 0.1 K, respectively. At 2 K, the magnetization curves exhibit noticeable deviations from the Heisenberg model pointing to a non-negligible anisotropy.
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http://dx.doi.org/10.1039/c3dt53367k | DOI Listing |
Inorg Chem
January 2025
Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, c/Marcel·lí Domingo 1, 43007 Tarragona, Spain.
Gas-phase synthesis and detection of boron-doped nitride clusterfullerenes and a large variety of monometallofullerenes have been achieved using a pulsed laser vaporization cluster source. Density functional theory (DFT) calculations show that the electronic structures of boron-doped endohedral metallofullerenes differ from those of the pristine all-carbon cages due to the lack of one electron upon boron substitution. For monometallofullerenes, this is likely the main reason for the somewhat different abundance distribution observed for boron-doped with respect to all-carbon cages.
View Article and Find Full Text PDFPrecis Chem
May 2024
Key Laboratory of Precision and Intelligent Chemistry, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Department of Materials Science and Engineering, University of Science and Technology of China, Hefei 230026, China.
Metal-nitrogen double bonds have been commonly reported for conventional metal complexes, but the coexistence of both transition metal-nitrogen and lanthanide-nitrogen double bonds bridged by nitrogen within one compound has never been reported. Herein, by encapsulating a ternary transition metal-lanthanide heteronuclear dimetallic nitride into a C fullerene cage, transition metal-nitrogen and lanthanide-nitrogen double bonds are costabilized simultaneously within the as-formed clusterfullerene TiCeN@C(12)-C, which is a representative heteronuclear dimetallic nitride clusterfullerene. Its molecular structure was unambiguously determined by single-crystal X-ray diffraction, revealing a slightly bent μ-bridged nitride cluster with short Ti-N (1.
View Article and Find Full Text PDFNd-based nitride clusterfullerenes NdMN@C with rare-earth metals of different sizes (M = Sc, Y, Lu) were synthesized to elucidate the influence of the cluster composition, shape and internal strain on the structural and magnetic properties. Single crystal X-ray diffraction revealed a very short Nd-N bond length in NdScN@C. For Lu and Y analogs, the further shortening of the Nd-N bond and pyramidalization of the NdMN cluster are predicted by DFT calculations as a result of the increased cluster size and a strain caused by the limited size of the fullerene cage.
View Article and Find Full Text PDFNanoscale
December 2022
State Key Laboratory of Materials Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, 1037 Luoyu Road, Wuhan, 430074 China.
While the strong interaction between the internal unit and the fullerene cage inside metallofullerenes is widely acknowledged, how the cage transformation interacts with the cluster configuration remains elusive. For this purpose, we herein synthesized three metallofullerene molecules with an easy-to-compare cluster configuration and cage arrangement, namely LuN@(17 490)-C, LuN@(22 010)-C, and LuN@(5)-C. The three lutetium-based nitride clusterfullerenes (NCFs) with small C carbon cages were synthesized by a modified arc-discharge method and their structures were unambiguously confirmed by X-ray crystallography.
View Article and Find Full Text PDFWe report on the discovery and detailed exploration of the unconventional photo-switching mechanism in metallofullerenes, in which the energy of the photon absorbed by the carbon cage π-system is transformed to mechanical motion of the endohedral cluster accompanied by accumulation of spin density on the metal atoms. Comprehensive photophysical and electron paramagnetic resonance (EPR) studies augmented by theoretical modelling are performed to address the phenomenon of the light-induced photo-switching and triplet state spin dynamics in a series of Y Sc N@C ( = 0-3) nitride clusterfullerenes. Variable temperature and time-resolved photoluminescence studies revealed a strong dependence of their photophysical properties on the number of Sc atoms in the cluster.
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