Recent advances in single molecule magnetism of dysprosium-metallofullerenes

This article outlines the magnetic properties of single molecule magnets based on Dy-encapsulating endohedral metallofullerenes. The factors that govern these properties, such as the influence of different non-metal species in clusterfullerenes, the cage size, and cage isomerism are discussed, as well as the recent successful isolation of dimetallofullerenes with unprecedented magnetic properties. Finally, recent advances towards the organization of endohedral metallofullerenes in 1D, 2D, and 3D ordered structures with potential for devices are reviewed

Mixed 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

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

Health Industries in the Twentieth Century. Introduction

This article is the introduction to the special issue' Health Industries in the Twentieth Century'. It offers a broad literature review of scholarly works about the history of health and medicine, and stresses the opportunities for business historians to tackle the field of healthcare

Rotation of fullerene molecules in the crystal lattice of fullerene porphyrin C60 and Sc3N C80

The dynamics of molecules in the solid-state is important to understand their physicochemical properties. The temperature-dependent dynamics of Sc3N@C80 and C60 in the crystal lattice containing nickel octaethylporphyrin (NiOEP) was studied with variable temperature X-ray diffraction (VT-XRD). The results indicate that the fullerene cages (both C60 and C80) in the crystal lattice present stronger libration than the co-crystallized NiOEP in the temperature range of 100–280 K. In contrast to the fullerene cage, the Sc3N cluster shows pronounced rotation roughly perpendicular to the plane of the co-crystallized NiOEP molecule driven by temperature. The obtained temperature dependent dynamic behavior of the Sc3N cluster is different from that of Ho2LuN and Lu3N, regardless of their rather similar structure, indicating the effect of the mass and size of the metal ions