Implications of Nitrogen Doping on Geometrical and Electronic Structure of the Fullerene Dimers

Abstract

Because of its unsaturated bonds, C 60 is susceptible to polymerize into dimers. The implications of nitrogen doping on the geometrical and electronic structure of C 60 dimers have been ambiguous for years. A quarter-century after the discovery of azafullerene dimer (C 59 N) 2 , we reported its single crystallographic structure in 2019. Herein, the unambiguous crystal structure information of (C 59 N) 2 is elucidated specifically, revealing that the inter-cage CC single bond length of (C 59 N) 2 is comparable with that of an ordinary C(sp 3)-C(sp 3) single bond, and that the most stable conformer of (C 59 N) 2 is gauche-conformer with a dihedral angle of 66°. To amend the structural deviations, geometrical structure of (C 59 N) 2 is optimized by a B3LYP-D3BJ function, which is proved to be more consistent with its single crystal structure than those by the commonly used B3LYP function. Moreover, the calculation method is also suitable for other representative fullerene dimers, such as (C 60) 2 and its divalent anion. Additionally, the dissociation of (C 59 N) 2 at 473 K under mass spectrometric conditions suggests the inter-cage CC bond is relatively weaker than an ordinary CC single bond, which can be explained by the interaction energies of inter-cages.

TmCN@C82: Monometallic Clusterfullerene Encapsulating a Tm3+ Ion

“…A pristine fullerene comprises 12 pentagons and several hexagons according to the number of carbon atoms, forming a cage-like structure with a hollow cavity. Based on the unique structures of fullerenes, three strategies, including exohedral [2][3][4], cage skeletal [5][6][7], and endohedral [8][9][10] modifications, have been widely employed for the chemical functionalization of fullerenes. In particular, the hollow cavity can serve as a nanoscale container to encapsulate various metal atoms or metal clusters, resulting in the formation of endohedral metallofullerenes (EMFs), which have attracted significant interest due to their unique structures and excellent physical and chemical properties, which are different from those of empty fullerenes, in versatile research fields [11][12][13].…”

Synthesis of pendant fullerene dimers by an aminomethylation reaction of fulleropyrrolidines bearing ketone moieties

“…Since the macroscopic manufacture of fullerenes in 1990, 1 various effective methods for fullerene functionalization have been discovered and a large number of fullerene derivatives with wide structural diversities have been prepared. 2–5 As a new type of all-carbon or modified fullerene containing two fullerene moieties, fullerene dimers 3–5 have attracted tremendous attention over the past decades due to their promising applications in many fields such as perovskite solar cells (PSCs), 6 in which fullerene dimers relative to the corresponding monomers generally exhibit superior stability and efficiency improvements by coordinating with both metal oxides and perovskites via halogen terminals. Dimerization of fullerene or a suitably functionalized fullerene provides a powerful tool for the preparation of fullerene dimers.…”

“…Dimerization of fullerene or a suitably functionalized fullerene provides a powerful tool for the preparation of fullerene dimers. 4,5 In addition, as an alternative method, bifunctional cycloaddition with two fullerene units also provides a new strategy for the synthesis of fullerene dimers. 3 c Generally speaking, fullerene dimers can be divided into three major groups based on the mode of linkage between the two fullerene moieties.…”

“…1a) as the simplest fullerene dimer in 1997 by using solid-state mechanochemical reactions. 4 c Singly-bonded dimers 5 with a general form of RC n -C n R (Fig. 1c) are another type of fullerene dimer and are generally prepared by the recombination of two in situ generated RC n ˙ from the addition of R˙ to fullerene.…”

Highly Active Amino-Fullerene Derivative-Modified TiO2 for Enhancing Formaldehyde Degradation Efficiency under Solar-Light Irradiation

“…Typically, the C 60 -TiO 2 nanocomposites have been reported to be able to efficiently catalyze degradation multiple organic substrates [ 12 ]. The incorporated C 60 not only inhibits the charge recombination, but also broadens the light absorption range to a certain degree [ 23 , 26 , 30 , 31 , 32 , 33 ]. Nevertheless, the photocatalytic performance and the range of application of this kind of composites is still not satisfactory.…”