The high-yield synthesis of Dy3N@C80 (I) opens the possibility of characterizing its molecular and vibrational structures. We report on the structure determination of Dy3N@C80 (I) by X-ray crystallographic study of single crystal of Dy3N@C80.Ni(OEP).2C6H6, revealing a nearly planar Dy3N cluster encapsulated in an Ih-C80 cage. The vibrational structure of Dy3N@C80 (I) is studied by Fourier transform infrared (FTIR) and Raman spectroscopy in combination with force-field calculations. A correlation was found between the antisymmetric metal-nitrogen stretching vibration and the structure of the M3N cluster of M3N@C80 (I) (M = Y, Gd, Tb, Dy, Ho, Er, Tm). Moreover, a stronger interaction between the encaged nitride cluster and the C80 carbon cage was found in the class II M3N@C80 (I) (M = Y, Gd, Tb, Dy, Ho, Er, Tm) than in Sc3N@C80 (I). This study demonstrates that the cluster size plays the dominating role in the structure of the M3N cluster in M3N@C80 (I).

The highly chlorinated, thermally stable [60]fullerene C 60 Cl 30 contains a cylinder-shaped carbon cage consisting of two aromatic six-membered rings and one equatorial 18p-trannulene belt separated by two 15-membered belts of sp 3 carbon atoms bearing Cl substituents. Find out more about the synthesis and properties of C 60 [1] To date, considerable success has been achieved in preparation and structural characterization of fullerene bromides [2] and fluorides.[3] Despite numerous reports on chlorination of C 60 by different reagents, [4] only two individual compounds have been isolated so far. The structure of C 60 Cl 6 formed in the reaction of ICl with C 60 in benzene was deduced from the 13 C NMR and IR spectra.[4b] C 60 Cl 24 was synthesized using VCl 4 and SbCl 5 ; a tetrahedral structure similar to that of C 60 Br 24 [2a, d] was assigned to this chloride on the basis of a comparison between the experimental and theoretically calculated IR spectra.[5]Here we report the synthesis and structural characterization of the novel, highly chlorinated fullerene C 60 Cl 30 . This chlorofullerene can be prepared using chlorinating agents such as ICl, ICl 3 , and SbCl 5 . Typically, 50-100 mg of C 60 and a large excess (~2 g) of chlorinating agents were sealed in glass ampules and heated at 220-250 8C for one to three days. Then, the ampules were opened, and the excess of the chlorinating agents and their decomposition products were removed in vacuo at 150 8C. Pure C 60 Cl 30 (1) was formed in the reaction of C 60 with SbCl 5 , whereas chlorination by ICl yielded the C 60 Cl 30 ·2 ICl solvate (2), both as dark-orange crystals stable in air. The IR spectrum of C 60 Cl 30 is presented in Figure 1. The most prominent bands are observed at ñ = 439, 450, 471, 479, 730, 775, 822, 854, 895, 903, 918, 958, 993, and 1447 cm À1 .[6]C 60 Cl 30 is insoluble in most common organic solvents such as diethyl ether, 1,4-dioxane, CH 2 Cl 2 , CHCl 3 , and CCl 4 ; it is poorly soluble in CS 2 , toluene, and chlorobenzene; and its solubility in 1,2-dichlobenzene was estimated at roughly 0.2 mg mL À1 . The thermal stability of C 60 Cl 30 appears to be remarkably high: its decomposes into C 60 and Cl 2 at 450-500 8C (Figure 2), which is about 120 8C higher than the temperature ranges previously reported for C 60 Cl 24 .[4b, 5] The mass loss for C 60 Cl 30 , 60.1 %, corresponds well to the calculated value of 59.75 %.

Unexpected selectivity: [60]Fullerene and CF3I react selectively at 440 °C to synthesize C60(CF3)12. In the product with S6 symmetry, 12 CF3 groups form a continuous loop of alternating para‐ and meta‐C6(CF3)2 hexagons. In the crystal, the chains of molecules are strengthened owing to stacking interactions and shielding effects from the CF3 groups, thus accounting for the low volatility and solubility of the compound.

Fluoride can do it too! Sol-gels of metal fluorides play an important role in the formation of high surface area metal fluorides. The synthesis of amorphous high surface area metal fluorides via a recently discovered two-step synthetic route was investigated in detail, exemplified for aluminium fluoride. The first step is fluorination of aluminium alkoxide with anhydrous HF in organic solvents, which proceeds as a sol-gel process known until now only for metal oxide formation. The reaction pathway is illustrated including crystal structure determination of the intermediate aluminium alkoxide fluoride. The resulting amorphous aluminium alkoxide fluoride has to be freed in a second step of solvating alcohol and of residual alkoxidic groups. This is done by heating in a stream of a mild fluorinating agent like a HCFC or CFC or in HF to obtain high surface area and very high Lewis acidity; an inert gas such as N 2 is not sufficient. Using a variety of analytical techniques, including liquid and solid state NMR, X-ray structure analysis and XPS, the reaction pathways have been elucidated. 1