Self-assembly of a halogenated molecule on oxide-passivated Cu(110)

Article abstract of DOI:10.1002/asia.201300283

The supramolecular self-assembly of brominated molecules was investigated and compared on Cu(110) and Cu(110)-O(2×1) surfaces under ultrahigh vacuum. By using scanning tunnelling microscopy, we show that brominated molecules form a disordered structure on Cu(110), whereas a well-ordered supramolecular network is observed on the Cu(110)-O(2×1) surface. The different adsorption behaviors of these two surfaces are described in terms of weakened molecule-substrate interactions on Cu(110)-O(2×1) as opposed to bare Cu(110). The effect of oxygen-passivation is to suppress debromination and it can be a convenient approach for investigating other self-assembly processes on copper-based substrates. Passive resistance: The supramolecular self-assembly of halogenated molecules is achieved on an oxide-passivated Cu(110) surface by tuning the molecule-surface interactions. The Cu(110)-O(2×1) oxygen atoms do not undergo Ullmann cross-coupling reactions, although this reaction is catalyzed by a bare Cu surface, instead suppressing molecule-molecule interactions. Copyright

Full text of DOI:10.1002/asia.201300283

FULL PAPER
DOI: 10.1002/asia.201300283
Self-Assembly of a Halogenated Molecule on Oxide-Passivated CuACTHNUTRGNE(NUG 110)
Mohamed El Garah,*[a] Josh Lipton-Duffin,[a] Jennifer M. MacLeod,[a] Rico Gutzler,[b]
Frank Palmino,[c] Vincent Luzet,[c] Frꢀdꢀric Chꢀrioux,[c] and Federico Rosei*[a, d]
ꢀ
Abstract: The supramolecular self-as-
sembly of brominated molecules was
served on the Cu
The different adsorption behaviors of
these two surfaces are described in
(110) O
E
terms of weakened molecule–substrate
ꢀ
interactions on Cu
posed to bare Cu
T
C
investigated and compared on Cu
N
N
ꢀ
and Cu
(110) O
E
oxygen-passivation is to suppress de-
bromination and it can be a convenient
approach for investigating other self-
assembly processes on copper-based
substrates.
trahigh vacuum. By using scanning tun-
nelling microscopy, we show that bro-
minated molecules form a disordered
Keywords: copper
tion · scanning tunneling microsco-
py self-assembly template
synthesis
·
dehalogena-
·
·
structure on CuACHTUNGTRENNUNG(110), whereas a well-
ordered supramolecular network is ob-
Introduction
strates provides possibilities for enhancing or impeding the
molecule–surface interactions and, by extension, affecting
the structural and electronic properties of the supramolec-
ular structures.[7] Most studies of this nature have focused on
the use of bare substrates; only a handful have reported the
differences between the growth modes of organic molecules
on passivated surfaces.[8] Most of the results show that sur-
face passivation decreases reactivity and favors the forma-
tion of large self-assembled and ordered structures, whereas
the corresponding bare surfaces cause the molecules to
chemisorb in a disordered geometry, such as terephthalic
On-surface noncovalent intermolecular interactions can
drive supramolecular organization in two dimensions, which
can lead to the stabilization of structures that may be used
as active layers in organic electronic devices.[1] Known ex-
amples of 2D self-assembled molecular networks are stabi-
lized by several interactions, such as hydrogen bonds,[2] van
der Waals forces,[3] metal–organic coordination,[4] and halo-
gen bonds.[5] Other interactions based on electrostatic forces
between molecules and the support surfaces can offer addi-
tional pathways for molecular self-assembly.[6] A number of
structures that are based on these intermolecular interac-
tions have been investigated on metal surfaces under ultra-
high vacuum (UHV) and the wide range of available sub-
acid (TPA) on SiACTHNUTRGNEUNG
(111)-7ꢀ7.[8a] Some species may even be
destroyed by certain surfaces, owing to dissociative adsorp-
tion, such as 3,4,9,10-perylene-tetracaboxylic-dianhydride
(PTCDA) on NiACTHNUTRGNEUNG
(111).[9] However, the passivation of Ni with
oxygen decreases its reactivity and allows PTCDA to form
an ordered network.[10] By contrast, some reports have sug-
gested oxidation may even increase a given substrate’s reac-
tivity, such as the self-metalation of porphyrins on Cu-
[a] Dr. M. El Garah, Dr. J. Lipton-Duffin, Dr. J. M. MacLeod,
Prof. Dr. F. Rosei
Centre ꢁnergie, Matꢂriaux et Tꢂlꢂcommunication
Institut National de la Recherche Scientifique
Universitꢂ du Quꢂbec
1650 boulevard Lionel-Boulet
Varennes, QC J3X 1S2 (Canada)
Fax : (+1)450-929-8102
AHCTUNGTRENNUNG
(001).[11]
The {110} facet of copper is a model surface for the study
of molecular adsorption and self-assembly, owing to its high
anisotropy and moderate reactivity. This facet possesses
a strong ability to template molecular orientation and to
direct epitaxial growth, as in the case of pentacene.[12] More-
E-mail: elgarah@emt.inrs.ca
[b] Dr. R. Gutzler
Max Planck Institute for Solid State Research
Heisenbergstraße 1, 70569 Stuttgart (Germany)
over, CuACHTNUTRGNE(UNG 110) can also act as a catalyst for the Ullmann de-
[c] Prof. Dr. F. Palmino, V. Luzet, Dr. F. Chꢂrioux
Institut FEMTO-ST
halogenation of organic molecules at room temperature, as
has been demonstrated for diiodo- and dibromobenzene,[13]
as well as for larger and more-complicated precursors.[14]
However, the mitigation of this catalytic effect by passiva-
ꢀ
Universitꢂ de Franche-Comtꢂ, CNRS, ENSMM
32 Avenue de l’Observatoire
F-25044 Besancon cedex (France)
[d] Prof. Dr. F. Rosei
tion has not been reported so far. The CuACTHNUGRTENNU(G 110) OACHUTGNTREN(NUNG 2ꢀ1) sur-
Center for Self-Assembled Chemical Structures
McGill University
H3A 2K6, Montrꢂal, QC (Canada)
E-mail: rosei@emt.inrs.ca
face can be used as a template for supramolecular self-as-
sembly,[8b,12,15] on which the adsorbed oxygen species lead to
a passivation of the bare CuACTHNUGRTENNUG ACHTUNGTRENNUNG(2ꢀ1)
(110) surface.[8b] The O
overlayer has the advantage of being well-ordered (as op-
posed to having only local order, as found in the oxidations
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/asia.201300283.
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M. El Garah et al.
of other low-index facets of copper),[16] and it also preserves
the inherent anisotropy of the {110} facet.
Herein, we describe the effect of passivating a CuACTHUNTGRNEUNG(110)
surface to facilitate the self-assembly of an ordered network
of halogenated molecules. We compare the growth of
2,3,2’,3’-(tetrabromophenyl-6,6’)biquinoxalinyl
(TBPBQ,
(110) surfaces
ꢀ
Scheme 1) layers on Cu
N
C
N
at room temperature under UHV. X-ray photoelectron spec-
troscopy (XPS) and STM investigations show that TBPBQ
Scheme 1. Chemical structure of TBPBQ.
ꢀ
remains intact on Cu
with a compact 2D structure, whereas the bare surface deha-
logenates the molecule at room temperature.
G
G
Figure 1. STM images of the CuACTHNURTGNEU(GN 110) surface after exposure to TBPBQ
Results and Discussion
at RT: a) Low coverage. Single (blue circle) and dimer structures (black
circle) are observed (45ꢀ45 nm2, Us =ꢀ1.23 V, It =0.59 nA); inset shows
a single TBPBQ dimer (4.1ꢀ4.1 nm2, Us =ꢀ0.65 V, It =1.0 nA). b) Cover-
age close to 1 ML (50ꢀ50 nm2, Us =ꢀ0.90 V, It =1.0 nA).
Figure 1a shows an STM image of a bare CuACTHUNRTGNEUNG(110) surface
with a submonolayer coverage of TBPBQ. Individual mole-
cules appear as bright rectangular shapes. The TBPBQ mol-
ecules are aligned in two directions on the surface, as indi-
cated by the blue circle and the inset image. At room tem-
perature, we observe individual molecules, as well as a cova-
lent dimer structures (blue and black circles, respectively).
To form these structures, the Br atoms must be cleaved
from the TBPBQ, which is expected for halogenated organic
covalent linking or, possibly, by organometallic links
through copper atoms.
Exposing the CuACTHNUTRGNEUNG(110) crystal to oxygen forms a (2ꢀ1) re-
construction, which dramatically decreases the surface’s re-
activity. Densely packed, well-ordered islands in two domain
orientations are formed when TBPBQ is deposited onto Cu-
ꢀ
molecules on CuACHTUNGTRENNUNG
(110) at room temperature.[13] The surface’s
catalytic activity is high enough that we expect every mole-
cule to be completely dehalogenated at room temperature.
Thus, we interpret the single molecules that are imaged on
this surface as being bonded to the substrate at four points
ACHUTGTNREN(NUG 110) OACHTUNGTNER(NUGN 2ꢀ1) (see the Supporting Information, Figure S1).
At low coverages (0.2 ML), the perimeter of the domains is
poorly resolved (Figure 2a), owing to the diffusion of
TBPBQ molecules in and out of the ordered islands on
much-shorter timescales than the acquisition speed of the
STM data (approximately 10ꢀ12 s,[18] versus approximately
30 s for a typical acquisition of STM data). The high mobili-
ty of the molecules at RT is presumably responsible for the
large degree of order in the islands.
ꢀ
(which correspond to the former C Br positions) through
organometallic bonds, whereas the dimer and trimer struc-
tures represent interconnected dehalogenated TBPBQ mol-
ecules, either through direct covalent coupling or, possibly,
through organometallic links that involve surface Cu atoms.
Similar behavior was observed for the adsorption of 4,4’’-di-
We hypothesize that oxidation mitigates the catalytic ac-
tivity of the surface; ex situ XPS of these surfaces at the
Br 3p core level reveals a doublet with the 3p3/2 level at
a binding energy of 184.8 eV (Figure 2b). The same analysis
performed on powdered TBPBQ indicates an identical bind-
ing energy. The Br 3p binding energy for copper-bound bro-
bromo-p-terphenyle on CuACHTNUGRTNEUNG
(111),[17] thus indicating that the
dehalogenative property is present, even on less-reactive
facets of copper.
When the coverage of TBPBQ on CuACHTUNTRGNEUNG(110) is increased,
a network of dumbbell-shaped protrusions is formed on the
surface (Figure 1b) and it becomes more difficult to distin-
guish single molecules. These structures consist of dehalo-
genated molecules that are interconnected by either direct
mine should appear at significantly lower energy (3p3/2
=
182.4 eV)[19] and, thus, we conclude that the TBPBQ mole-
ꢀ
cules remain intact when deposited onto Cu
(110) O
N
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M. El Garah et al.
of individual molecules. Based on these images, we may de-
termine the experimental unit-cell parameters and the mo-
lecular orientation (a1 =1.1
(ꢁ0.1), b1 =3.0(ꢁ0.1 nm; a1 =
138(ꢁ1)8), which may also be written by using the epitaxy
matrix (6ꢀ1j 1 2), thus indicating commensurability with
the surface. The matrix is written with respect to the lattice
vectors as =(0.361 nm, 0) and bs =(0, 0.512 nm) of the under-
ꢀ
lying CuACTHNUGRTNENUG(110) OACHTUNGTRENN(UGN 2ꢀ1) surface. From the packing geometry
as observed by STM, we may determine the particular ad-
sorption site of TBPBQ on the surface. Both the molecules
and the surface are clearly identified in the same STM
image (Figure 2a). A model of the molecular network can
be superimposed over the image, with reference to the un-
derlying substrate as indicated by the black grid (Figure 2c).
We hypothesize that the diagonally opposite bromine atoms
of TBPBQ are positioned above oxygen atoms (Figure 3) in
the substrate, by using the interpretation that the bright pro-
Figure 3. STM images that show the chirality of the TBPBQ domains:
a) 5.1ꢀ5.1 nm2, b) 5ꢀ5 nm2 (Us =ꢀ1.42 V, It =0.7 nA). c) Determination
of the adsorption site of the molecules on the surface (7.7ꢀ8 nm2, Us =
ꢀ0.74 V, It =0.77 nA). d) Tentative structural model of adsorbed TBPBQ
ꢀ
ꢀ
Figure 2. a) STM images of TBPBQ/CuACHTUNTGRENNUG(110) OACHTUNGTNER(NUGN 2ꢀ1) with atomic resolu-
tion (30ꢀ12 nm2, Us =ꢀ0.74 V, It =0.77 nA). b) XPS Br 3p core-level
ꢀ
spectra of TBPBQ powder (red) and TBPBQ on Cu
(blue). c) High-resolution STM image of TBPBQ on Cu
(110) O
E
ꢀ
(110) O
A
150 K (7ꢀ7 nm2, Us =ꢀ1.42 V, It =0.74 nA).
molecules on the CuACTHNUTRGENNUG(110) OACHTUNGTRENN(UGN 2ꢀ1) surface.
ꢀ
room temperature. By extension, we hypothesize that
oxygen passivation of Cu(110) may be sufficient to suppress
the dehalogenative adsorption of all brominated polycyclic
aromatic molecules.
trusions of the CuACTHUNGRTENNU(G 110) OACTHUNGTRENUN(NG 2ꢀ1) surface correspond to the
G
oxygen atoms in the CuO strings.[16b] The long axis of the
molecule is oriented at an angle of 358 to the [001] axis of
the copper lattice.
The driving force for self-assembly must be inherently dif-
ferent from the covalent coupling that is observed on the
bare surface. To better understand the growth of the or-
dered structure, a surface with a coverage of 0.2 ML was
cooled to low temperatures (150 K) and imaged (following
deposition at room temperature). Figure 2c shows the
TBPBQ structure at 150 K, which allows the identification
The use of the epitaxy matrix highlights the observation
that the ordered structure of TBPBQ molecules is commen-
surate with the lattice surface. Each domain is chirally pure
because they only contain a single TBPBQ enantiomorph,
as shown in Figure 3a,b. Whilst gas-phase TBPBQ is not
chiral, prochiral surface adsorption has received considera-
ble attention.[2a,b,20] The second domain orientation can be
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M. El Garah et al.
described by the matrix (6ꢀ1j 1ꢀ2), thus indicating mirror
symmetry about the [001] direction of the copper lattice.
The formation of large 2D molecular self-assembled net-
ꢀ
need for surface interactions was demonstrated by the fact
that the molecules were observed to self-assemble at the so-
lution/AuACTHNUTRGNEUG(N 111) interface but not at the solution/HOPG in-
works of TBPBQ on a Cu
(110) O
G
terface, because HOPG is much less reactive than gold.
because of the weakened molecule–surface interactions
compared to the bare substrate. The packing geometry im-
plies the presence of several intermolecular bonds between
each TBPBQ molecule and its nearest neighbours. Density
functional theory (DFT) calculations were used to provide
a fuller description of the forces that drive supramolecular
organization. However, calculations that were performed by
using periodic boundary conditions (PBCs) with the experi-
mentally observed unit-cell parameters (a2 =3.0, b2 =1.1 nm;
a2 =1388) did not converge. Allowing a2 to vary during the
geometry optimization produced the model as shown in the
Supporting Information, Figure S2, in which the a2 angle in-
creased to 1428. However, a change in the angle by 48 led to
an incommensurate structure, as indicated by a schematic
representation of the simulated model (a2 =1428), compared
ꢀ
Experimental Section
Starting materials were purchased from Aldrich and used without further
purification. This synthesis is based on the method of Wang et al.[22]
A
mixture of 4,4’-dibromobenzil (6.0 mmol, 2.25 g) and 3,3’-diaminobenzi-
dine tetrachloride hydrate (2.5 mmol, 1.0 g) in nBuOH (50 mL) was
heated at reflux under a nitrogen atmosphere for 16 h. After cooling to
RT, the solvent was removed under reduced pressure and the residue was
washed with hot CH2Cl2 (150 mL) and then with hot DMSO (150 mL).
The pure compound was isolated as an orange powder (see the Support-
ing Information, Figure 6).
A
saturated solution of 2,3,2’,3’-(tetrabromophenyl-6,6’)biquinoxalinyl
(TBPBQ) was prepared in 1,2,4-trichlorobenzene. This solution was de-
posited onto either freshly cleaved HOPG(0001) or flame-annealed Au
AHCTUNGTRENNUNG
on mica, whose (111) surface was confirmed by the presence of a herring-
bone reconstruction in the STM images. STM images were obtained in
constant-current mode on a NanoScope IIIa STM from Digital Instru-
ments Inc. (Veeco) at RT under ambient conditions. STM tips were me-
chanically cut from platinum/iridium wire.
to the structure observed on CuACHTUNTRGNEN(GU 110) OACHTUTGNREN(NUGN 2ꢀ1) (a2 =1388;
see the Supporting Information, Figure S3). Thus, although
gas-phase modelling is an adequate method for describing
self-assemblies on inert substrates,[21] it cannot reproduce
ꢀ
STM experiments on Cu substrates were performed by using a variable-
temperature microscope (Omicron NanoTechnology GmbH) in an ultra-
high-vacuum chamber at a base pressure of lower than 5ꢀ10ꢀ11 mbar.
the experimentally observed structure on CuACTHUNRGTENNUG(110) OHCATUNGTRENN(UGN 2ꢀ1).
We conclude that the surface has a non-negligible effect on
self-assembly. Because the gas-phase DFT calculations do
not give a unit cell that is close the experimental one, we
conclude that the surface must drive some aspects of the as-
sembly, in particular given the commensurability of the mo-
lecular islands. This interpretation is supported by experi-
ments at the solution/solid interface on highly oriented pyro-
lytic graphite (HOPG), which is a much more inert surface
that can be used to investigate intermolecular forces during
self-assembly with a much lower degree of influence on the
The Cu
(Ar+, 1.5 keV) and annealing (800 K). The O
prepared by dosing 0.5–1 Langmuir (1 L=10ꢀ6 Torrsꢀ1
oxygen whilst keeping the Cu
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
)
AHCTUNGTRENNUNG
where.[17] STM images were acquired in constant-current mode by using
etched tungsten tips. For the studies at low temperatures, the system was
cooled by using liquid nitrogen. The data were subsequently corrected by
using the free WSxM software.[23]
The Gaussian 09[24] program package was employed for the density func-
tional theory calculations, by using the 6–31GACTHNUTRGENUG(N d,p) basis set and the M06-
L functional to calculate the weak intermolecular interactions.[5c] Calcula-
tions were performed on single molecules and with periodic boundary
conditions (PBCs). Several models with different parameters were simu-
lated to mimic the 2D crystalline nature of the observed structures. Unit
cells with both free and frozen parameters and both flat and twisted
cores were calculated.
adsorption site, and AuACTHUNRGTNE(NUG 111), which is a somewhat more-re-
active surface than HOPG. Under identical conditions, no
self-assembly of TBPBQ was observed on HOPG, but small
domains of ordered molecules were formed on AuACTHNUTRGENUG(N 111) (see
the Supporting Information, Figure S4). This result is in line
with our hypothesis that a non-negligible surface interaction
is required to stabilize a conformation that favours the for-
mation of intermolecular bonds. Gas-phase TBPBQ possess-
es a twisted conformation at room temperature (see the
Supporting Information, Figure S5). A strong interaction
with the surface is likely necessary to flatten the core and to
provide an optimal packing geometry.
Acknowledgements
This work was supported by the Natural Sciences and Engineering Re-
search Council of Canada (NSERC) through a Discovery Grant, the
Fonds Quebecois sur la Recherche en Nature et Technologies (FQRNT)
through a Team Grant, and the Ministere du Developpement Economi-
que de l’Innovation et de l’Exportation (MDEIE) through an internation-
al collaboration grant. F.R. is grateful to the Canada Research Chairs
Program for partial salary support. The DFT calculations were performed
by using the computing resources that were provided by WestGrid and
Compute/Calcul Canada. The authors are grateful to Prof. Dmitrii Pere-
pichka for his helpful comments during the preparation of this manu-
script.
Conclusions
By pre-oxidizing a CuACTHNUGRTENUNG(110) surface, we are able to obtain
a 2D ordered pattern of TBPBQ, which is driven by a bal-
ance between molecule–molecule and molecule–surface in-
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Received: March 1, 2013
Published online: && &&, 0000
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Chem. Asian J. 2013, 00, 0 – 0
ꢃ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
These are not the final page numbers! ÞÞ

FULL PAPER
Self-Assembly
Passive resistance: The supramolecular
self-assembly of halogenated molecules
is achieved on an oxide-passivated Cu-
Mohamed El Garah,*
Josh Lipton-Duffin,
ACHTUNGTRENN(UNG 110) surface by tuning the molecule–
ꢀ
Jennifer M. MacLeod, Rico Gutzler,
Frank Palmino, Vincent Luzet,
Frꢀdꢀric Chꢀrioux,
surface interactions. The CuACHTUNGTRNE(NUNG 110) O-
AHCTUNGTRENGN(UN 2ꢀ1) oxygen atoms do not undergo
Ullmann cross-coupling reactions,
although this reaction is catalyzed by
a bare Cu surface, instead suppressing
molecule–molecule interactions.
Federico Rosei*
&&&& — &&&&
Self-Assembly of a Halogenated Mole-
cule on Oxide-Passivated CuACTHNUTRGNE(UNG 110)
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Chem. Asian J. 2013, 00, 0 – 0
ꢃ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!