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Carbon Nanostructures
Synthesis of a Porous [14]Annulene Graphene Nanoribbon and a
Porous [30]Annulene Graphene Nanosheet on Metal Surfaces
Tianchen Qin, Dezhou Guo,* Juanjuan Xiong, Xingyu Li, Lei Hu, Weishan Yang,
Zijie Chen, Yulun Wu, Honghe Ding, Jun Hu, Qian Xu, Tao Wang,* and Junfa Zhu*
Abstract: The electrical and mechanical properties of
graphene-based materials can be tuned by the introduc-
tion of nanopores, which are sensitively related to the
size, morphology, density, and location of nanopores.
The synthesis of low-dimensional graphene nanostruc-
tures containing well-defined nonplanar nanopores has
been challenging due to the intrinsic steric hindrance.
Herein, we report the selective synthesis of one-dimen-
sional (1D) graphene nanoribbons (GNRs) containing
periodic nonplanar [14]annulene pores on Ag(111) and
two-dimensional (2D) porous graphene nanosheet con-
taining periodic nonplanar [30]annulene pores on Au-
(111), starting from a same precursor. The formation of
distinct products on the two substrates originates from
the different thermodynamics and kinetics of coupling
reactions. The reaction mechanisms were confirmed by
a series of control experiments, and the appropriate
thermodynamic and kinetic parameters for optimizing
the reaction pathways were proposed. In addition, the
combined scanning tunneling spectroscopy (STS) and
density functional theory (DFT) calculations revealed
the electronic structures of porous graphene structures,
demonstrating the impact of nonplanar pores on the π-
conjugation of molecules.
[*] T. Qin, J. Xiong, X. Li, L. Hu, W. Yang, Z. Chen, Y. Wu, Dr. H. Ding,
Dr. J. Hu, Q. Xu, Prof. Dr. J. Zhu
National Synchrotron Radiation Laboratory, Department of Chem-
ical Physics and Key Laboratory of Surface and Interface Chemistry
and Energy Catalysis of Anhui Higher Education Institutes,
University of Science and Technology of China
Hefei 230029 (P. R. China)
E-mail: jfzhu@ustc.edu.cn
Prof. Dr. D. Guo
State Key Laboratory of Explosion Science and Technology, Beijing
Institute of Technology
Beijing 100081 (P. R. China)
E-mail: dezhoug@bit.edu.cn
Dr. T. Wang
Donostia International Physics Center
20018 San Sebastián (Spain)
E-mail: taowang@dipc.org
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Introduction
The reduction of dimension, heteroatom doping, and the
introduction of nanopores have turned out to be efficient
and routine methods to open the band gap of graphene.[1] In
particular, for porous low-dimensional graphene-based
nanostructures, previous studies revealed that the precise
control of the size, type, location, and arrangement of
nanopores could fine-tune the electronic structures and
might bring in intriguing physical properties into graphene
nanomaterials, such as flat band,[2] tunable
[3] [4]
semiconductivity, and π-magnetism. By using rationally
designed precursor molecules, on-surface synthesis (OSS)
approach has emerged as a powerful platform for the
synthesis of porous low-dimensional graphene-based nano-
structures with atomic precision.
To date, a planar [18]annulene pore and a nonplanar
[14]annulene pore have been the most representative nano-
pores obtained by OSS (Figure 1). [18] and [14]annulene
pores can be considered to be formed by the removal of six
and two internal degree-3 vertices from the graphene
skeleton, respectively. Different from the planar structure of
[18]annulene pore, [14]annulene pore typically exhibits a
nonplanar character due to the steric hindrance between
adjacent hydrogen atoms. In the past decade, various porous
graphene structures containing planar [18]annulene pores
have been successfully synthesized on metal surfaces,
including zero-dimensional (0D) nanographenes,[5] one-
dimensional (1D) graphene nanoribbons (GNRs),[6] and
two-dimensional (2D) graphene nanosheets.[7] However, the
synthesis of graphene structures containing nonplanar
[14]annulene pores[8] has been much more challenging due
to the large steric hindrance inside the pores, resulting in a
high energy barrier for the formation of target structures.
To date, few nanographenes[9] and GNRs[10] containing
[14]annulene pores have been fabricated on surfaces.
However, the quality of the reported [14]annulene porous
GNRs is rather limited, which either contain a number of
defects[10a] or only grow near step edges.[10b] For more
extended systems, i.e., 2D porous graphene nanosheets
containing periodic nonplanar pores, their syntheses still
remained elusive, presumably due to the significant struc-
tural strain and steric hindrance as well as competing side
reactions (e.g., formation of porous GNRs). Therefore, two
open questions (as well as major challenges) arise upon the
synthesis of porous graphene nanomaterials containing
periodic nonplanar pores: 1) how to obtain long-range
ordered nonplanar porous 1D GNRs and 2) how to
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Figure 1. Progress in the synthesis of planar ([18]annulene, filled in red) and nonplanar ([14]annulene, filled in yellow) porous low-dimensional
graphene nanostructures. The nonplanar pores in this work are filled in cyan.
introduce ordered nonplanar pores into 2D graphene
structures.
Herein, by rationally designing the precursor molecule
and using appropriate thermodynamic and kinetic strategies,
we report the selective synthesis of two different graphene-
based nanostructures containing [18] and [14]annulene pores
on different metal substrates. With the aid of scanning
tunneling microscopy (STM), synchrotron radiation photo-
emission spectroscopy (SRPES), and density functional
theory (DFT) calculations, we demonstrate the successful
fabrication of 1D porous GNRs containing periodic
[14]annulene pores on Ag(111) and 2D porous graphene
nanosheet containing periodic [30]annulene pores on Au-
(111), starting from the same precursor 2,7,10,15-
tetrabromodibenzo[a,c]triphenylene (TBDBTP), as illus-
trated in Scheme 1. Together with a series of control
experiments, we unravel that 1) the formation of 1D GNRs
containing [14]annulene pores on Ag(111) is a thermody-
namically controlled pathway due to the reversibility and
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flexibility of C Ag C linked organometallic intermediate
motifs; 2) the formation of 2D graphene nanosheet contain-
ing [30]annulene pores on Au(111) is a kinetics-driven
pathway where the debromination process is the rate limit-
ing step for the initial C C coupling reaction. The electronic
properties of these graphene structures containing periodic
nonplanar pores were investigated by the combination of
scanning tunneling spectroscopy (STS) and DFT calcula-
tions. To our knowledge, porous [30]annulene graphene
nanosheet obtained in our work is the first example for the
synthesis of 2D graphene nanosheets containing periodic
nonplanar pores via OSS approach. This work not only
paves a way to precisely introduce periodic nonplanar pores
to low-dimensional graphene-based nanostructures but also
offers a fundamental mechanistic insight into the thermody-
namic and kinetic strategies for tuning corresponding
reaction pathways.
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Scheme 1. Reaction pathway for the formation of 1D porous GNRs on Ag(111) and 2D porous graphene nanosheets on Au(111), starting from
TBDBTP precursors. Color code: Ag, blue; Br, orange; C, gray; H, white.
Results and Discussion
Synthesis of 1D porous GNRs containing periodic [14]annulene
pores on Ag(111)
Figures 2a–b display the overview and magnified STM
images of the well-ordered supramolecular structure as-
sembled by intact TBDBTP molecules respectively, upon
depositing TBDBTP on a Ag(111) surface held at 150 K. Br
atoms exhibit as bright spots at the terminus of the
molecules,[11] thus the self-assembled structure is most
probably stabilized by the synergy of Br···Br[12] and Br···H
interactions,[13] as visualized by the attached molecular
models in Figure 2b.
Next, we deposited TBDBTP molecules on a Ag(111)
surface preheated at 410 K to trigger the dissociation of
C Br bonds, leading to the formation of linear porous
organometallic polymers (Figures 2c–d). In the high-resolu-
tion STM image in Figure 2d, the H-type motifs are assigned
to the debrominated monomers and the bright protrusions
between monomers are attributed to Ag adatoms (marked
by the yellow circle), as exhibited by the overlaid molecular
model. SRPE spectra support the conclusions above. As
shown in Figure 3a, at 410 K, only the low binding energy
peaks of the Br 3d doublet can be observed, indicating the
complete debromination of TBDBTP, i.e., Br C to Br
adatom transformation.[14] The generated Br adatoms (green
circles in Figure 2d) inlay between organometallic chains via
C H···Br hydrogen bonding stabilization. The formation of
C Ag bonds is evidenced by C 1s SRPE spectra. A 410 K
thermal treatment leads to the disappearance of the C Br
signal observed at 150 K and the appearance of a new peak
at a low binding energy of 383.5 eV, which corresponds to
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C-metal species according to a number of previous
studies.[12b,15] To further verify the formation of C Ag C
bridged porous organometallic polymers, DFT simulation of
the STM image on the basis of an optimized adsorption
configuration of porous organometallic polymers on Ag-
(111) was performed and a good agreement between the
experimental and DFT simulated results was achieved (Fig-
ure S1).
The formation of porous covalent GNRs on Ag(111)
was achieved by further annealing the sample covered by
porous organometallic polymers to 510 K, upon releasing
the interstitial Ag adatoms (Figures 2e–f). The covalent
linkage and formation of [14]annulene pores are clearly
resolved in the high-resolution STM image overlaid with a
structural model (Figure 2f). The morphology of the porous
covalent GNRs revealed in the STM image also matches
perfectly with the DFT simulated results (Figures 2g–h).
Interestingly, in contrast to its nonplanar configuration in
the gas phase,[8] [14]annulene pores in the porous covalent
GNR on Ag(111) display a quasi-planar adsorption geome-
try (Figure 2g), due to a relatively strong molecule-substrate
interaction. The formation of porous covalent GNRs is also
supported by C 1s SRPES, in which the C Ag component
disappears and only the C C component remains at 510 K.
In addition, a ratio of 1:0.9 between C[C3] (a carbon
connecting other three neighboring carbons) and C[C2H] (a
carbon connecting other two neighboring carbons and one
hydrogen) at 510 K is derived from our experiment. This
implies that high-quality porous GNRs are obtained because
the theoretical ratio between C[C3] and C[C2H] changes
monotonically from 1 : 1.6 (a monomer with radical sites
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Figure 2. a,b) Overview and zoom-in STM images of the self-assembled structure obtained by depositing TBDBTP precursors on Ag(111) held at
150 K. Corresponding molecular models are overlaid on (b). Hydrogen and halogen bonds are marked by blue and green dotted lines, respectively.
c,d) Overview and zoom-in (white framed region in c) STM images of the sample prepared by depositing TBDBTP molecules on Ag(111) preheated
at 410 K, forming porous organometallic polymers. Corresponding molecular models are overlaid on (d). The three highly symmetric directions of
the Ag(111) substrate are marked in (c). e,f) Overview and zoom-in (white framed region in e and rotated by 90° to the right) STM images
obtained by annealing the sample in (c) to 510 K, forming porous GNRs containing periodic [14]annulene pores. The three highly symmetric
directions of the Ag(111) substrate are marked in (e). Tunneling parameters: (a,b) U = 0.6 V, I = 139 pA; (c,d) U = 0.7 V, I = 150 pA; (e)
U = 0.5 V, I = 160 pA; (f) U = 0.9 V, I = 140 pA. g,h) DFT-optimized top and front views of the adsorption model (g) and simulated STM image
(h) of porous covalent GNRs on Ag(111). Color code: C, black; surface Ag, gray; H, pink. Ubias is set to 0.7 V.

Figure 3. SRPE spectra of TBDBTP/Ag(111) taken with increasing temperature. Br 3d (a) and C 1s (b) core level spectra were recorded after the
deposition of TBDBTP on Ag(111) at 150 K followed by step-by-step annealing until 510 K. The photon energies used for Br 3d and C 1s are 180
and 380 eV, respectively. (c) Structure models of the main products in each reaction stage. Different atoms are depicted by different colors to
illustrate their chemical environments. The ideal ratios of these C atoms are shown on the right.

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passivated by hydrogen[16]) to 1 : 0.86 (an infinitely porous
GNR) as the GNR length increases (Figure 3c).
Thermodynamic mechanism and control for the formation of
porous GNRs on Ag(111)
As already shown in Scheme 1, starting from TBDBTP
molecules, the formation of porous GNRs and open chains
are two competing pathways. However, in our experiment, a
highly selective synthesis of porous GNRs was achieved on
Ag(111). Next, we focus on elucidating the mechanism.
According to previous studies,[11,17] the formation of a
macrocycle vs. an open-chain (or other thermodynamically
less stable structures) via OSS approach is typically
determined by the competition between reaction thermody-
namics and entropy. In these examples, the reversibility of
organometallic structures plays a decisive role in the
selective synthesis of macrocycles. Although the formation
of organometallic open chains is entropically favorable, they
could transform into a thermodynamically stable state, i.e.,
formation of organometallic macrocycles upon annealing,[17b]
which can be further facilitated by high-dilution synthesis.[17]
Such thermodynamics driven process in organometallic
intermediate state can be thought as a self-healing mecha-
nism. In the next step, these thermodynamically favored
organometallic macrocycles serve as a template for the final
formation of covalent macrocycle products upon higher
annealing. Here, we demonstrate that a similar self-healing
mechanism of organometallic intermediates is equally suit-
able to the high-quality synthesis of porous [14]annulene
GNRs on Ag(111). In our work, the formation of organo-
metallic open chains dominates at a relatively low temper-
ature, e.g., room temperature (RT) (Figure S2), which is a
natural result when only partial debromination of TBDBTP
occurs (as revealed by SRPES in Figure 3). In addition, the
formation of open-chain structures is entropically enhanced
because of their diverse possible geometries. However, after
annealing, these organometallic chains transformed into
thermodynamically more stable porous organometallic poly-
mers and eventually formed porous covalent GNRs upon
higher annealing (Figure S3). Note that the length and
quality of both porous organometallic and covalently linked
GNRs obtained via RT deposition and subsequent annealing
are not as good as those samples prepared by deposition of
TBDBTP onto a 410 K preheated Ag(111) surface followed
by further annealing, as shown in Figures 2c–f. This is
because the surface is covered by organometallic chains,
thus, both inter- and intra-chain steric hindrance could
suppress the diffusion and flipping of monomers.[6,7b,14a,18] In
other words, the thermodynamic self-healing ability trans-
forming the open-chain organometallic structure into porous
organometallic structure is diminished in this case. In
contrast, deposition on a hot surface at a moderate
coverage[19] is similar to a high-dilution synthesis procedure,
thus the steric hindrance effect between molecules is
negligible for the formation of thermodynamically stable
porous organometallic polymers. As a result, high-quality
porous organometallic and eventually covalent GNRs were
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obtained thanks to the high reversibility of organometallic
structures.
The reaction mechanism proposed above is also sup-
ported by previous works and control experiments. Since
the reversibility of organometallic structures plays a decisive
role in this thermodynamics-driven reaction, the reaction
pathway can be tuned by confining the reversibility of the
related organometallic structures. Firstly, in a study from
Wang et al.,[20] two structurally similar molecules with back-
bones longer than that of TBDBTP were used as the
precursors. As reported, relatively disordered structures
were obtained on Ag(111), though including short porous
GNRs. We note that because of the large molecular back-
bone, the molecular motion, particularly molecular flipping
on the surface is significantly suppressed. As a result, the
reversibility of organometallic structures decreases, lowering
the quality of porous organometallic polymer and covalent
GNR. Secondly, on a more reactive Cu(111) surface,[21]
TBDBTP formed rather disordered products (Figure S4). In
the reaction system of TBDBTP/Cu(111), a stronger mole-
cule-substrate interaction[21a,22] also suppresses molecular
motion thus decreasing the reversibility of organometallic
chains. Thirdly, a direct deposition of TBDBTP molecules
onto the Ag(111) substrate preheated at a high temperature
of 530 K also reduced the quality of the porous GNRs, as
shown in Figure S5. This is because the lifetime of C Ag
bonds at a high surface temperature significantly decreases
(forming irreversible C C bonds quickly after
debromination[17]), making the self-healing thermodynamic
effect of organometallic structure less effective.
Overall, the prerequisite for the selective synthesis of
porous GNRs on metal surfaces is the formation of a long
lifetime and highly reversible organometallic structure. This
requires a small precursor (such as TBDBTP), a substrate
with medium reactivity (such as Ag(111)), and a medium
deposition temperature (avoiding direct C C couplings at a
high temperature and steric hindrance at a low temper-
ature).
According to a variety of previous studies, only a few
C Au C linked organometallic intermediates were ob-
served in Ullmann coupling reactions on Au(111).[1,3a,23] This
is because the debromination of organic molecules on
Au(111) typically requires a high temperature, thus, direct
C C coupling occurs immediately after debromination on
Au(111). As stated above, without the participation of
reversible organometallic structures, the thermodynamically
favored pathway, i.e., formation of porous GNRs should not
prevail on Au(111). It probably follows a different reaction
mechanism.
Synthesis of 2D porous graphene nanosheet containing periodic
[30]annulene pores on Au(111)
Figures 4a–b display the overview and magnified STM
images of the sample prepared by the deposition of
TBDBTP on Au(111) at RT. The self-assembled structure
of TBDBTP molecules on Au(111) is similar to that on
Ag(111). TBDBTP molecules remain intact on Au(111) at
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Figure 4. a,b) Overview and zoom-in STM images of the self-assembled structure after depositing the TBDBTP precursors on Au(111) at RT.
Corresponding molecular models are overlaid on (b). c,d) Overview and zoom-in (white framed region in c) STM images obtained by annealing the
sample in (a) to 450 K, revealing the formation of partially debrominated segments and covalently staggered chains. Corresponding molecular
models are overlaid on (d). e,f) Overview and high-resolution (rotated clockwise by 90°) STM images recorded after annealing to 510 K, forming
porous graphene nanosheet containing periodic [30]annulene pores. Tunneling parameters: (a,b) U = 1.2 V, I = 139 pA; (c,d) U = 0.7 V,
I = 131 pA; (e,f) U = 0.7 V, I = 112 pA. g,h) DFT-optimized top, side and front views of the adsorption model (g) and DFT-simulated STM image
(h) of porous graphene nanosheet containing periodic nonplanar [30]annulene pores on Au(111). Color code: C, black; surface Au, yellow; H, pink.
Ubias is set to 0.7 V.

RT, and the four Br terminals are recognized as four bright
protrusions in the high-resolution STM image shown in
Figure 4b, which is supported by previous works[24] and
SRPES in Figure 5. Only one Br 3d doublet is identified and
the C 1s signal corresponding to C Br is clearly resolved.
Staggered chain-like structures were formed after an-
nealing the above sample to 450 K, as shown in Figures 4c–d
and Figure S6 (contours of staggered chains overlaid). The
smooth and seamless connection between monomers implies
their covalent linking, as illustrated by the attached molec-
ular model in Figure 4d. The center-to-center distance
between two next-nearest neighboring monomers is meas-
ured to be 17.63 Å (Figures 4d and S7), supporting the
formation of covalent bonds.[1b,19,21b,23c] The DFT-optimized
adsorption geometry is presented in Figure S8a, showing a
quasi-planar configuration. Based on this adsorption config-
uration, a simulated STM image was obtained, as shown in
Figure S8b, in line with the experimental result. We note
that the formation of the staggered chain is a natural result
of partial debromination at 450 K since only debrominated
sites can couple into covalent motifs. This is supported by Br
3d SRPES (Figure 5), where two Br 3d doublets are
resolved at 450 K. The surviving C Br groups are identified
as bright protrusions, as pointed by the blue arrow in
Figure 4d. In turn, the dissociated Br adatoms filling
between polymeric chains exhibit small and dark feature.
However, not all the terminals of the monomer bear bright
protrusions (C Br bonds) at their uncoupled sites, e.g., the
site pointed by the green arrow in Figure 4d, probably
leaving a σ-radical there. The σ-radical may interact with the
Au surface, leading to the appearance of a C Au signal in C
1s spectrum,[14a,25] although no organometallic intermediates
are formed. Apart from Br adatoms, the relatively bright
and large dots neighbored a C Br terminus (pointed by the
white arrows), which are most probably attributed to Au
adatoms, interacting with a C Br motif via C Br···Au
Coulomb interaction.[12b,22b,26]
Further annealing at 510 K leads to the formation of 2D
porous graphene nanosheet, as shown in Figures 4e–f, which
should be generated from the lateral fusion of covalent
polymers after the desorption of Br adatoms from the
Au(111) surface.[3a,27] According to the SRPES results, only
30 % Br species with respect to the amount of 450 K case is
observed at 510 K (Figure 5a; magnified Br 3d spectra are
shown in Figure S9). In addition to these chemisorbed Br
adatoms, a few Br C components still survive even at such a
high temperature, which corresponds to the bright terminals
of monomers in STM image, as pointed by the yellow arrow
in Figure 4f. This is also in agreement with the Br 3d
spectrum at 510 K, where a Br C component still exists
(Figure S9).
The high-resolution STM image in Figure 4f indicates
that the 2D porous graphene nanosheet possesses an out-of-
plane adsorption configuration on Au(111). Two bright
spots on each monomer (white circle in Figure 4f) corre-
spond to the phenyls pointing outward from the surface, as

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Figure 5. SRPE spectra of TBDBTP/Au(111). Br 3d (a) and C 1s (b) core level spectra were recorded after depositing TBDBTP on Au(111) at 300 K
and then stepwise annealing to 560 K. The photon energies for Br 3d and C 1s are 180 and 380 eV, respectively. (c) Structure models of the main
products in each reaction stage. Different atoms are depicted by different colors to illustrate their chemical environments. The ideal ratios of these
C atoms are shown on the right.
perfectly supported by the DFT-simulated STM image based
on the optimized adsorption model on Au(111) (Figures 4g–
h). Herein, we considered two possible conformations
regarding the relative distortion between adjacent phenyl
rings (Figure S10). The energetically favorable structure
shown in Figure S10a corresponds to our experimental
observation, while the other conformation (ΔE = 1.12 eV)
was not observed. As revealed by DFT calculations, the
monomers have to twist significantly to avoid the huge steric
hindrance between twelve hydrogen atoms inside the narrow
[30]annulene pore, and the phenyl rings form a dihedral
angle of (25° � 5°) with respect to the Au(111) surface.
Because of the twisted conformation, the center-to-center
distance between two next-nearest neighboring monomers
of this 2D covalent structure (17.25 Å; Figures 4f and S7) is
slightly smaller than that from covalent chains in Figure 4d
(17.63 Å). Further annealing to 560 K leads to the quasi-
complete desorption of Br adatoms from the Au(111)
surface, as evidenced by the Br 3d SRPE spectrum in
Figure 5. However, the quality of 2D porous graphene
nanosheet does not improve significantly (Figure S11)
compared to the sample obtained at 510 K.
Kinetic mechanism and control for the formation of 2D porous
graphene nanosheet on Au(111)
According to the experimental and theoretical analyses
above, we propose that the formation of a 2D porous
graphene nanosheet on Au(111) is a kinetics-driven process.
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Because C C coupling is initiated immediately after debro-
mination in this reaction system, debromination is the rate-
limiting step for Ullmann coupling. As a result, the slow
debromination process of TBDBTP on Au(111) (as evi-
denced by SRPES) leads to the preferential formation of
staggered covalent chains.[28] Next, after further debromina-
tion and simultaneous desorption of chemisorbed Br
adatoms on Au(111), these covalent chains fuse laterally,
forming 2D porous graphene nanosheet containing periodic
[30]annulene pores. Experimentally, the starting point for
the lateral fusion between covalent chains is captured at
480 K (Figure S12). As soon as two chains fuse together, the
non-planarization configuration appears at the fusion junc-
tions.
Because of the irreversibility of covalent motifs, a
staggered covalent chain lacks thermodynamic self-healing
ability as an organometallic chain. Therefore, the thermody-
namically favored porous GNR product was not observed
on the Au(111) sample prepared by the step-by-step
annealing procedure. We note that slow debromination is
indispensable for the formation of high-quality staggered
covalent chains and of 2D porous graphene nanosheets in
the following step. As a counter-experiment, we deposited
TBDBTP on a 530 K preheated Au(111) surface to
debrominate most of the molecules once they attached to
the substrate. The obtained structures are less ordered
compared to those from the slow annealing procedure, and
only a few porous GNRs can be observed (Figure S13).
Considering the reaction between TBDBTP after full
debromination, the formation of covalent chains and porous
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GNRs are two competing processes: the former is an
entropically and kinetically (less steric hindrance) favored
pathway and the latter is the thermodynamically favored
pathway. It is thus not surprising to see their coexistence. In
contrast, in an annealing procedure, the slow debromination
process drives the reaction pathway toward the direction for
the formation of covalent chains (debromination is the rate
limiting step for C C coupling), and the irreversibility of
covalent chains makes the generation of porous GNRs
impossible. Therefore, the selective synthesis of porous
graphene nanosheet can be achieved by a slow annealing
experimental strategy.
Electronic structures of the two low-dimensional carbon-based
nanostructures containing periodic nonplanar pores
The topology, aromaticity, and electronic properties of
carbon nanostructures are significantly influenced by their
π-electron conjugation.[29] In particular, the frontier molec-
ular orbitals of graphene-based nanostructures are typically
contributed by π-electrons of carbon atoms. Therefore, 3D
contorted polycyclic aromatic hydrocarbons display quite
different electronic band structures compared to the 2D
analogs.[29b] Herein, we show how the 2D surface confine-
ment influences the band structures and band gaps of the
two carbon-based nanostructures containing periodic non-
planar pores, i.e. 1D porous GNRs containing [14]annulene
pores and 2D porous graphene nanosheet containing
periodic [30]annulene pores, by performing first-principle
calculations (Figure 6). We compare the gas-phase band
structures of the two products with fully relaxed geometry
and surface-confined geometry, respectively. For the porous
GNR, DFT-optimized structural model of the fully-relaxed
and as-adsorbed geometries (optimized on Ag(111)) present
similar configurations, with the molecular dihedral angles
slightly changing from 25.7° to 22.9°. Consequently, they
Figure 6. a,b) DFT-optimized side view of molecule models for the full-relaxed geometry and corresponding band structures of 1D porous GNRs.
c.d) DFT-optimized side view of molecule models for the as-adsorbed geometry on Ag(111) and corresponding band structures of 1D porous
GNRs. e,f) DFT-optimized side view of molecule models for the full-relaxed geometry and corresponding band structures of 2D porous graphene
nanosheet. g,h) DFT-optimized side view of molecule models for the as-adsorbed geometry on Au(111) and corresponding band structures of 2D
porous graphene nanosheet. Color code: C, black; H, pink.
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Angewandte
Chemie
hold comparable π-electron delocalization, thus showing
similar band structures and band gaps (2.1 vs. 2.0 eV).
Compared to 7-AGNR (band gap ~1.6 eV),[30] porous
[14]annulene GNRs open the band gap by about 0.4 eV,
which is attributed to the local confinement of π-electrons
induced by nanopores as well as the weaker π-conjugation
induced by its nonplanarity. In addition, two quasi-flat bands
at both sides of the Fermi level are observed in the band
structure of surface-confined porous GNRs, which is again
probably attributed to an interruption of the delocalization
of π-electrons due to the introduction of nanopores.[31] For
the nonplanar porous graphene nanosheet, the surface-
confined structure (optimized on Au(1111)) presents a much
smaller out-of-plane character than that of the fully relaxed
counterpart. This leads to a more efficient π-conjugation
between pz electrons, thus decreasing the band gap signifi-
cantly from 2.0 to 1.2 eV.
To further investigate the electronic structures of the
novel nonplanar porous 2D graphene nanosheet on Au(111)
experimentally, we employed STS measurements. Figure 7a
illustrates the dI/dV spectra recorded on porous
[30]annulene graphene nanosheet, together with a substrate
background. Two evident resonances at 1.3 and 1.65 V are
resolved in the wide range spectra (Figure 7a) and the other
peak ( 0.8 V) is identified in the zoom-in spectrum with
higher resolution (Figure 7b). We obtained dI/dV maps at
the corresponding energies (Figures 7c–e) and the signals
are attributed to the contribution from conduction band
(CB, at 1.65 V), valence band (VB, at 0.8 V) and VB-1
( 1.3 V), respectively. The band assignment is supported by
a series of additional bias-dependent dI/dV maps (Fig-
ure S14) as well as the good agreement on the density of
state (DOS) distribution between experimental and DFT
(Figures 7f–h) results. Therefore, the band gap of the porous
graphene nanosheet on Au(111) is determined as 2.45 eV.
The relatively large band gap arises from the weak π-
conjugation induced by tilting phenylene units.[7a] Interest-
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Research Articles
Figure 7. Electronic properties of 2D porous graphene nanosheet containing periodic [30]annulene pores. a) long-range and b) zoom-in dI/dV
spectra measured on porous [30]annulene graphene nanosheet at the positions as marked with different colored points in the inset STM image
( 0.5 V, 100 pA). c–e) Constant-current dI/dV maps taken at the voltages of 1.65, 0.8, and 1.3 V, respectively. f–h) DFT-calculated local DOS
distribution of CB, VB and VB-1. All scale bars, 7 Å.
ingly, the electronic wavefunctions corresponding to the
three bands are all predominantly localized on the phenyl
rings pointing outwards from the Au(111) surface. This
implies that the two carbon atoms in the center of a
monomer preferentially take participate into the π-conjuga-
tion of the twisted phenylene units, instead of the quasi-
planar ones. Since the global π-conjugation is disrupted in
the nonplanar structure, the DOS of VB and CB would
distribute over the segments with a larger local π-
conjugation.[32]
Conclusion
In conclusion, we report the surface-mediated synthesis of
two low-dimensional carbon-based nanostructures contain-
ing periodic nonplanar pores, i.e., 1D GNR containing
[14]annulene pores on Ag(111) versus 2D graphene nano-
sheet containing [30]annulene pores on Au(111). The differ-
ence originates from the competition between debromina-
tion and C C coupling of TBDBTP. On Ag(111), the
activation temperature of TBDBTP debromination is much
lower than that of covalent coupling, leading to the
formation of organometallic motifs in the first step. Because
of the reversibility of the C Ag C bond, the organometallic
chain structures transform into porous organometallic poly-
mers as a thermodynamically more stable structure upon
thermal treatment, which acts as a template for the
formation of final porous covalent GNRs upon further
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Chemie
annealing. In contrast, the covalent Ullmann coupling
reaction of TBDBTP occurs immediately after debromina-
tion on Au(111), thus, no organometallic structures are
formed. Instead, staggered covalent chains are generated on
Au(111) after partial debromination of TBDBTP, as a
kinetics-driven pathway. These chains fuse laterally upon
further annealing, forming the final product of porous 2D
graphene nanosheet. These reaction mechanisms are corro-
borated by various control experiments. Supported by DFT
calculations, we revealed the realization of the tunable band
gap by introducing periodic nonplanar pores into low-
dimensional graphene nanostructures, and emphasized the
influence of surface confinement on their band structures.
The experimental band gap and DOS distribution of frontier
molecular orbitals of porous [30]annulene graphene nano-
sheet are revealed by STS and dI/dV maps, showing the
disruption of a global π-conjugation. The synthetic strategies
presented in this work shed light on the controllable
embeddedness of nanopores into low-dimensional carbon
nanostructures.
Acknowledgements
This work was financially supported by the National Natural
Science Foundation of China (22272157, 21872131, and
U1932214), the National Key R&D program of China
(2019YFA0405601), the Users with Excellence Program of
Hefei Science Center CAS (2020HSCUE004), and the
© 2023 Wiley-VCH GmbH

Research Articles
European Union’s Horizon 2020 Research and Innovation
program (Marie Skłodowska-Curie Actions Individual Fel-
lowship, no. 101022150).
Conflict of Interest
The authors declare no conflict of interest.
Data Availability Statement
The data that support the findings of this study are available
from the corresponding author upon reasonable request.
Keywords: Carbon Nanomaterials · Photoemission
Spectroscopy · Reaction Kinetics and Thermodynamics ·
Scanning Tunneling Microscopy · on-Surface Synthesis
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Manuscript received: May 7, 2023
Accepted manuscript online: July 4, 2023
Version of record online: ■■■, ■■■■
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Research Articles Chemie

Research Articles
Carbon Nanostructures Selective syntheses of one-dimensional
graphene nanoribbons containing peri-
T. Qin, D. Guo,* J. Xiong, X. Li, L. Hu, odic nonplanar [14]annulene pores on
W. Yang, Z. Chen, Y. Wu, H. Ding, J. Hu, Ag(111) and two-dimensional porous
Q. Xu, T. Wang,* J. Zhu* e202306368 graphene nanosheet containing periodic
nonplanar [30]annulene pores on Au-
Synthesis of a Porous [14]Annulene Gra- (111) have been achieved. The reaction
phene Nanoribbon and a Porous mechanisms were confirmed by a series
[30]Annulene Graphene Nanosheet on Met- of control experiments, and the appro-
al Surfaces priate thermodynamic and kinetic pa-
rameters for optimizing and tuning the
reaction pathways were proposed.

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