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org/JACS Communication

Direct Construction of 2D Conductive Metal−Organic Frameworks

from a Nonplanar Ligand: In Situ Scholl Reaction and Topological
Modulation
Meiling Qi,# Yi Zhou,# Yongkang Lv, Weiben Chen, Xi Su, Ting Zhang, Guolong Xing, Gang Xu,
Osamu Terasaki, and Long Chen*
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ABSTRACT: Two-dimensional conductive metal−organic frameworks (2D c-MOFs) are an emerging class of promising porous
materials with high crystallinity, tunable structures, and diverse functions. However, the limited topologies and difficulties in
synthesizing suitable organic linkers remain a great challenge for 2D c-MOFs synthesis and applications. Herein, two layered 2D c-
MOF polymorphs with either a rhombus structure (sql-TBA-MOF) or kagome structure (kgm-TBA-MOF) were directly
constructed via in situ Scholl reaction and coordination chemistry from a flexible and nonplanar tetraphenylbenzene-based ligand
(8OH-TPB) in a one-pot manner. Interestingly, the kgm-TBA-MOF comprising hexagonal and triangular dual pores exhibit higher
conductivities of 1.65 × 10−3 S/cm at 298 K and 3.33 × 10−2 S/cm at 353 K than that of sql-TBA-MOF (4.48 × 10−4 and 2.90 ×
10−3 S/cm, respectively). Moreover, the morphology and topology can be modulated via the addition of ammonium hydroxide as
modulator. The present work provides a new pathway for design, synthesis, and topological regulation of 2D c-MOFs.

T wo-dimensional conductive metal−organic frameworks

(2D c-MOFs), featuring a graphene-like 2D layered
structure, are typically constructed via reticular chemistry
between transition metal ions and highly planar ligands
containing multitopic ortho-substituted coordination sites
(−NH2, −OH, −SH, or −SeH).1−4 The merits of strong in-
plane d-π conjugation between metallic nodes and π-
conjugated organic ligands together with compact interlayer
π−π stacking interaction render 2D c-MOFs as an emerging
class of 2D functional porous materials.5 Benefiting from the
delightful structural adjustability, high porosity with open
channels, intrinsic electrical conductivity, and efficient
conjugation over the 2D skeleton, 2D c-MOFs have been
recently explored in magnetism, electrocatalysis, energy
storage, etc.6−13 Especially, the structurally adjustable π-
conjugated ligands and tunable metal ions are beneficial to
achieving high conductivity and explore new applications.14,15
Nevertheless, the structural diversity (e.g., chemical composi-
tion, topology) of 2D c-MOFs is quite limited probably due to
the lack of suitable ligands. One promising strategy for
developing new ligands for 2D c-MOFs lies in enlarging the
molecular size of the central polycyclic aromatic core, which
could enhance the interlayer π−π interactions as well as the
electron delocalization. However, this approach unfortunately
not only requires multistep synthesis but also affords
polyfunctional ligands that are hardly soluble and prone to
oxidation. On the other hand, starting from flexible nonplanar
monomers with good solubility to obtain 2D c-MOFs through
postmodification synthesis is an alternative, which, however, in
most cases results in 3D MOFs.16
Besides, the reported topologies of 2D c-MOFs are mainly
limited to triangular, tetragonal, hexagonal structures. Kagome
lattices bearing inherent triangular and hexagonal pores are
known to exhibit exotic quantum magnetic states17 and high
conductivity,18 which are usually observed for 2D covalent
organic frameworks (COFs).19 Unfortunately, to the best of
our knowledge, 2D c-MOFs with kagome structure have not
yet been reported. The reported organic ligands for
constructing 2D c-MOFs are mainly C3, C4, and C6 symmetric
linkers, which mainly afford 2D c-MOFs with hexagonal,
tetragonal, and hexagonal structures, respectively.20−22 Organic
linkers with D2 symmetry capable of constructing both
rhombic and kagome 2D c-MOFs are extremely scarce. In
addition, the morphologies of 2D c-MOFs usually affect the
eventual properties.23,24 It has been revealed that the
morphologies and topologies of 2D c-MOFs largely depend
on a variety of factors (solvent, temperature, additive, etc.).25,26
Various approaches including modulating the electronic
structure of ligands,27 regulating metal nodes,25−27 and varing
preparation techniques28 have been developed to tune the
morphologies of 2D c-MOFs. Nonetheless, it remains a great
challenge to modulate the topologies of 2D c-MOFs at will.
Herein, we reported the in situ synthesis of 2D c-MOFs by
employing a flexible nonplanar octahydroxyl tetraphenylben-
zene (8OH-TPB) as the ligand in a one-pot manner.
Systematic structural analysis indicates that the one-pot
Received: October 10, 2022
Published: December 14, 2022

© 2022 American Chemical Society https://doi.org/10.1021/jacs.2c10717

2739 J. Am. Chem. Soc. 2023, 145, 2739−2744
Journal of the American Chemical Society
synthesized 2D c-MOFs adopted an identical layered structure
with that prepared from the planar counterpart of octahydroxyl
tetrabenzoanthracene (8OH-TBA), which was synthesized
from 8OH-TPB via a further cyclodehydrogenation. Moreover,
tunable topologies of either a single pore rhombic structure
(sql-TBA-MOF) or a dual pore kagome structure (kgm-TBA-
MOF) are easily accessible from both ligands by simply
adjusting the dosage of ammonium hydroxide as the
modulator. Interestingly, these two 2D c-MOFs with distinctly
different topologies exhibit different morphologies (rhombus
nanorods for sql-TBA-MOF and hexagonal nanoflakes for
kgm-TBA-MOF). Thus, our current work not only realizes the
adjustment of the topology and morphology of 2D c-MOFs
but also provides a new approach for facile preparation of 2D c-
MOFs directly from flexible nonplanar ligands which could
greatly simplify the synthesis.
The nonplanar 8OH-TPB with D2 symmetry was prepared
through modified Suzuki coupling and further demethylation
reactions (Scheme S1). As a comparison, planar 8OH-TBA
with the same symmetry was synthesized by Scholl reaction
and further demethylation from octamethoxy tetraphenylben-
zene (8OCH3-TPB) and both were ambiguously characterized
(Figures S1−S11). Single-crystal X-ray analyses reveal that
8OH-TBA possesses a nearly planar structure, whereas 8OH-
TPB adopts a twisted butterfly structure (Figures 1, S12 and
Figure 1. Schematic illustration of the one-pot synthesis, topological
modulation and digestion of sql-TBA-MOF and kgm-TBA-MOF. The
top and side views of the single crystal structures of the ligands of
8OH-TPB and 8OH-TBA were compared.
S13). The rotation of carbon−carbon (C−C) single bonds
between the adjacent phenyl rings of 8OH-TPB endows the
ligand with excellent solubility. Then, starting from 8OH-TPB
and 8OH-TBA, two 2D c-MOF samples were respectively
prepared with copper acetate monohydrate in a mixture of
N,N-dimethylformamide (DMF)/deionized water (H2O) (1/
4, v/v) at 85 °C for 3 days as purple-black solids in ∼85% yield
(Figure 1, Schemes S2 and S3). To our great suprise, the
powder X-ray diffraction (PXRD) patterns of the 2D c-MOF
samples synthesized from different monomers (i.e., 8OH-TPB
and 8OH-TBA) are identical (Figures S14 and S15). Such an
unexpected result suggests that cyclodehydrogenation of the
TPB cores might occur during the solvothermal synthesis. In
contrast, when adding ammonium hydroxide as the modulator,
an obviously different PXRD pattern was observed, demon-
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strating the possibility for topologies and morphologies
modulation.
As one of the most straightforward methods, digestion has
been commonly applied to dissociate COFs and MOFs to
confirm the actual building units.29 To verify our hypothesis,
sql-TBA-MOF and kgm-TBA-MOF obtained from 8OH-TPB
and 8OH-TBA were digested under acidic conditions
according to the literatures,30 which are further characterized
by 1H NMR. 1H NMR spectra show that the digested products
are 8OH-TBA but not 8OH-TPB in all cases (Figures S16−
S18). These results demonstrate that 8OH-TPB probably
undergoes cyclization during the 2D c-MOF preparation. The
occurrence of the unexpected cyclization could be further
verified by ultraviolet−visible (UV−vis) and MALDI-TOF-MS
spectra (Figures S19−S21). To exclude the influence of
digestion, identical digestion treatments were applied for the
monomer 8OH-TPB. The reserved 1H NMR spectrum of
8OH-TPB illustrates the absence of cyclization under the
digestion conditions (Figure S22). These results indicate the in
situ oxidative cyclodehydrogenation of 8OH-TPB occurs
during the solvothermal synthesis. Fourier-transform infrared
(FT-IR) spectra reveal the near disappearance of the O−H
stretching vibration bands belonging to the ligand 8OH-TBA
in both sql-TBA-MOF and kgm-TBA-MOF (Figures S23 and
S24), indicating the deprotonation and subsequent formation
of Cu−O coordination bonds. Moreover, the UV−vis spectra
of sql-TBA-MOF and kgm-TBA-MOF are broadened
compared to the monomer, demonstrating the formation of
large conjugated structures (Figures S25 and S26). X-ray
photoelectron spectroscopy (XPS) results indicate successful
coordination between the monomers and metal ions with a
trace amount of NH4OH existing in the structure of kgm-TBA-
MOF (Figures S27−S28). These results indicated that layered
sql-TBA-MOF and kgm-TBA-MOF were readily obtained via a
one-pot synthesis procedure using the nonplanar ligand 8OH-
TPB via in situ Scholl reaction and coordination.
Notably, conjugated polyhydroxyl ligands were generally
synthesized from their corresponding methoxy monomers via
Scholl coupling and further demethylation reactions. Unfortu-
nately, Scholl reaction inevitably requires the use of Lewis
acids (Al2O3, FeCl3, Ni(OAc)2, CF3O(Et)2, TfOH, etc.),31−33
oxidants (DDQ),31,34 and hazardous solvents (e.g., MeNO2).31
Inspired by the above phenomenon, we found that 8OH-TBA
could be directly synthesized from 8OH-TPB in water through
simply heating at 85 °C for 3 days in a high yield of 98%
(Scheme S1, Figure S29). This process could also occur in
other solvents like DMF, DMF/H2O, H2O/NH4OH, and
H2O/CH3COOH (Figure S30), while no reactions are
observed in the case of the counterpart without phenolic
hydroxyl groups (Figure S31). One possible reason is that the
electron-rich phenolic hydroxyl groups promote the formation
of radical cations as the key intermediates for cyclo-
dehydrogenation as demonstrated before.35,36 The above
results further demonstrate the feasibility of in situ cyclo-
dehydrogenation of the nonplanar ligand 8OH-TPB during the
MOF synthesis process.
The topologies and detailed structures of the two 2D c-
MOFs (sql-TBA-MOF and kgm-TBA-MOF) were determined
by comparative analysis of the experimental data with
structural simulation. The experimental PXRD patterns
(purple for sql-TBA-MOF and blue for kgm-TBA-MOF,
Figure S32) are in good agreement with calculated ones with
AA stacking (sql-AA in green and kgm-AA in pink, Figure
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Journal of the American Chemical Society
S32). The profile of Pawley refinement shows a good match
between experimental data and calculations (Figure 2a and
Figure 2. Characterization of the 2D c-MOFs. PXRD patterns of (a)
sql-TBA-MOF and (b) kgm-TBA-MOF. Experimental patterns
(black), refined patterns (red), the difference between experimental
and refined patterns (pink), simulated pattern (blue) and positions of
reflections (green), insets are top views of the slipped AA stacking
modes of sql-TBA-MOF and kgm-TBA-MOF, respectively. N2
sorption isotherms measured from (c) sql-TBA-MOF and (d) kgm-
TBA-MOF at 77 K, and pore size distribution and BET surface area
obtained from the isotherms.
2b). In addition, the Rwp and Rp values of sql-TBA-MOF and
kgm-TBA-MOF converged to 3.58% and 2.58%, 2.75% and
1.96%, respectively. Finally, an orthorhombic unit cell with
parameters (a = 22.662 Å, b = 21.570 Å, and c = 3.191 Å, α = β
= γ = 90°) could be reasonably assigned to sql-TBA-MOF. In
sharp contrast, a kagome lattice with unit cell parameters of a =
30.201 Å, b = 30.201 Å and c = 3.256 Å, α = β = 90°, γ = 120°
was determined for kgm-TBA-MOF. The Brunauer−Emmett−
Teller (BET) surface areas calculated from the N2 adsorption
isotherms for sql-TBA-MOF and kgm-TBA-MOF are 513 and
460 m2 g−1 (Figures 2c, 2d, S35 and S36), respectively. The
pore size distributions for kgm-TBA-MOF and sql-TBA-MOF
were calculated by the nonlocal density functional theory
(NLDFT) method. Two dominant pore sizes centered at 0.86
and 1.66 nm were obtained for kgm-TBA-MOF, which fit well
with the hexagonal and triangular channel widths in the
kagome lattice. In contrast, a single pore size of 1.25 nm was
observed for sql-TBA-MOF (Figure 2c and 2d).
Scanning electron microscopy (SEM) and high-resolution
transmission electron microscopy (HR-TEM) reveal that sql-
TBA-MOF features a 100 nm-wide rhombus nanorods
morphology (Figures 3a and 3b, S33a and S33b), while kgm-
TBA-MOF exhibits a hexagonal nanoflake morphology with a
diameter of ca. 200−400 nm and thickness of ca. 50 nm
(Figures 3d and 3e, S33d, S33e and S34). HR-TEM images
reveal the distances between the lattice fringes are 1.52 nm
(Figures 3c and S33c, sql-TBA-MOF) and 2.6 nm (Figure
S33f, kgm-TBA-MOF), which agree well with the d-spacing of
the (110) plane for sql-TBA-MOF and the (100) plane for
kgm-TBA-MOF, respectively. The kinks feature of sql-TBA-
MOF might originate from the unfinished growth process, as
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Figure 3. SEM images of (a) sql-TBA-MOF and (d) kgm-TBA-MOF.
TEM images of (b) sql-TBA-MOF, (e) kgm-TBA-MOF, (c) zoom-in
view image from the red squares in (b), and (f) high-magnification
image for kgm-TBA-MOF.
they are found to be constructed into the final orthorhombic
crystals gradually (Figure S33b). Notably, a direct proof of the
kagome topology with hexagonal and triangular dual pores for
kgm-TBA-MOF was clearly visualized as presented in the HR-
TEM image (Figure 3f). A central larger hexagonal channel
was surrounded by six triangular shaped smaller channels as
illustrated by the two types of white spots with different shapes
and sizes in Figure 3f. These results further confirm the
feasibility of topological modulation by regulating ammonium
hydroxide as a modulator.
To further investigate the electrical properties of sql-TBA-
MOF and kgm-TBA-MOF, the electrical conductivities were
measured by the two-probe method using pressed pellet
samples under air. As shown in Figure 4a and 4b, the electrical
conductivity of kgm-TBA-MOF is larger than that of sql-TBA-
MOF at room temperature and exhibits a positive temperature
correlation in the range 298 to 353 K, which might be
attributed to the hexagonal nanoflake morphology of kgm-
TBA-MOF that facilitates the in-plane charge transport.6 The
values are as high as 1.65 × 10−3 S/cm at 298 K and 3.33 ×
10−2 S/cm at 353 K, which are significantly higher than that of
sql-TBA-MOF (4.48 × 10−4 S/cm at 298 K and 2.90 × 10−3
S/cm at 353 K). Additionally, kgm-TBA-MOF and sql-TBA-
MOF present thermally activated charge transport behavior
according to the variable temperature conductivity measure-
ments, which reveals an apparent semiconducting behavior in
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J. Am. Chem. Soc. 2023, 145, 2739−2744
Journal of the American Chemical Society
Figure 4. (a) I−V curves of kgm-TBA-MOF (pink line) and sql-TBA-
MOF (blue line). (b) Variable-temperature conductivity for kgm-
TBA-MOF (pink line) and sql-TBA-MOF (blue line). (c and d)
Arrhenius fitting of temperature-dependent conductivity data for kgm-
TBA-MOF (pink line) and sql-TBA-MOF (blue line), respectively.
these two 2D c-MOFs (Figure 4c and 4d). The plot of lnσ
versus T−1/4 can be well fitted to the Mott variable range
hoping (Mott-VRH) model,37 which indicates the temperature
dependence of hopping conductivity in the polycrystalline
MOF pellets (Figure S44). Moreover, the chemical stability
tests indicate that sql-TBA-MOF and kgm-TBA-MOF are
stable in common organic solvents and aqueous NaOH
solutions as verified by PXRD patterns and FT-IR spectra
(Figures S37−S41). Thermogravimetric analysis (TGA) shows
that sql-TBA-MOF and kgm-TBA-MOF start to decompose
likely above 250 °C (Figures S42−S43).
In summary, we synthesized two 2D c-MOFs (sql-TBA-
MOF and kgm-TBA-MOF) with different topologies by simply
tuning the modulator of ammonium hydroxide. The formation
of kgm-TBA-MOF might be a synergistic result of thermody-
namic favorability and the efficient coordination between the
ligands and sterically less-hindered [Cu(NH3)4]2+ (Figure
S45). Instead of using the conventional planar ligand with poor
solubility, these 2D c-MOFs can be directly synthesized from a
flexible D2 symmetrical ligand with good solubility via a one-
pot strategy. kgm-TBA-MOF represents the first dual-
channeled 2D c-MOFs with kagome structure. Interestingly,
the kgm-TBA-MOF comprising hexagonal and triangular dual
pores exhibits larger conductivities than those of sql-TBA-
MOF. This work provides not only an efficient pathway to
synthesize layered 2D c-MOFs directly from easily accessible
nonplanar ligands with better solubility but also new insights
into morphological regulation. Such 2D c-MOFs with the
kagome lattice may find great application potentials in
electromagnetism, sensing, and energy-related areas, which is
currently ongoing in our laboratory.
■ ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/jacs.2c10717.
Experimental details and characterization of the ligands,
sql-TBA-MOF, and kgm-TBA-MOF. (PDF)
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pubs.acs.org/JACS Communication
Accession Codes
CCDC 2162070 and 2162072 contain the supplementary
crystallographic data for this paper. These data can be obtained
free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by
emailing data_request@ccdc.cam.ac.uk, or by contacting The
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
■ AUTHOR INFORMATION
Corresponding Author
Long Chen − Department of Chemistry, Tianjin Key
Laboratory of Molecular Optoelectronic Science, Tianjin
University, Tianjin 300072, China; State Key Laboratory of
Supramolecular Structure and Materials, College of
Chemistry, Jilin University, Changchun 130012, China;
orcid.org/0000-0001-5908-266X; Email: long.chen@
tju.edu.cn, longchen@jlu.edu.cn
Authors
Meiling Qi − Department of Chemistry, Tianjin Key
Laboratory of Molecular Optoelectronic Science, Tianjin
University, Tianjin 300072, China
Yi Zhou − School of Physical Science and Technology and
Shanghai Key Laboratory of High-Resolution Electron
Microscopy, ShanghaiTech University, Shanghai 201210,
China
Yongkang Lv − Department of Chemistry, Tianjin Key
Laboratory of Molecular Optoelectronic Science, Tianjin
University, Tianjin 300072, China
Weiben Chen − Department of Chemistry, Tianjin Key
Laboratory of Molecular Optoelectronic Science, Tianjin
University, Tianjin 300072, China
Xi Su − Department of Chemistry, Tianjin Key Laboratory of
Molecular Optoelectronic Science, Tianjin University, Tianjin
300072, China
Ting Zhang − Department of Chemistry, Tianjin Key
Laboratory of Molecular Optoelectronic Science, Tianjin
University, Tianjin 300072, China
Guolong Xing − Department of Chemistry, Tianjin Key
Laboratory of Molecular Optoelectronic Science, Tianjin
University, Tianjin 300072, China
Gang Xu − Fujian Institute of Research on the Structure of
Matter, Chinese Academy of Sciences, Fuzhou, Fujian
350002, China; orcid.org/0000-0001-8562-0724
Osamu Terasaki − School of Physical Science and Technology
and Shanghai Key Laboratory of High-Resolution Electron
Microscopy, ShanghaiTech University, Shanghai 201210,
China; orcid.org/0000-0001-5803-0817
Complete contact information is available at:
https://pubs.acs.org/10.1021/jacs.2c10717
Author Contributions
#
M.Q. and Y.Z. contributed equally to this work.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was financially supported by National Natural
Science Foundation of China (51973153, 21875140) and the
National Key Research and Development Program of China
(2017YFA0207500). This work was also supported by the
center for high-resolution electron microscopy (CℏEM),
https://doi.org/10.1021/jacs.2c10717
J. Am. Chem. Soc. 2023, 145, 2739−2744
Journal of the American Chemical Society
ShanghaiTech University (EM02161943) and Shanghai
Science and Technology Plan (21DZ2260400). The authors
thank Prof. Yanhang Ma at ShanghaiTech University for his
scientific discussions.
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