Catalytic asymmetric synthesis of chiral covalent organic frameworks from prochiral monomers for heterogeneous asymmetric catalysis

Article abstract of DOI:10.1021/jacs.0c07461

Direct synthesis, postsynthetic modification, and chiral induction have been recognized as three powerful methods to synthesize chiral covalent organic frameworks (CCOFs). However, catalytic asymmetric methodology, as the most important and effective synt

Full text of DOI:10.1021/jacs.0c07461

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Communication
Catalytic Asymmetric Synthesis of Chiral Covalent Organic Frameworks
from Prochiral Monomers for Heterogeneous Asymmetric Catalysis
Jian-Cheng Wang, xuan kan, Jin-Yan Shang, Hua Qiao, and Yu-Bin Dong
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.0c07461 • Publication Date (Web): 17 Sep 2020
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Catalytic Asymmetric Synthesis of Chiral Covalent Organic Frameworks
from Prochiral Monomers for Heterogeneous Asymmetric Catalysis
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‡
‡
Jian-Cheng Wang, Xuan Kan, Jin-Yan Shang, Hua Qiao, and Yu-Bin Dong*
College of Chemistry, Chemical Engineering and Materials Science, Collaborative Innovation Center of Functionalized
Probes for Chemical Imaging in Universities of Shandong, Key Laboratory of Molecular and Nano Probes, Ministry of
Education, Shandong Normal University, Jinan 250014, P. R. China
ABSTRACT: Direct synthesis, post-synthetic modification and chiral induction have been recognized as three powerful
methods to synthesize chiral covalent organic frameworks (CCOFs). However, catalytic asymmetric methodology, as the most
important and effective synthetic approach to access chiral organics, has not been enabled for CCOFs synthesis thus far.
Herein we report, for the first time, the construction of CCOFs from prochiral monomers via catalytic asymmetric
polymerization. The obtained propargylamine-linked CCOFs can be the highly reusable chiral catalysts to promote
asymmetric Michael addition reactions. The concept of catalytic asymmetric polymerization might open a new route for
constructing the CCOFs that are not possible with the existing CCOF synthetic methods.
Since Yaghi et al. reported the first example of covalent
organic framework (COF) in 2005, COF-chemistry has
Inspired by the large library of asymmetric organic
reactions, we surmise that CCOFs can also be prepared by
catalytic asymmetric polymerization of the prochiral
monomers with the aid of chiral catalysts. To test the
possibility, we chose to employ the multicomponent one-
1
grown at
a
breathtaking pace. In addition to
2
3
4
adsorption/separation, sensing, and biomedical uses, a
surge of interest has occurred in COF-based catalysis.
5
1
1
Compared with the vigorous development of achiral COF
synthesis and their symmetric catalysis, the chiral covalent
organic framework (CCOF) synthesis and CCOF-based
asymmetric catalysis, however, has drawn much less
pot in situ catalytic asymmetric polymerization of
divergent achiral dialdehyde, triamine with terminal aryl
alkyne to prepare the propargylamine-linked CCOFs. As we
1
2
know, the chiral pyridine-2,6-bis(oxzolines)-Cu(I)
6
attention. Nevertheless, as new appointee in asymmetric
complexes are highly efficient catalysts for the synthesis of
chiral propargylamines from prochiral aldehydes, amines,
catalysis, the CCOF-based catalysts are walking into the
sight field of chemists. For example, several recent reports
3
and alkynes under mild conditions via A -coupling
7
8
13
show that the organocatalysts, metal nano particles, and
reactions.
9
metal-ion loaded CCOFs can efficiently promote
As shown in Scheme 1, the model reaction among
benzaldehyde, aniline and phenylacetylene afforded model
asymmetric organic transformations in heterogeneous way.
Therein, the highly ordered arrangement of chiral entity in
the well-defined inner channels, together with the rigid COF
skeleton, can endow CCOFs with the tenacious chiral
confined space, consequently, ensures the optical purity of
the products under the reaction conditions.
compound
of
N-((S)-1,3-diphenylprop-2-
ynyl)benzenamine (N-(S)-DPPYBA) in 92% yield with 99%
ee in the presence of CuOTf·toulene/(S, S)-2,6-bis(4-phenyl-
2-oxazolinyl)pyridine ((S, S)-pybox) at room temperature
(Figure S1). Based on this, we performed the catalytic
asymmetric synthesis of CCOF from the corresponding
prochiral monomers. As a result, the chiral propargylamine-
linked (S)-DTP-COF was successfully synthesized via
To date, the reasonable synthetic approaches for CCOFs
have been known as direct synthesis (direct polymerization
of the chiral organic monomers), post-synthetic
modification (PSM, decoration of the established COFs by
chiral species) and chiral induction methods (chiral
catalytic
dimethoxyterephthaldehyde
asymmetric
polymerization
(DMTP),
of
2,5-
1,3,5-tris(4-
6
additives involved polymerization). As the most powerful
aminophenyl)benzene (TAPB) and phenylacetylene (PA) in
61% yield as dark red crystalline solids with the assistance
of CuOTf·toluene/(S, S)-pydox (Scheme 1). Of note, the
optimized conditions were established as crystallization at
and efficient synthetic strategy to access chiral organics,
1
0
asymmetric catalysis, however, has not yet debuted. We
anticipate that the conversion of prochiral monomers to the
CCOFs via asymmetric catalysis would not only provide a
new dimension to the design and synthesis of CCOFs, but
could allow the CCOFs synthesis to be more powerful.
3
room temperature for six days in CHCl with HOAc. Unlike
conventional COF synthesis, this approach did not require
any vigorous reaction conditions, such as solvothermal at
high temperature and high pressure.
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Scheme 1. Synthesis of (S)- and (R)-DTP-COFs via Catalytic Asymmetric Polymerization, with the Corresponding
Model Reaction in the Inset
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The measured powder X-ray diffraction (PXRD) pattern of
S)-DTP-COF (Figure 1a, black) indicated that it was
(
microcrystalline material, and a series of observed peaks at
2.7°, 4.7°, 5.4°, 7.2° and 9.6° were assigned to the (100),
(110), (200), (210) and (220) facets, respectively.
Simulation of its PXRD pattern with Materials Studio14
suggested that it possessed the most probable structure
with 2D eclipsed (AA) stacking, and the Pawley refinement
showed a negligible difference between the simulated and
experimental PXRD pattern (Figure 1a, red). (S)-DTP-COF
was assigned to the chiral space group P6 with optimized
parameters of a = b = 36.83 Å, c = 4.70 Å, α = β = 90°, γ =
1
20°, residuals wRp = 9.81% and Rp = 7.61% (Table S1).
Figure 1. Indexed experimental (black), Pawley-refined (red),
and simulated (blue) PXRD patterns of (S)-DTP-COF (a) and
(
R)-DTP-COF (b). The difference plots are presented in green.
Eclipsed structures proposed for (S)- and (R)-DTP-COF are
shown as top insets (C, dark gray; N, blue; O, red; H, white).
Formation of the propargylamine linkage was confirmed
1
3
by FT-IR and C CP-MAS solid-state NMR spectroscopy. The
-
FT-IR spectra showed typical bands for C≡C-H at 3293 cm
1
-1
in PA, NH
2
at 3434 and 3454 cm in TAPB, and CHO at
670 cm in DMTP basically disappeared, meanwhile the
characteristic peaks at 3377 (NH), and 1286 cm (C-N)
appeared after polymerization (Figure S2a). The observed
-1
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-1
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carbon resonances in 13C NMR showed that (S)-DTP-COF
the (S)-DTP-COF-catalyzed Michael addition, together with
a series of control experiments, are displayed in Table 1
(entries 1-8). The best result was obtained when the
reaction was performed in EtOH with (S)-DTP-COF (5 mg,
3.3 mol % based on NH) and p-TsOH at room temperature
for 13 h (entry 1). The desired γ-nitroketone of 1 was
generated in 97% yield with 96% ee and 72:28 dr (TON =
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contains methoxyl (∼56 ppm) and aromatic (∼109−128
ppm) species. Furthermore, the weak peaks at
approximately 49 and 74 ppm respectively attributed to the
-CNH- and -C≡C- species unambiguously verified the
formation of propargylamine linkage (Figure S2b). All these
assignments were determined according to the chemical
shifts of corresponding carbons on model compound and
literature reports.
-1
29.4, TOF = 2.7 h ). Without acid (entry 2) or with other
kinds of acids (entries 3-5), the reactions afforded the
desired product in much lower yields (13-78%). In the
absence of (S)-DTP-COF, no conversion was observed
under the same conditions (entry 6). In addition, when the
reaction was carried out with a lower catalyst loading, 2.0
mol % instead of 3.3 mol %, the desired product was
isolated in a slightly lower 92% yield but with excellent ee
(95%) and dr (72:28) values (entry 7). Also, more CCOF
loading (4.5 mol%) could not substantially enhance the
yield (97%), ee (96%) and dr (72:28) values (entry 8). In
The porosity of (S)-DTP-COF was examined by gas
adsorption−desorption measurement, and its sorption
profile can be described as a type IV isotherm, which is
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characteristic of mesoporous materials. N
2
adsorption at 77
K revealed absorption of 282 cm /g for (S)-DTP-COF
Figure S2c), and its surface area calculated on the basis of
3
(
2
the BET model was determined to be 684 m /g. The pore
size distribution curves, calculated via nonlocal density
functional theory (NLDFT) analysis (Figure S2c inset),
showed that the pore width of (S)-DTP-COF is centered at
~2.9 nm, which is in good agreement with its simulated
structure. (S)-DTP-COF is stable against organic (THF,
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b
comparison with the reported [(S)-Py]0.17-TPB-DMTP-COF
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d
and Tfp2-COF, (S)-DTP-COF provided better yield and ee
values, but with worse anti/syn ratio for the synthesis of 1.
DMSO, DMF, EtOH, CHCl
3
), water, basic (NaOH aqueous
Table 1. Optimization of Reaction Conditions for the
solution, 12M) and acidic (HCl aqueous solution, 2M) media
Model Asymmetric Michael Addition Catalyzed by (S)-
a
(
Figure S2d).
DTP-COF
Scanning electron microscopy (SEM) image indicated that
(S)-DTP-COF was nanometer-scale material (Figure S2e),
and no different morphology was observed, further
indicating that it was obtained in single phase. Its
transmission electron microscope (TEM) image again
evidenced its high crystalline nature (Figure S2f).
Thermogravimetric analysis (TGA) suggested that it is
thermally stable up to ~300 °C (Figure S2g).
yield (%)b
drc
ee (%)c
EN
1
cat.
additive
p-TsOH
-
(S)-DTP-COF
(S)-DTP-COF
(S)-DTP-COF
(S)-DTP-COF
(S)-DTP-COF
-
97
33
35
78
13
-
72:28
76:24
75:25
73:27
74:26
-
96
86
95
94
95
-
2
3
CH
CF
PhCO
3
CO
2
H
4
3
SO
3
H
5
2
H
6
p-TsOH
p-TsOH
p-TsOH
p-TsOH
7d
8e
9
(S)-DTP-COF
(S)-DTP-COF
N-(S)-DPPYBA
92
97
21
72:28
72:28
55:45
95
96
74
aReaction conditions: cyclohexanone (10 mmol), 1-((E)-2-
nitrovinyl)benzene (0.5 mmol), additive (20% mol), acid (0.05
M), EtOH (2 mL), catalyst (5 mg, 3.3 mol % based on NH), 13h.
Figure 2. CD spectra showing that the pairs of (S)- and (R)-
DTP-COF are mirror images of one another.
b
c
Isolated yield. The dr and ee values were determined by chiral
d
e
HPLC (Figure S3). (S)-DTP-COF (2.0 mol %). (S)-DTP-COF
The chiral nature of (S)-DTP-COF was proved by its
circular dichroism (CD) spectrum. As shown in Figure 2, (S)-
DTP-COF is optically active and displayed negative Cotton
effect at ca. 250, 580 and 704 nm, and positive dichroic
signals at ca. 450 and 753 nm in its CD spectrum.
(
4.5 mol %).
In contrast, the synthesis of 1 catalyzed by molecular
model compound of N-(S)-DPPYBA only provided 21%
yield with 55:45 dr and 74% ee in a homogeneous way
(Table 1, entry 9), indicating that the (S)-DTP-COF
displayed much better activity and chiral templating effect
to its homogeneous control.
As shown above, (S)-DTP-COF is an amino-enriched chiral
porous material, so we envision that it could be the
asymmetric organic catalyst to promote aminocatalytic
1
5
reactions, such as Michael addition, in a heterogeneous
way. We then chose the reaction of cyclohexanone with 1-
The hot leaching test confirmed that (S)-DTP-COF is a
typical heterogeneous catalyst (Figure S4a), and it could be
reused and gave a 96% yield with 72:28 dr and 95% ee at
the tenth catalytic run (Figure S4b). The slightly decreased
yield and ee value might result from a modestly reduced
(
(E)-2-nitrovinyl)benzene as a model Michael addition
reaction to optimize the reaction conditions. The yield,
diastereomeric ratio (dr), and enantiomeric excess (ee) for
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surface area (Figure S4c) although no detectable
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morphology (Figure S4d) and crystallinity (Figure S4e)
changes were observed after ten catalytic cycles.
Table 2. Scope of the Michael Addition Reactions
a
Catalyzed by (S)-DTP-COF
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Figure 3. X-ray single-crystal crystal structures (insets) and CD
spectra indicating the pair of 2 and 2’ are mirror images of each
other.
Moreover, we performed the same catalytic asymmetric
polymerization for DTP-COF synthesis, but with (R, R)-
pybox instead of (S, S)-pybox. As expected, the (R)-DTP-
COF was readily generated (Scheme 1, Figure S7).
Simulation of its PXRD pattern with Materials Studio
indicated that it features the same eclipsed 2D structure as
(
S)-DTP-COF (Figure 1b, Table S3), but with the opposite
chirality (Figure 2). With the aid of (R)-DTP-COF,
compound 2’, a mirror-image isomer of 2 (Figure 3), was
legitimately obtained in 99% yield with dr = 87:13 and 99%
ee under the same reaction conditions (Figure S8). Its
absolute configuration was once again confirmed by the
single-crystal analysis (Figure 3, Table S4, CCDC 2015688).
The result revealed that the chiral DTP-COF herein
possessed a powerful chiral confinement effect which could
regulate the product enantioselectivity by expediently
tuning the CCOF chirality.
aReaction conditions: cyclohexanone (10 mmol), aromatic
nitroolefin (0.5 mmol), p-TsOH (20% mol, 0.05M), EtOH (2
mL), (S)-DTP-COF (5 mg, 3.3 mol % based on NH), 13 h.
1
Isolated yield. Compounds 1-8 were characterized by H
1
3
NMR, C NMR and MS spectra, and their dr and ee values
were determined by chiral HPLC (Figure S5).
The generality of this CCOF-catalyzed Michael addition
was also verified. As shown in Table 2, the Michael addition
reactions of cyclohexanone with -OCH , -Cl, -CH and -OH
3 3
The excellent catalytic stereoselectivity of both (S)- and
R)-DTP-COFs clearly resulted from their high-optical
substituted β-nitrostyrenes at different positions
proceeded smoothly under the optimal conditions, and
provided 82-99% yields with dr = 68:32-88:12 and 90-99%
ee values, respectively (Figure S5). However, the larger-
sized β-tetralone with 9-(2-nitrovinyl)anthracene could not
afford the desired product (yield, ∠1%), suggesting that (S)-
DTP-COF possesses substrate size effect. Besides, we are
pleased that this (S)-DTP-COF-catalyzed Michael addition
can be readily scaled up. For example, 1 was generated in
(
purity (93% ee) (Figure S9, Table S5). Worth noting is that
non-optically active COF could be obtained by using racemic
pybox than chiral one (Figure S10, Table S5). Additionally,
the generality of asymmetric polymerization methodology
for CCOF synthesis was further demonstrated via the same
3
asymmetric A -coupling reactions with different monomers
(
Figure S11-S15, Supporting Information).
In conclusion, we have successfully designed and
9
3% yield (1.6 g) with 96% ee and 72:28 dr via gram-scale
synthesized a series of propargylamine-linked CCOFs via
asymmetric catalysis from prochiral monomers under
ambient conditions. Catalytic asymmetric polymerization
herein convincingly complements the existing approaches
of CCOFs synthesis. In addition, the obtained chiral
propargylamine-linked DTP-COFs can be the highly active
reusable catalysts to promote asymmetric Michael addition
reactions (Table S6), even at a gram-scale level. We believe
that the concept of catalytic asymmetric polymerization is
general, moreover, significantly broadens the scope of
CCOFs synthesis.
reaction under the given conditions (Figure S6).
The absolute configuration of Michael addition product
was determined by the single-crystal analysis. For example,
2 crystallizes in a chiral orthorhombic crystal system with
1 1 1
space group P2 2 2 (No. 19, CCDC 2015687) (Figure 3,
Tables S2). The absolute configuration of the chiral centers
is as follows: С9 (S), С8 (R), which is further supported by
the positive (~250 nm) and negative dichroic signals (~294
nm) in its CD spectrum (Figure 3).
ASSOCIATED CONTENT
Supporting Information. Instruments and methods; synthesis
and additional characterization of CCOFs; catalytic procedure;
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catalytic
products
characterization;
crystallographic
Frameworks. Science 2005, 310, 1166-1170. (b) Diercks, C.; Yaghi,
O. M. The atom, the molecule, and the covalent organic framework.
Science 2017, 355, 923-931.
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information (PDF). This material is available free of charge via
the Internet at http://pubs.acs.org.
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Covalent Organic Frameworks as Exceptional Hydrogen Storage
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Carbon Dioxide in Highly Porous Covalent Organic Frameworks for
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AUTHOR INFORMATION
Corresponding Author
*
Yu-Bin Dong − College of Chemistry, Chemical Engineering
and Materials Science, Collaborative Innovation Center of
Functionalized Probes for Chemical Imaging in Universities of
Shandong, Key Laboratory of Molecular and Nano Probes,
Ministry of Education, Shandong Normal University, Jinan
250014, P. R. China; orcid.org/0000-0002-9698-8863;
Email: yubindong@sdnu.edu.cn
8
883. (c) Lü, J.; Perez-Krap, C.; Suyetin, M.; Alsmail, N. H.; Yan, Y.;
Yang, S.; Lewis, W.; Bichoutskaia, E.; Tang, C. C.; Blake, A. J.; Cao, R.;
Schröder, M. A Robust Binary Supramolecular Organic Framework
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(SOF) with High CO Adsorption and Selectivity. J. Am. Chem. Soc.
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Authors
1
0098.
‡ Jian-Cheng Wang − College of Chemistry, Chemical
Engineering and Materials Science, Collaborative Innovation
Center of Functionalized Probes for Chemical Imaging in
Universities of Shandong, Key Laboratory of Molecular and
Nano Probes, Ministry of Education, Shandong Normal
University, Jinan 250014, P. R. China
(3) (a) Lin, G.; Ding, H.; Yuan, D.; Wang, B.; Wang, C. A Pyrene-
Based, Fluorescent Three-Dimensional Covalent Organic
Framework. J. Am. Chem. Soc. 2016, 138, 3302-3305. (b) Hao, Q.;
Zhao, C.; Sun, B.; Lu, C.; Liu, J.; Liu, M.; Wan, L.-J.; Wang, D. Confined
Synthesis of Two-Dimensional Covalent Organic Framework Thin
Films within Superspreading Water Layer. J. Am. Chem. Soc. 2018,
140, 12152-12158. (c) Ascherl, L.; Evans, E. W.; Hennemann, M.; Di
Nuzzo, D.; Hufnagel, A. G.; Beetz, M.; Friend, R. H.; Clark, T.; Bein, T.;
Auras, F. Solvatochromic Covalent Organic Frameworks. Nat.
Commun. 2018, 9, 3802. (d) Wu, X.; Han, X.; Xu, Q.; Liu, Y.; Yuan, C.;
Yang, S.; Liu, Y.; Jiang, J.; Cui, Y. Chiral BINOL-Based Covalent
Organic Frameworks for Enantioselective Sensing. J. Am. Chem. Soc.
2019, 141,17, 7081-7089.
‡
Xuan Kan − College of Chemistry, Chemical Engineering and
Materials Science, Collaborative Innovation Center of
Functionalized Probes for Chemical Imaging in Universities of
Shandong, Key Laboratory of Molecular and Nano Probes,
Ministry of Education, Shandong Normal University, Jinan
2
50014, P. R. China.
(
4) Qun G.; Zhou, L.-L.; Li, W.-Y.; Li, Y.-A.; Dong, Y.-B. Covalent
Jin-Yan Shang − College of Chemistry, Chemical Engineering
and Materials Science, Collaborative Innovation Center of
Functionalized Probes for Chemical Imaging in Universities of
Shandong, Key Laboratory of Molecular and Nano Probes,
Ministry of Education, Shandong Normal University, Jinan
250014, P. R. China.
Organic Frameworks (COFs) for Cancer Therapeutics. Chem. Eur. J.
2020, 26, 5583 – 5591 and references therein.
(5) (a) Ding, S. Y.; Gao, J.; Wang, Q.; Zhang, Y.; Song, W. G.; Su, C.
Y.; Wang, W. Construction of Covalent Organic Framework for
Catalysis: Pd/COF-LZU1 in Suzuki-Miyaura Coupling Reaction. J.
Am. Chem. Soc. 2011, 133, 19816-19822. (b) Vyas, V. S.; Haase, F.;
Stegbauer, L.; Savasci, G.; Podjaski, F.; Ochsenfeld, C.; Lotsch, B. V. A
Tunable Azine Covalent Organic Framework Platform for Visible
Light-Induced Hydrogen Generation. Nat. Commun. 2015, 6, 8508.
(c) Lin, S.; Diercks, C. S.; Zhang, Y.-B.; Kornienko, N.; Nichols, E. M.;
Zhao, Y.; Paris, A. R.; Kim, D.; Yang, P.; Yaghi, O. M.; Chang, C. J.
Covalent Organic Frameworks Comprising Cobalt Porphyrins for
Hua Qiao − College of Chemistry, Chemical Engineering and
Materials Science, Collaborative Innovation Center of
Functionalized Probes for Chemical Imaging in Universities of
Shandong, Key Laboratory of Molecular and Nano Probes,
Ministry of Education, Shandong Normal University, Jinan
2
50014, P. R. China.
Author Contributions
These authors contributed equally.
2
Catalytic CO Reduction in Water. Science 2015, 349, 1208-1213.
(
d) Sun, Q.; Aguila, B.; Perman, J.; Nguyen, N.; Ma, S. Q. Flexibility
Matters: Cooperative Active Sites in Covalent Organic Framework
and Threaded Ionic Polymer. J. Am. Chem. Soc. 2016, 138, 15790-
1596. (e) Li, H.; Pan, Q.; Ma, Y.; Guan, X.; Xue, M.; Fang, Q.; Yan, Y.;
Valtchev, V.; Qiu, S. Three-Dimensional Covalent Organic
Frameworks with Dual Linkages for Bifunctional Cascade Catalysis.
J. Am. Chem. Soc. 2016, 138, 14783-14788. (f) Lu, S.; Hu, Y.; Wan, S.;
McCaffrey, R.; Jin, Y.; Gu, H.; Zhang, W. Synthesis of Ultrafine and
Highly Dispersed Metal Nanoparticles Confined in a Thioether-
Containing Covalent Organic Framework and Their Catalytic
Applications. J. Am. Chem. Soc. 2017, 139, 17082-17088. (g)
Pachfule, P.; Acharjya, A.; Roeser, J.; Langenhahn, T.; Schwarze, M.;
Schomäcker, R.; Thomas, A.; Schmidt, J. Diacetylene Functionalized
Covalent Organic Framework (COF) for Photocatalytic Hydrogen
Generation. J. Am. Chem. Soc. 2018, 140, 1423-1427. (h) Rotter, J.
M.; Weinberger, S.; Kampmann, J.; Sick, T.; Shalom, M.; Bein, T.;
Medina, D. D. Covalent Organic Framework Films through
Electrophoretic Deposition-Creating Efficient Morphologies for
Catalysis. Chem. Mater. 2019, 31, 10008-10016. (i) Wang, Y.; Liu,
H.; Pan, Q.; Wu, C.; Hao, W.; Xu, J.; Chen, R.; Liu, J.; Li, Z.; Zhao, Y.
Construction of Fully Conjugated Covalent Organic Frameworks
‡
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
We are grateful for financial support from NSFC (Grant Nos.
2
1971153, 21802090 and 21671122), Chang-Jiang Scholars
Program of China, Taishan Scholars Construction Project of
Shandong Province, Shandong Provincial Natural Science
Foundation (No. ZR2018MB005), Shandong Provincial Natural
Science Foundation (Grant ZR2018BB006), and a Project of the
Shandong Province Higher Educational Science and
Technology Program (J18KA066). We thank Dr. Xiaowei Wu for
help with COFs structural analysis.
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