Monatsh Chem (2014) 145:891896
DOI 10.1007/s00706-014-1181-1
ORIGINAL PAPER
[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
finite-size graphene has been investigated by means of the
B3LYP/SVP approach. Three different sites of function-
alization were studied. The results show that cycloaddition
on the edge or corner positions can not significantly distort
the planar framework of graphene, but center functionali-
zation changes its structure dramatically. Reaction energies
were calculated, and they show that the peripheral areas of
graphene are much more reactive than the center sites. The
electronic properties of graphene are weakly modified by
the [2?1] cycloaddition. Finally, we propose that the
[2?1] cycloaddition of dichlorocarbene, owing to its sim-
plicity, can be a promising way to fine-tune the bandgap of
graphene.
Keywords Carbenes  Density functional theory 
Cycloadditions  Graphene  Adsorption
Introduction
Unique properties and perfect structures of fullerenes and
carbon nanotubes (CNTs) predetermine their great influ-
ence on nanotechnologies. These nanoclusters demonstrate
outstanding mechanical, physical, chemical, electronic, and
Electronic supplementary material The online version of this
article (doi:10.1007/s00706-014-1181-1) contains supplementary
material, which is available to authorized users.
I. K. Petrushenko (&)
Physical and Technical Institute, Irkutsk State Technical
University, Irkutsk, Russia
e-mail: igor.petrushenko@istu.edu
optical properties and have attracted enormous attention of
researchers worldwide [17].
Graphene, a planar sheet of sp2-bonded carbon atoms, is
the fundamental component of graphite and carbon nano-
tubes. The discovery by Geim and Novoselov in 2004 [8]
has generated intense activity in graphene research. The
sophisticated low-dimensional features and exceptional
mechanical properties have given rise to many technolog-
ical applications of pristine graphene in various fields. Its
usage in electronic and optical devices, energy storage
systems, composite materials, chemical sensors, and drug
delivery has been suggested [916]. Soon after, the
chemical functionalization of graphene became a center of
interest in modern physics and chemistry [11]. The main
motivations of these experimental and theoretical studies
were a modification of electronic properties via changing
the band gap, potential use of functionalized graphene for
hydrogen storage, a search for techniques to massively
produce cheap graphene by chemical reduction of
graphene oxide, and oxidation with subsequent unzipping
of graphene as a method to create graphene nanostructures
of a given size [1720]. However, the reactivity of
graphene as a planar sheet is much worse than those of
CNTs and fullerenes. Therefore, only a few functionali-
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
divalent carbon species. They have been widely applied for
the synthesis of cyclopropanes and have received much
attention, both experimentally and theoretically. Recently,
the addition of carbenes onto fullerenes and nanotubes has
been studied in detail. Most of the works reported the
addition of dichlorocarbene (CCl2) on sidewalls of both
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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

123
[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
a
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
also observed.
The perfect structure of investigated graphene acquires a
curved character on functionalization (Fig. 2 a, d). The
reaction on the center bond is expected to be energetically
unfavorable as it causes large graphene distortion. Our
calculations decidedly approve this conclusion (Table 1).
Reactions on edge (2) and corner (3) will be more
favored, as such a functionalization substantially distorts
only one benzene ring. In Fig. 2, it is shown that infini-
tesimal changes occur in the case of 2. The corner
functionalization results in a minor distortion of one ben-
zene ring, which extends slightly from the plane of the
graphene sheet. This distortion has a modest effect on the
whole graphene sheet. Thus, in terms of deformation, the
reactions at the periphery are much easier than those at the
center. The data obtained show that 2 (Er = -49.199 eV)
is the most favorable position of functionalization of
graphene with dichlorocarbene.
In order to extend our results with respect to other
addends, we collect available data on azomethine and
carbonyl ylides. Table 2 shows the reaction energies of
these compounds with graphene depending on the site of
addition.
The data entirely confirm our conclusion about the ease
of dichlorocarbene addition to edge and corner positions.

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894
Table 2 Reaction energies of 1,3-dipoles with graphene
Additive Er/eV
Carbonyl ylide [25] -15.7a, -69.4b, -60.6c
Azomethine ylide [25] 7.2a, -44.9b, -35.5c
Azomethine ylide [54] 14.99d, 10.84e
a
Cycloaddition to 1 position of 5 9 5 graphene sheet
b
Cycloaddition to 2 position of 5 9 5 graphene sheet
c
Cycloaddition to 3 position of 5 9 5 graphene sheet
d
Cycloaddition to an infinite graphene sheet
e
Cycloaddition to 1 position of 4 9 4 graphene sheet
The reactions of azomethine ylide on center bonds were
shown to be endothermic and cannot occur spontaneously
[25]. Carbonyl ylide was reported to be even more reactive
than azomethine ylide [25] and leads to exothermic reac-
tions on center bonds (Table 2). Besides, the results of this
work coincide well with the paper by Cao et al. [25],
namely that the most favorable position for dichlorocar-
bene addition is 2; the least favorable is 1, and the
intermediate is 3. The same holds for azomethine and
carbonyl ylides (Table 2). Nevertheless, there is a small
possibility for dichlorocarbene molecules being attached to
the center bonds that is in contrast with the addition of
azomethine ylide to graphene.
In the experimental paper [41] a successful functional-
ization of graphene with dichlorocarbene has been
reported. It is very likely that such a modification occurs
mainly at the periphery of graphene and adjacent areas.
Secondly, we considered the addition of dichlorocar-
bene in the presence of chloroform in which it can be
readily generated. In general, the solvent affects the
structural parameters of the functionalized graphene only
marginally. Carboncarbon distances C1C3 remain the
same as in the gas phase. On the other hand, the
underlying C2C3 bond in position 1 becomes smaller
compared to the case of gas phase cycloaddition (1.549
and 1.552 A). Such a tiny change may lead, however, to
a smaller deformation of the graphene sheet; therefore,
dichlorocarbene addition on center bonds in the presence
of chloroform is energetically more favorable (Table 1).
The influence of the solvent on reaction energies in the
cases of 2 and 3 is minor.
All in all, although chloroform introduces small changes
in certain cases, e.g. in the case of 1, it does not appear to
be generally useful to significantly enhance the addition of
various species to graphene.
To sum up, cycloadditions to all studied positions are
exothermic, both in the gas phase and solvent. All these
reactions are spontaneous; additions on positions 2 and 3
are much more favorable than on center bonds. Our ana-
lysis shows that previously reported functionalization of
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I. K. Petrushenko
graphene [41] should occur mostly on the peripheral spots.
The edge reaction is more favorable than the corner by ca.
14 eV, whereas the corner reaction is more favorable than
the center by ca. 44 eV (39 eV if chloroform is used as the
solvent). Our future works will review a series of graphene
models and reactions with a wide range of carbenes. On
account of the similarity in reaction mechanisms, we may
expect the same selectivity in their cycloaddition on the
graphene surface.
Electronic properties
In Fig. 3 we present calculated density of states (DOS) for
pristine and functionalized graphene in the gas phase (the
DOS of the same species in chloroform are presented in the
supplementary material).
The DOS of the pristine graphene sheet shows that it is a
semiconductor. The same holds true for 1, 2, and 3 that
have nearly identical DOS. The solvent affects the elec-
tronic structure of graphene feebly. Although the
functionalization of graphene introduces major changes in
its structure, it alters its electronic properties only moder-
ately (Fig. 3). We can observe, however, that these
properties of graphene are still modified depending on the
site of the [2?1] cycloaddition (Fig. 3). A careful adjust-
ment such as this can help a researcher in obtaining
graphene with fine-tuned properties.
The largest modifications are in the cases of 1 and 3;
CCl2 additions to a corner or center bond sufficiently affect
the HOMOLUMO gap (Fig. 3; Table 1). On the other
hand, dichlorocarbene attack on the edge bond leaves the
HOMOLUMO gap intact (Fig. 3; Table 1). Our results on
a graphene sheet with a larger degree of functionalization
(two or three attached species) show that the value of the
energy gap is also site-selective. However, the difference in
the band gap values of species with various modification
ratios is small. The work of Kumar et al. [42] reports that
the 30 % modification ratio affects the band gap of CNTs
strongly; therefore, we may expect that a higher degree of
functionalization introduces bigger changes in those values
for graphene, but this challenging work requires a massive
array of additional calculations, and it is beyond the scope
of this paper.
Thus, using such a method, one can fine-tune the
bandgap of finite-size graphene. Recently, Chen et al. [43]
have reported an experimental technique for modifying
graphene nanoribbon bandgaps. It is worth mentioning that
they have designed atomically precise nanoribbons, which
permits us to expand our theoretical findings to a practical
side. Therefore, dichlorocarbene functionalization, owing
to its simplicity, can be a good way to tune a HOMO
LUMO gap of graphene. One can control this by alternat-
ing the position and degree of functionalization. Such
[2?1] Cycloaddition of dichlorocarbene to finite-size graphene sheets
Fig. 3 DOS for both graphene and functionalized graphene 13
readily modified graphene should help track the way
towards development of graphene-based miniature semi-
conductor devices.
Conclusions
We have presented the DFT study of the addition of di-
chlorocarbene to graphene. Three different positions of
cycloaddition have been investigated: center (1), edge (2),
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
structure. On the other hand, reactions on edges or corners
mainly influence the adjacent six-membered carbon cycle
and keep the overall graphene surface planar. Any di-
chlorocarbene reaction on graphene is exothermic.
However, the peripheral spots of graphene are more reac-
tive than the center ones. In comparison with use of
azomethine ylide, dichlorocarbene is the better modifier of
graphene. In fact, we can predict that usage of addends as
reactive as dichlorocarbene should be an effective way to
introduce anchoring points onto graphene for further
compatibility with different compounds.
895
At low concentrations of attached dichlorocarbene, the
electronic properties of the graphene sheet are moderately
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
result in a shift of HOMO and LUMO energy levels, but the
energy gaps remain practically the same. The solvent
affects electronic properties of graphene only marginally.
Our future studies will review a series of graphene
models and reactions with a wide range of carbenes.
Computational methods
Geometry optimizations were performed on a 5 9 5 graph-
ene sheet (constructed from 70 carbon atoms) terminated by
hydrogen atoms. The structure is shown in Fig. 1. Although
coronene C24H12 was proven to be the smallest graphene-
like model compound, which is widely used in quantum
chemistry studies [4446], we still employed the larger
system that more resembles real graphene. Orca 2.9.1 [47]
molecular modeling software was used to perform DFT
calculations on the investigated systems. Calculations were
carried out using gradient-corrected DFT with Beckes
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896
three-parameter hybrid exchange functional and the Lee
YangParr correlation functional (B3LYP) [48, 49]. As is
well known, the B3LYP functional was employed in many
research works on CNTs and graphene as well as in studies of
organic molecules [5052]. Moreover, the B3LYP results
agree well with those obtained by ab initio MP2 [53]. In order
to calculate the equilibrium geometry of studied structures
we used an SVP (split-valence polarization) basis set, which
is equivalent to the commonly used 6-31G* basis set [54]. In
SVP the inner shell atomic orbitals are described by a single
basis function; two basis functions are provided for each
valence shell atomic orbital, augmented by a set of polari-
zation functions.
Reaction energy (Er) of a dichlorocarbene molecule with
graphene was defined as follows:
Er ECCl2 =graphene  Egraphene  ECCl2 27. Lu X, Tian F, Zhang Q (2003) J Phys Chem B107:8388
where E(CCl2/graphene) is the total energy of dichloro-
carbene adsorbed on a graphene surface; E(graphene) and
E(CCl2) are the total energies of pristine graphene and an
isolated dichlorocarbene molecule.
Solvation effects were included through the use of a
COSMO model as implemented in Orca 2.9.1. The
GaussSum program was used to obtain the DOS results
[55]. A full width at half the maximum of 0.2 was used to
make the DOS peaks smooth.
Acknowledgment The reported study was supported by RFBR,
research Project No. 14-03-31231 vok_a. Generous allotment of
computational time from Computational Center of Novosibirsk State
University (www.nusc.ru) is gratefully acknowledged.
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