A Theoretical Study on the Functionalisation Process of C₁₈NB Fullerene Through its Open [5,5] Cycloaddition with 4-Pyridine Nitrile Oxide

Abstract

C 20 nanofullerene and its derivatives, as the smallest carbon cages, are amongthe most important compounds in the field of nanoscience. As a result, it is very important to find a procedure to functionalise these precious compounds to exploit their numerous benefits. So, in this study, the process was investigated of adding a functional group to one of the C 20 fullerene derivatives, via its open [5,5] cycloaddition reaction with 4-pyridine nitrile oxide. This showed that the open [5,5] cycloaddition reaction between 4-pyridine nitrile oxide and C 18 NB fullerene takes place with sufficient speed that would need no catalyst. According to the calculations, a highly asynchronous concerted mechanism operates in this reaction. It seems that oxygen-boron interaction causes the mechanism to be asynchronous. All calculations were performed at the B3LYP/6-311G(d,p) level of theory.

The extraordinary gravity of three atom 4π-components and 1,3-dienes to C20-nXn fullerenes; a new gate to the future of Nano technology

“…Also, in parallel with those studies, investigations on the other properties of this small carbon cage, such as its electronic [125], magnetic moment formation [126], its memory effects on the other surfaces [127], energy storage [128], electron transport [129], and optoelectronic behavior [130] were performed. Moreover, Baei's works [131,132] and Siadati et al systematic studies on especial adsorption [37][38][39][40], sensing [133][134][135][136], and nanosized actuating applications [137] might be of important reports in this especial field.…”

“…Thus, many precious attempts have been done by scientists to reach to this goal [33][34][35]. Researches were ongoing until in some of the recent reports, an extraordinary tendency of some fullerene especially the smallest one (C20 fullerene and its derivatives, to three atom 4π-components (TACs) or dienes were observed [36][37][38][39][40]. In this paper, these reports about such attraction have been reviewed, in a quick glance.…”

A [1 + 2] cycloaddition instead of usual [2 + 3] cycloaddition between the B12N12 cluster and methyl azide: Potential energy surface calculations and Born–Oppenheimer molecular dynamics simulations

“…One of those two had a 2.88 Å distance between a hydrogen atom of methyl azide and a nitrogen atom (N21) of the cluster (''Reactants'' in Figure 2), and the other one had a 2.54 Å distance between the terminal nitrogen atom of the azide Some previous reports revealed that [2 + 3] cycloaddition reactions between the 1,3dipoles and C 20 fullerene (or its derivatives) as dipolarophile proceed in a very fast and spontaneous manner. [45][46][47][48][49][50] However, in this project, it was observed that the [2 + 3] (Figure 2 and Table 1). On the other hand, TS (Con-A) and TS (Con-B) refer to [2 + 3] cycloadditions at positions A and B, respectively, while TS (Con-E) refers to [1 + 2] cycloaddition at position B (leaving an N 2 molecule).…”

“…Some previous reports revealed that [2 + 3] cycloaddition reactions between the 1,3dipoles and C 20 fullerene (or its derivatives) as dipolarophile proceed in a very fast and spontaneous manner. [45][46][47][48][49][50] However, in this project, it was observed that the [2 + 3] cycloaddition between the B 12 N 12 fullerene-like cluster (as dipolarophile) and methyl azide (as dipole) has a DG # of 29.38 kcal mol 21 (on position A) and 31.95 kcal mol 21 (on position B). Thus, [2 + 3] cycloaddition of azide to the B 12 N 12 cluster occurs very slowly or is nearly impossible.…”

On Searching for a Stepwise Channel for the Mechanism of a 1,3-Dipolar Cycloaddition between a Thiocarbonyl S-Oxide and C20 Fullerene using Born–Oppenheimer ab Initio QM/MM Molecular Dynamics

“…It should be noted that a high active surface of activation of C 20 fullerene in pericyclic reactions was demonstrated by some recent reports [23,24]. It is noteworthy that the functionalisation of fullerenes, especially C 20 fullerene as the smallest, seems to be an interesting issue for nanotechnology research and the 1,3-dipolar reaction is a suitable approach for achieving this [25,26].…”