Current progress on the chemical functionalization and supramolecular chemistry of M@C82

Abstract

Since the first discovery of fullerenes in 1985, the insertion of one or more atoms into a hollow fullerene cage has been attempted. Furthermore, synthesis and extraction of metallofullerene, La@C(n), were reported in 1991. Recent successful isolation and purification of metallofullerenes have facilitated the investigation of their chemical properties. This mini-review presents a summary of the recent progress of chemical functionalization and supramolecular chemistry of M@C(82). Selective functionalization and successful structural analysis of derivatives have revealed their chemical features arising from endohedral metal doping.

Urea as a New and Cheap Nitrogen Source for the Synthesis of Metal Nitride Clusterfullerenes: The Role of Decomposed Products on the Selectivity of Fullerenes

“…The optimum ratio of Sc 2 O 3 /COA C H T U N G T R E N N U N G (NH 2 ) 2 /C has been determined and the yield of Sc 3 N@C 80 (I h + D 5h ) per gram of Sc 2 O 3 by using COA C H T U N G T R E N N U N G (NH 2 ) 2 as the new nitrogen source was compared with that obtained by using other reAbstract: By using urea as the new nitrogen source, for the first time, Scbased metal nitride clusterfullerenes (NCFs), Sc 3 N@C 2n (2n = 80, 78, 70, 68), have been synthesized successfully. The optimum molar ratio of Sc 2 3 , using COA C H T U N G T R E N N U N G (NH 2 ) 2 as the new nitrogen source, was quantitatively compared to those obtained when using the reported nitrogen sources, including N 2 , NH 3 , and guanidinium thiocyanate. We find that there is a clear difference on the selectivity of Sc-based NCFs within the extract mixture obtained from one rod and accumulative two rods.…”

“…Finally the difference in the decomposition behavior of COA C H T U N G T R E N N U N G (NH 2 ) 2 and melamine was studied in detail and a possible decomposition process of COA C H T U N G T R E N N U N G (NH 2 ) 2 during discharging was proposed. Accordingly, the difference in the selectivity and yield of Sc NCFs for COA C H T U N G T R E N N U N G (NH 2 ) 2 and melamine was interpreted.…”

“…[1] Among the endohedral fullerenes, metal nitride clusterfullerenes (NCFs) exhibit a variety of new structural and electronic properties for potential applications in electronics and biomedicines. [2] Thanks to the establishment of synthetic methods for NCFs, a wealth of new NCFs have been isolated in the past decade by means of either tuning the encaged metal atoms or stabilizing a large variety of cage sizes, including different isomeric structures. [1, To date, all of the isolated NCFs have been synthesized primarily by two methods: the "trimetallic nitride template" (TNT) process reported by Dorn et al in 1999 [4] and the "reactive gas atmosphere" route developed by Dunsch et al in 2003, [5] with gaseous N 2 and NH 3 as the nitrogen source, respectively.…”

Emergence of Highly Elaborated π-Space and Extending Its Functionality Based on Nanocarbons: New Vistas in the Fullerene World

“…Chemical reactivity of La@C 2v (9)-C 82 has been investigated extensively as the representative of paramagnetic EMFs. 98 As stated, La@C 2v (9)-C 82 is more reactive than C 60 because of its smaller HOMOLUMO gap. However, a critical problem arises from the fact that the molecular symmetry of La@C 2v (9)-C 82 , as well as those of many other EMFs, is lower than that of C 60 .…”

Electron transfer modifies chemical properties of C70 fullerene surface: An ab initio molecular dynamics study of C70O3 molozonides doped with light atoms

“…2 The list of structurally characterized monometallofullerenes is dominated by the higher members (C n , n > 70) doped with heavy metal atoms (such as lanthanides or group 3 metals), and many interesting results have been obtained in the chemistry of such complexes. [2][3][4][5] However, much less is known about the properties of C 60 and C 70 doped with lighter metal atoms, despite the fact that lithium complexes with these fullerenes were amongst the first EMFs to be obtained using ion implantation techniques. 6,7 This method was also used to prepare endohedral complexes of light fullerenes encapsulating a single N atom, 8 creating materials with potential application in quantum computing.…”