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Monatsh Chem (2014) 145:891896

DOI 10.1007/s00706-014-1181-1


[2+1] Cycloaddition of dichlorocarbene to finite-size graphene

sheets: DFT study
Igor K. Petrushenko

Received: 10 January 2014 / Accepted: 13 February 2014 / Published online: 8 April 2014
Springer-Verlag Wien 2014

Abstract The [2?1] cycloaddition of dichlorocarbene to optical properties and have attracted enormous attention of
finite-size graphene has been investigated by means of the researchers worldwide [17].
B3LYP/SVP approach. Three different sites of function- Graphene, a planar sheet of sp2-bonded carbon atoms, is
alization were studied. The results show that cycloaddition the fundamental component of graphite and carbon nano-
on the edge or corner positions can not significantly distort tubes. The discovery by Geim and Novoselov in 2004 [8]
the planar framework of graphene, but center functionali- has generated intense activity in graphene research. The
zation changes its structure dramatically. Reaction energies sophisticated low-dimensional features and exceptional
were calculated, and they show that the peripheral areas of mechanical properties have given rise to many technolog-
graphene are much more reactive than the center sites. The ical applications of pristine graphene in various fields. Its
electronic properties of graphene are weakly modified by usage in electronic and optical devices, energy storage
the [2?1] cycloaddition. Finally, we propose that the systems, composite materials, chemical sensors, and drug
[2?1] cycloaddition of dichlorocarbene, owing to its sim- delivery has been suggested [916]. Soon after, the
plicity, can be a promising way to fine-tune the bandgap of chemical functionalization of graphene became a center of
graphene. interest in modern physics and chemistry [11]. The main
motivations of these experimental and theoretical studies
Keywords Carbenes  Density functional theory  were a modification of electronic properties via changing
Cycloadditions  Graphene  Adsorption the band gap, potential use of functionalized graphene for
hydrogen storage, a search for techniques to massively
produce cheap graphene by chemical reduction of
Introduction graphene oxide, and oxidation with subsequent unzipping
of graphene as a method to create graphene nanostructures
Unique properties and perfect structures of fullerenes and of a given size [1720]. However, the reactivity of
carbon nanotubes (CNTs) predetermine their great influ- graphene as a planar sheet is much worse than those of
ence on nanotechnologies. These nanoclusters demonstrate CNTs and fullerenes. Therefore, only a few functionali-
outstanding mechanical, physical, chemical, electronic, and zation techniques have been transferred from fullerene to
graphene chemistry: azo, aryne, and nitrene additions [21
23], Claisen rearrangement [24], 1,3-dipolar and Diels
Alder cycloadditions [25, 26].
Carbenes (CR2, R = H, F, Cl, CH3, CN, and NO2) are
Electronic supplementary material The online version of this
article (doi:10.1007/s00706-014-1181-1) contains supplementary divalent carbon species. They have been widely applied for
material, which is available to authorized users. the synthesis of cyclopropanes and have received much
attention, both experimentally and theoretically. Recently,
I. K. Petrushenko (&)
the addition of carbenes onto fullerenes and nanotubes has
Physical and Technical Institute, Irkutsk State Technical
University, Irkutsk, Russia been studied in detail. Most of the works reported the
e-mail: addition of dichlorocarbene (CCl2) on sidewalls of both

892 I. K. Petrushenko

CNTs [27] and boron nitride nanotubes [28], whereas a few Results and discussion
papers investigated diaryl-carbene [29], modified diazirines
[30], and carbene introduction [31] on fullerenes. Thus, Structural parameters
Ismaili et al. [32], involving a photoinitiated carbene
addition approach, prepared a nanohybrid consisting of The structures of the C70H22 graphene cluster and attached
gold nanoparticles covalently attached to multiwalled dichlorocarbene are presented in Fig. 1; the notations used
CNTs. Luksirikul et al. [33], using the high reactivity of to determine key structural parameters are also given. In
carbenes, obtained functionalized single-walled CNTs with Table 1, we summarize information about structural
different substituents. The authors pointed out that they parameters determined for the [2?1] cycloaddition of di-
enhance dispersibility of such CNTs and promote their chlorocarbenes to carbon sheets both in the gas phase and
further derivatization. Additionally, they considered the solvent.
attached groups as anchoring points for further compati- First, we considered a gas phase cycloaddition of di-
bility with other compounds. chlorocarbene. The three positions of its addition, center
To date, there are two significant fields of interest in (1), edge (2), or corner (3) differ significantly with respect
fullerene chemistry in which modification of properties of to their properties (the numbering system is the same as
fullerenes by carbene addition is studied [29]. The first one described previously [25]). Carboncarbon bonds of pris-
deals with carbene additions to empty fullerenes. The tine graphene are elongated from 1.416 to 1.552 (1), from
pioneering paper by Nogami et al. [34] describing the 1.358 to 1.522 (2), and from 1.395 to 1.541 A (3) upon
addition of dichlorocarbene to C60 was published in 1993. functionalization (Table 1). The changes of bond lengths
It was followed by the works of Fabre et al. [35], Yinghuai propagate to adjacent carbon hexagons, and it is clear that
et al. [36], and Gao et al. [37]. The second field is devoted the induced distortion will be the largest in the case of 1, as
to carbene additions to endohedral metallofullerenes the number of neighbor carbon hexagons decreases on
(EMFs). Recent progress in this contemporary topic has going from 1 to 3 (Fig. 1). Thus, the reaction on the center
revealed that chemical reactivities of EMFs differ consid- bond 1 will affect directly four benzene rings, changing
erably from those of common fullerenes [29, 3840]. In their aromaticity and degree of pp conjugation. For this
those works, EMF properties were thoroughly investigated
both experimentally and theoretically. EMF-based com-
pounds are promising materials for active components in
new photovoltaic and photosynthetic systems [29].
One can see that there exists a massive array of papers
devoted to fullerene/nanotube modifications; graphene
attracted less attention. Not until 2012 did the first evidence
of the actual functionalization of graphene with dichloro-
carbene come forth [41]. In this communication, the
synthesis procedure and investigation techniques were
described. Therefore, it is interesting to consider the
structural changes in graphene affected by dichlorocarbene.
The influence of the position of the attached carbene spe-
cies on the graphene framework is also an important issue.
Besides, to the best of our knowledge, no attempts have
been made to ascertain what influence solvents have on the
binding energy of carbenes as well as on the band gap of
functionalized graphene.
As described in the previous paragraphs, the function-
alization of nanotubes and fullerenes with carbenes is
important. Taking into consideration the significance that
graphene holds nowadays, herein we report a comprehen- Fig. 1 The models used herein to define structural parameters of
sive density functional theory study on the CCl2 functionalized graphene. (Top) dichlorocarbene attached to a graph-
functionalization of finite-size graphene sheets, focusing on ene sheet: C2C3 is the graphene bond attacked by dichlorocarbene;
equilibrium structures of the CCl2-attached graphene and C1C3 is the bond between graphene and dichlorocarbene. C2C1
C3 is the valence angle between two CC bonds. (Bottom) 5 9 5
the effects of attached dichlorocarbene on the electronic graphene model system. Positions of carbene cycloaddition: 1
properties of graphene. center, 2edge, 3corner. Hydrogen atoms omitted for clarity

[2?1] Cycloaddition of dichlorocarbene to finite-size graphene sheets 893

Table 1 Reaction energies, HOMOLUMO gaps/eV, and basic structural parameters (d/A, a/8) determined for the addition of dichlorocarbene
to graphene
Gas phase Chloroform
G 1 2 3 G 1 2 3

dC1C3 1.539 1.513 1.506 1.539 1.512 1.505

daC2C3 1.416; 1.358; 1.395 1.552 1.522 1.541 1.416; 1.359; 1.396 1.549 1.522 1.542
aC2C1C3 60.536 60.439 61.117 60.442 60.476 61.203
Er -4.865 -49.199 -35.286 -8.902 -48.378 -34.489
HOMOLUMO gap 0.651 0.745 0.658 0.574 0.654 0.749 0.661 0.577
For the case of pristine graphene, we present the initial lengths of center, edge, and corner bonds

Fig. 2 Top views ac and side views df of functionalized graphene 13. Hydrogen atoms omitted for clarity

case, the dramatic effect on the planar morphology was graphene sheet. This distortion has a modest effect on the
also observed. whole graphene sheet. Thus, in terms of deformation, the
The perfect structure of investigated graphene acquires a reactions at the periphery are much easier than those at the
curved character on functionalization (Fig. 2 a, d). The center. The data obtained show that 2 (Er = -49.199 eV)
reaction on the center bond is expected to be energetically is the most favorable position of functionalization of
unfavorable as it causes large graphene distortion. Our graphene with dichlorocarbene.
calculations decidedly approve this conclusion (Table 1). In order to extend our results with respect to other
Reactions on edge (2) and corner (3) will be more addends, we collect available data on azomethine and
favored, as such a functionalization substantially distorts carbonyl ylides. Table 2 shows the reaction energies of
only one benzene ring. In Fig. 2, it is shown that infini- these compounds with graphene depending on the site of
tesimal changes occur in the case of 2. The corner addition.
functionalization results in a minor distortion of one ben- The data entirely confirm our conclusion about the ease
zene ring, which extends slightly from the plane of the of dichlorocarbene addition to edge and corner positions.

894 I. K. Petrushenko

Table 2 Reaction energies of 1,3-dipoles with graphene graphene [41] should occur mostly on the peripheral spots.
Additive Er/eV
The edge reaction is more favorable than the corner by ca.
14 eV, whereas the corner reaction is more favorable than
Carbonyl ylide [25] -15.7a, -69.4b, -60.6c the center by ca. 44 eV (39 eV if chloroform is used as the
Azomethine ylide [25] 7.2a, -44.9b, -35.5c solvent). Our future works will review a series of graphene
Azomethine ylide [54] 14.99d, 10.84e models and reactions with a wide range of carbenes. On
Cycloaddition to 1 position of 5 9 5 graphene sheet account of the similarity in reaction mechanisms, we may
Cycloaddition to 2 position of 5 9 5 graphene sheet expect the same selectivity in their cycloaddition on the
Cycloaddition to 3 position of 5 9 5 graphene sheet graphene surface.
Cycloaddition to an infinite graphene sheet
Cycloaddition to 1 position of 4 9 4 graphene sheet
Electronic properties

In Fig. 3 we present calculated density of states (DOS) for

The reactions of azomethine ylide on center bonds were pristine and functionalized graphene in the gas phase (the
shown to be endothermic and cannot occur spontaneously DOS of the same species in chloroform are presented in the
[25]. Carbonyl ylide was reported to be even more reactive supplementary material).
than azomethine ylide [25] and leads to exothermic reac- The DOS of the pristine graphene sheet shows that it is a
tions on center bonds (Table 2). Besides, the results of this semiconductor. The same holds true for 1, 2, and 3 that
work coincide well with the paper by Cao et al. [25], have nearly identical DOS. The solvent affects the elec-
namely that the most favorable position for dichlorocar- tronic structure of graphene feebly. Although the
bene addition is 2; the least favorable is 1, and the functionalization of graphene introduces major changes in
intermediate is 3. The same holds for azomethine and its structure, it alters its electronic properties only moder-
carbonyl ylides (Table 2). Nevertheless, there is a small ately (Fig. 3). We can observe, however, that these
possibility for dichlorocarbene molecules being attached to properties of graphene are still modified depending on the
the center bonds that is in contrast with the addition of site of the [2?1] cycloaddition (Fig. 3). A careful adjust-
azomethine ylide to graphene. ment such as this can help a researcher in obtaining
In the experimental paper [41] a successful functional- graphene with fine-tuned properties.
ization of graphene with dichlorocarbene has been The largest modifications are in the cases of 1 and 3;
reported. It is very likely that such a modification occurs CCl2 additions to a corner or center bond sufficiently affect
mainly at the periphery of graphene and adjacent areas. the HOMOLUMO gap (Fig. 3; Table 1). On the other
Secondly, we considered the addition of dichlorocar- hand, dichlorocarbene attack on the edge bond leaves the
bene in the presence of chloroform in which it can be HOMOLUMO gap intact (Fig. 3; Table 1). Our results on
readily generated. In general, the solvent affects the a graphene sheet with a larger degree of functionalization
structural parameters of the functionalized graphene only (two or three attached species) show that the value of the
marginally. Carboncarbon distances C1C3 remain the energy gap is also site-selective. However, the difference in
same as in the gas phase. On the other hand, the the band gap values of species with various modification
underlying C2C3 bond in position 1 becomes smaller ratios is small. The work of Kumar et al. [42] reports that
compared to the case of gas phase cycloaddition (1.549 the 30 % modification ratio affects the band gap of CNTs
and 1.552 A). Such a tiny change may lead, however, to strongly; therefore, we may expect that a higher degree of
a smaller deformation of the graphene sheet; therefore, functionalization introduces bigger changes in those values
dichlorocarbene addition on center bonds in the presence for graphene, but this challenging work requires a massive
of chloroform is energetically more favorable (Table 1). array of additional calculations, and it is beyond the scope
The influence of the solvent on reaction energies in the of this paper.
cases of 2 and 3 is minor. Thus, using such a method, one can fine-tune the
All in all, although chloroform introduces small changes bandgap of finite-size graphene. Recently, Chen et al. [43]
in certain cases, e.g. in the case of 1, it does not appear to have reported an experimental technique for modifying
be generally useful to significantly enhance the addition of graphene nanoribbon bandgaps. It is worth mentioning that
various species to graphene. they have designed atomically precise nanoribbons, which
To sum up, cycloadditions to all studied positions are permits us to expand our theoretical findings to a practical
exothermic, both in the gas phase and solvent. All these side. Therefore, dichlorocarbene functionalization, owing
reactions are spontaneous; additions on positions 2 and 3 to its simplicity, can be a good way to tune a HOMO
are much more favorable than on center bonds. Our ana- LUMO gap of graphene. One can control this by alternat-
lysis shows that previously reported functionalization of ing the position and degree of functionalization. Such

[2?1] Cycloaddition of dichlorocarbene to finite-size graphene sheets 895

Fig. 3 DOS for both graphene and functionalized graphene 13

readily modified graphene should help track the way At low concentrations of attached dichlorocarbene, the
towards development of graphene-based miniature semi- electronic properties of the graphene sheet are moderately
conductor devices. modified by the [2?1] cycloaddition. We observe, however,
that these properties are dependent on the site of dichloro-
carbene addition. Higher concentrations of the addend
Conclusions result in a shift of HOMO and LUMO energy levels, but the
energy gaps remain practically the same. The solvent
We have presented the DFT study of the addition of di- affects electronic properties of graphene only marginally.
chlorocarbene to graphene. Three different positions of Our future studies will review a series of graphene
cycloaddition have been investigated: center (1), edge (2), models and reactions with a wide range of carbenes.
and corner (3). Cycloaddition on the center region stimu-
lates considerable changes of the morphology of graphene.
When functionalized, the sheet of graphene acquires a bent Computational methods
structure. On the other hand, reactions on edges or corners
mainly influence the adjacent six-membered carbon cycle Geometry optimizations were performed on a 5 9 5 graph-
and keep the overall graphene surface planar. Any di- ene sheet (constructed from 70 carbon atoms) terminated by
chlorocarbene reaction on graphene is exothermic. hydrogen atoms. The structure is shown in Fig. 1. Although
However, the peripheral spots of graphene are more reac- coronene C24H12 was proven to be the smallest graphene-
tive than the center ones. In comparison with use of like model compound, which is widely used in quantum
azomethine ylide, dichlorocarbene is the better modifier of chemistry studies [4446], we still employed the larger
graphene. In fact, we can predict that usage of addends as system that more resembles real graphene. Orca 2.9.1 [47]
reactive as dichlorocarbene should be an effective way to molecular modeling software was used to perform DFT
introduce anchoring points onto graphene for further calculations on the investigated systems. Calculations were
compatibility with different compounds. carried out using gradient-corrected DFT with Beckes

896 I. K. Petrushenko

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