Electrochemistry of Carbon Nanoparticles

Endohedral Fullerenes

“…Recently, the 45 Sc NMR spectra of Sc 2 S@C 82 - C 3 v (8), Sc 2 S@C 72 - C s (10528), and Sc 3 CN@C 80 - I h (7) were reported. Sc 2 S@C 82 exhibits one line at 290 ppm in CS 2 pointing to the fast rotation of the Sc 2 S cluster at room temperature, whereas in Sc 2 S@C 72 position of the Sc signal is shifted to 183 pm . For Sc 3 NC@C 80 , two signals in a 2:1 intensity ratio were found at 298 K (Figure a), which suggests the rigid structure of the Sc 3 NC cluster with two types of nonequivalent Sc atoms in good agreement with single-crystal X-ray diffraction study …”

“…9,135 In Sc 2 O, a Sc− O−Sc angle of 157°has been found. 370 13 C and 45 Sc NMR spectroscopic study for Sc 4 O 2 @C 80 reported in 2012 showed that the cluster is rotating fast at the NMR time scale giving only two 13 C signals as in many other EMFs with the C 80 -I h (7) carbon cage (Table 1). 371 4.3.5.…”

“…Chemical properties of EMFs were discussed in refs , , , , and were a subject of a dedicated review by Lu, Akasaka and Nagase in 2011 . Electrochemical behavior of EMFs was described in refs and , and the basic account on the endohedral electrochemistry appeared in 2011 . Finally, applications of EMFs in organic photovoltaic and especially their biomedical applications were extensively reviewed. − …”

“…35 On the other hand, chemical derivatization can also hinder the rotation of EMF molecules in the crystals, and the structures of many EMFs have been determined by single-crystal X-ray diffraction studies of their derivatives such as in the studies performed by Akasaka and coworkers (University of Tsukuba, Japan). 44 254 La, 252,253,408−414 Ce, 255 Gd, 229 Dy 258 X-ray (powder): Sc, 224 Y, 222 La, 225 Gd 226 X-ray: La, 259 Gd 260 M 2 @C 82 -II UV−vis: Er, 305 (Tm, HoTm) 306 M 2 C 2 @C 82 -II X-ray (Drv): Sc; 355 NMR-2D: Sc; 355 NMR: Sc, 403 Y; 193 UV−vis: Sc, 403 Er, 305 (40) Sm@C 90 -I X-ray 266 C 2 (42) Sm@C 90 -II X-ray 266 C 2 (45) Sm@C 90 -IV X-ray 266 C 2v (46) Sm@C 90 -III X-ray 266 C 92 C s (24) Sm@C 92 -II X-ray 264 C 1 (42) Sm@C 92 -I X-ray 264 D 3 (85) M 2 C 2 @C 92 X-ray: Gd; 363 In the field of NMR spectroscopy, structural studies gained significantly from the use of bulk electrolysis of solutions of paramagnetic EMFs, which yields their diamagnetic forms (usually monoanions) suitable for further 13 C NMR spectroscopic studies. 206 NMR studies have been also successfully performed for paramagnetic EMFs in which paramagnetism originated from encapsulated lanthanide atoms (such as Ce III in Ce 2 @C 72,78,80 ).…”

“…The list of structurally characterized monometallofullerenes has been recently extended by M@C 94 −C 3v (134) (M = Ca, Tm, Sm) (Figure 6h), 263,264 three isomers of Sm@C 84 (C 2 (11), C 2 (13), and D 3d (19)), 265 four isomers of Sm@C 90 (C 2 (40), C 2 (42), C 2 (45), and C 2v ( 46)), 266 and two isomers of Sm@C 92 (C s (24) and C 1 (42)). 264 For single-crystal X-ray diffraction studies, all these EMFs have been cocrystallized with Ni II (OEP).…”