Three-dimensional Salphen-based Covalent-Organic Frameworks as Catalytic Antioxidants

Article abstract of DOI:10.1021/jacs.9b00485

The development of three-dimensional (3D) functionalized covalent-organic frameworks (COFs) is of critical importance for expanding their potential applications. However, the introduction of functional groups in 3D COFs remains largely unexplored. Herein, we report the first example of 3D Salphen-based COFs (3D-Salphen-COFs) and their metal-containing counterparts (3D-M-Salphen-COFs). These Salphen-based COFs exhibit high crystallinity and specific surface area in addition to excellent chemical stability. Furthermore, the Cu(II)-Salphen COF displays high activity in the removal of superoxide radicals. This study not only presents a new pathway to construct 3D functionalized COFs but also promotes their applications in biology and medicine.

Full text of DOI:10.1021/jacs.9b00485

Subscriber access provided by UNIV OF BARCELONA
Communication
Three-Dimensional Salphen-Based Covalent
Organic Frameworks as Catalytic Antioxidants
Shichen Yan, Xinyu Guan, Hui Li, Daohao Li, Ming Xue,
Yushan Yan, Valentin Valtchev, Shilun Qiu, and Qianrong Fang
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.9b00485 • Publication Date (Web): 04 Feb 2019
Downloaded from http://pubs.acs.org on February 5, 2019
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a service to the research community to expedite the dissemination
of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in
full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully
peer reviewed, but should not be considered the official version of record. They are citable by the
Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore,
the “Just Accepted” Web site may not include all articles that will be published in the journal. After
a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web
site and published as an ASAP article. Note that technical editing may introduce minor changes
to the manuscript text and/or graphics which could affect content, and all legal disclaimers and
ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or
consequences arising from the use of information contained in these “Just Accepted” manuscripts.
is published by the American Chemical Society. 1155 Sixteenth Street N.W.,
Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.

Page 1 of 6
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
Three-Dimensional Salphen-Based Covalent Organic Frameworks as
Catalytic Antioxidants
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
∥
Shichen Yan,† Xinyu Guan,† Hui Li,† Daohao Li,† Ming Xue,† Yushan Yan,‡ Valentin Valtchev,†, Shilun
Qiu,† and Qianrong Fang,†
†
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130012, P. R.
China
‡
Department of Chemical and Biomolecular Engineering, Center for Catalytic Science and Technology, University of
Delaware, Newark, DE 19716, USA
∥
Normandie Univ, ENSICAEN, UNICAEN, CNRS, Laboratoire Catalyse et Spectrochimie, 6 Marechal Juin, 14050
Caen, France
Supporting Information Placeholder
Scheme 1. Strategy for preparing 3D-Salphen-COFsa
ABSTRACT: The development of three-dimensional (3D)
functionalized covalent organic frameworks (COFs) is of
critical importance for expanding their potential applications.
However, the introduction of functional groups in 3D COFs
remains largely unexplored. Herein we report the first example
of 3D Salphen-based COFs (3D-Salphen-COFs) and their metal-
containing counterparts (3D-M-Salphen-COFs). These Salphen-
based COFs exhibit high crystallinity and specific surface area
in addition to excellent chemical stability. Furthermore, the
Cu(II)-Salphen COF displays high activity in the removal of
superoxide radicals. This study not only presents a new
pathway to construct 3D functionalized COFs, but also
promotes their applications in biology and medicine.
Covalent organic frameworks (COFs), an emerging class of
crystalline porous materials, are composed of pure organic
skeletons connected by strong organic bonds.1-6. Since the
pioneering work of Yaghi in 2005, various COFs with different
backbones and functional groups have been synthesized and
employed as platforms for applications such as gas adsorption
and
separation,7-9
optoelectronics,10,11
heterogeneous
catalysis,12-14 and a number of others.15-21 Yet most of the
reported COFs are two-dimensional (2D) frameworks with
eclipsed stacking structures.22,23 Three-dimensional (3D) COFs
have recently attracted much attention due to their unique
porous structures and outstanding performances.24-29 We have
reported a series of 3D COFs by the meticulous design of
building units, including 3D ionic COFs for selective ion
exchange,30 3D ionic liquid containing COFs with high gas
separation ability,31 3D carboxy-functionalized COFs for
selective extraction of lanthanide ions,32 and so on.33-35 It must
be noted, however, that 3D COFs are still limited so far, and thus
the development of 3D COFs, especially 3D functionalized
COFs, is important for improving their structural diversity and
widening their potential applications.
a(a) The model reaction of Salphen unit and M-Salphen unit
based on 2-hydroxybenzaldehyde (HBA) and 4,5-
dichlorophenylene-1,2-diamine (DCPDA). (b) Condensation
of tetrahedral tetrakis(3-formyl-4-hydroxylphenyl)methane
(TFHPM) and two linkers containing diamine, 4,5-
difluorophenylene-1,2-diamine (DFPDA) or DCPDA, to give
novel 3D-Salphen-COFs, JUC-508 and JUC-509, respectively.
(c) The preparation of 3D-M-Salphen-COFs, JUC-509-Y (Y =
Mn, Cu or Eu), via the metal incorporation. (d) The non-
interpenetrated dia network in 3D-Salphen-COFs.
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 2 of 6
Herein, we addressed the above issues by designing 3D
Salphen-based COFs (3D-Salphen-COFs) and their
Typically, 3D-Salphen-COFs were synthesized by suspending
1
2
3
4
5
6
7
8
TFHPM with DFPDA or DCPDA in the mixed solvent of dioxane
and mesitylene in the presence of acetic acid followed by
heating at 120 °C for 3 days. Complementary characterization
have been employed for detailed structural definition of new
materials. Scanning electron microscopy (SEM) and
transmission electron microscopy (TEM) images of 3D-
Salphen-COFs showed flower-like microstructure composed of
prismatic several micrometers long crystals (Figures S1-S4).
Peaks around 1616 cm-1 for JUC-508 and 1618 cm-1 for JUC-509
in Fourier transform infrared (FTIR) spectra indicated the
formation of imine linkages, which is similar to that from the
model Salphen unit (1614 cm-1 for imine bands), and the
disappearance of peaks at 1659 cm-1 for both 3D-Salphen-COFs
confirmed the complete transformation of aldehyde groups
(Figures S5 and S6). The solid state 13C cross-polarization
magic-angle-spinning (CP/MAS) NMR spectra further
confirmed the presence of carbon from the C=N bond at 163
ppm for JUC-508 and 161 ppm for JUC-509 (Figures S8 and S9).
According to the thermogravimetric analysis (TGA), both 3D-
Salphen-COFs are stable up to about 350 °C under nitrogen
(Figures S10 and S11). Notably, their crystalline structures can
be preserved in a variety of organic solvents and the aqueous
solutions at pH = 1~14 (Figures S15-S18).
corresponding metal-containing isostructures (3D-M-Salphen-
COFs). The obtained COFs showed high crystallinity, open
channels, good chemical stability and large specific surface
area. Furthermore, various metal ions (Cu(II), Mn(II) and
Eu(III)) were successfully incorporated into the Salphen-based
COFs, as the Cu(II)-Salphen COF exhibited the best
performance in eliminating deleterious oxygen-derived free
radicals. To the best of our knowledge, this study is the first
case of 3D Salphen-based COFs and the application of COF
materials as catalytic antioxidants.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Figure 1. PXRD patterns of JUC-508 (a) and JUC-509 (b).
Our strategy for constructing 3D-Salphen-COFs embraces
the form of both COF frameworks and Salphen units
Figure 2. Structural representations of JUC-509 (a and b) and
JUC-509-Y (c and d).
synchronously.
As
shown
in
Scheme
1a,
2-
hydroxybenzaldehyde (HBA) and 4,5-dichlorophenylene-1,2-
diamine (DCPDA) afford the model Salphen unit, which can be
further assembled into Mn(II)-Salphen unit via the
complexation (see the Supporting Information, SI, Section S1).
On the basis of this reaction, we synthesized a tetrahedral
The crystal structures of 3D-Salphen-COFs were resolved by
the powder X-ray diffraction (PXRD) measurements in
conjunction with structural simulations (Figure 1). After a
geometrical energy minimization by using the Materials Studio
software package37 based on non-interpenetrated dia net for
3D-Salphen-COFs, the unit cell parameters were obtained (a =
b = 19.153 Å, c = 41.988 Å and α = β = γ = 90° for JUC-508; a = b
= 18.983 Å, c = 42.202 Å and α = β = γ = 90° for JUC-509).
Furthermore, full profile pattern matching (Pawley)
refinements were carried out on the experimental PXRD
patterns. Peaks at 5.41, 7.19, 8.02, 10.31, 10.84 and 11.65° for
JUC-508 correspond to the (101), (103), (112), (200), (202)
and (211) Bragg peaks of space group I-42d (No. 122),
respectively; peaks at 5.10, 7.80, 8.37, 9.31, 1021, 12.17 and
12.53° for JUC-509 correspond to the (101), (112), (004),
(200), (202), (213) and (204) Bragg peaks of space group I-
salicylaldehyde-based
monomer,
tetrakis(3-formyl-4-
hydroxylphenyl)methane (TFHPM). By the condensation of
TFHPM and amino-based linkers, 4,5-difluorophenylene-1,2-
diamine (DFPDA) or DCPDA, two extended 3D Salphen-based
COFs, denoted as JUC-508 and JUC-509 respectively, can be
obtained (Scheme 1b). Furthermore, JUC-509 can be gathered
into 3D-M-Salphen-COFs by the introduction of Mn(II), Cu(II)
or Eu(III) ions, denoted as JUC-509-Y (Y = Mn, Cu or Eu, Scheme
1c). Based on this design, TFHPM can be defined as a 4-
connected node, and DFPDA or DCPDA can act as a 2-connected
node, which results in the 3D network with the non-
interpenetrated dia topology due to the steric effect of Salphen
unit (Scheme 1d).36
ACS Paragon Plus Environment

Page 3 of 6
Journal of the American Chemical Society
42d, respectively. The refinement results matched well with
relative metal salts, giving JUC-509-Y (Y = Mn, Cu or Eu). The
metal complexation of Salphen COFs could be easily visualized
by their color change (Figure S30). Meanwhile, scanning
electron microscope-energy dispersive X-ray spectra (SEM-
EDS) analysis exhibited the uniform distribution of metal ions
in the crystals (Figure S31). The ICP analysis of the resulting M-
Salphen COFs showed that most of the Salphen pockets have
been occupied by the metal ions (see Section S1 in SI). FTIR
spectroscopy indicated the strong interaction between
Salphen-COF and metal ions based on the shift of the IR bands
for the imine groups from 1618 cm-1 (JUC-509) to 1608 cm−1
(JUC-509-Cu), 1606 cm−1 (JUC-509-Mn) or 1606 cm−1 (JUC-
509-Eu), which is similar with the results from the model
Salphen unit to Mn(II)-Salphen unit (from 1614 cm-1 to 1603
cm-1, Figure S7). X-ray photoelectron spectroscopy (XPS)
suggested Cu and Mn were in the +2 oxidtion state and Eu was
in the +3 oxidation state (Figures S32-34). In addition, the
retained PXRD patterns of 3D-M-Salphen-COFs pointed out
that the crystalline structure was preserved after the metal
incorporation (Figure 2 and Figures S24-26). The porosities
were evaluated by N2 adsorption and desorption analysis,
which showed values slightly lower than that of the pristine
material (Figure S29).
1
2
3
4
5
6
7
8
the observed patterns with good agreement factors (Rωp =
6.88% and Rp = 3.59% for JUC-508; Rωp = 8.72% and Rp =
5.46% for JUC-509). We also considered the alternative
structures based on the 2-fold interpenetrated dia net from the
same space group of I-42d for both 3D-Salen-COFs; however,
their simulated patterns did not match to the experimental
ones (Figures S19-22). On the basis of the above results, these
Salphen COFs were proposed to have the expected
architectures with non-interpenetrated dia topology, which
show microporous cavities with a diameter of about 1.2 nm
(Figure 2 and Figure S23). Remarkably, almost all of 3D COFs
with dia topology show multifold interpenetrated structures,
and thus the successful preparation of 3D-Salphen-COFs with
non-interpenetrated nets will benefit the development of 3D
COFs with large pores.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Figure 3. N2 adsorption-desorption isotherms of JUC-508 (a)
and JUC-509 (b). Inset: pore-size distribution calculated by
fitting on the NLDFT model to the adsorption data.
The porosity and surface areas were measured by N2
adsorption and desorption analysis (Figure 3). Both materials
show a sharp uptake at a low pressure of P/P0 < 0.05, which is
characteristic of the microporous material. The inclination of
isotherms in the 0.8-1.0 P/P0 range and slight desorption
hysteresis show the presence of textural mesopores, which is
the consequence of the agglomeration of COF crystals.34 The
Brunauer-Emmett-Teller (BET) equation was applied over the
0.05 < P/P0 < 0.30 range of the isotherms, revealing BET
surface areas of 1513 m2 g-1 for JUC-508 and 1443 m2 g-1 for
JUC-509 (Figures S27 and S28). Pore size distributions of 3D-
Salphen-COFs calculated by nonlocal density functional theory
(NLDFT) showed pore with sizes of 1.3 nm for JUC-508 and 1.2
nm for JUC-509, respectively (Figure 3, inset), which is in good
agreement with that of the proposed model (1.2 nm).
Figure 4. Adsorption spectra of JUC-509-Cu (a), JUC-509-Mn
(b), JUC-509-Eu (c) and JUC-509 (d) in antioxidant
experiments. (e) The clearance rate based on different
concentration. (f) Recyclability study of JUC-509-Cu, JUC-509-
Mn, JUC-509-Eu and JUC-509.
We further explored the application of M-Salphen COFs in
the removal of superoxide radical anion (O2·-). It is well known
that the overproduction of O2·- has been shown to contribute to
tissue damage and injury.38 Salens or Salphens with redox-
active metal centers are considered as major catalytic
·-
antioxidants that catalyze the dismutation reaction of O2
similar to superoxide dismutases (SODs).39 However, the
employments of traditional Salphens are strongly limited
because of stability and recyclability issues. Herein, 3D-M-
Salphen-COFs were chosen as effective oxygen radical removal
Encouraged by their high surface area and abundant Salphen
units, a series of 3D-M-Salphen-COFs were subsequently
acquired by immersing JUC-509 in a methanol solution of
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 4 of 6
agents due to their high surface area, chemical stability and
and V.V. acknowledge the support from Thousand Talents
program (China).
1
2
3
4
5
6
7
8
reusability. In addition, similar to those Salphen-based metal
complexes for superoxide radicals removal, Salphen-based
COFs are also biocompatible.40
REFERENCES
Typically, O2·- was generated under sunlight in the presence
of methionine and riboflavin, and further reacted with
nitrotetrazolium blue chloride (NBT) to form a deep blue
complex, which exhibited a characteristic absorption at about
560 nm in the UV-Vis spectroscopy.40 As shown in Figure 4, 3D-
M-Salphen-COFs had different activity in the elimination of
superoxide radicals accompanied by the change of catalyst
concentration. Among them, JUC-509-Eu had no obvious
antioxidant activity, and JUC-509-Cu displayed the best
performance (almost 100% clearance rate in only 0.875
mg/ml), which can be attributed to the high catalytic effect of
Cu(II) ion.41 As a comparison, the metal-free pristine material,
JUC-509, was tested under the same condition, and showed no
(1) Côté, A. P.; Benin, A. I.; Ockwig, N. W.; O'Keffe, M.; Matzger, A. J.;
Yaghi, O. M. Porous, Crystalline, Covalent Organic Frameworks. Science
2005, 310, 1166.
(2) Colson, J. W.; Woll, A. R.; Mukherjee, A.; Levendorf, M. P.; Spitler,
E. L.; Shields, V. B.; Spencer, M. G.; Park, J.; Dichtel, W. R. Oriented 2D
Covalent Organic Framework Thin Films on Single-Layer Graphene.
Science 2011, 332, 228.
(3) Ding, S. Y.; Wang, W. Covalent organic frameworks (COFs): from
design to applications. Chem. Soc. Rev. 2013, 42, 548.
(4) Huang, N.; Wang, P.; Jiang, D. L. Covalent organic frameworks: a
materials platform for structural and functional designs. Nat. Rev.
Mater. 2016, 1, 16068.
(5) Fang, Q. R.; Zhuang, Z. B.; Gu, S.; Kaspar, R. B.; Zheng, J.; Wang, J.
H.; Qiu, S. L.; Yan, Y. S. Designed synthesis of large-pore crystalline
polyimide covalent organic frameworks. Nat. Commun. 2014, 5, 4503.
(6) Wang, H.; Zeng, Z.; Xu, P.; Li, L.; Zeng, G.; Xiao, R.; Tang, Z.; Huang,
D.; Tang, L.; Lai, C.; Jiang, D.; Liu, Y.; Yi, H.; Qin, L.; Ye, S.; Ren, X.; Tang,
W. Recent progress in covalent organic framework thin films:
fabrications, applications and perspectives. Chem. Soc. Rev. 2019, 48,
488.
(7) Kuhn, P.; Antonietti, M.; Thomas, A. Porous, Covalent Triazine-
Based Frameworks Prepared by Ionothermal Synthesis. Angew. Chem.
Int. Ed. 2008, 47, 3450.
(8) Furukawa, H.; Yaghi, O. M. Storage of Hydrogen, Methane, and
Carbon Dioxide in Highly Porous Covalent Organic Frameworks for
Clean Energy Applications. J. Am. Chem. Soc. 2009, 131, 8875.
(9) Doonan, C. J.; Tranchemontagne, D. J.; Glover, T. G.; Hunt, J. R.;
Yaghi, O. M. Exceptional ammonia uptake by a covalent organic
framework. Nat. Chem. 2010, 2, 235.
(10) Wan, S.; Guo, J.; Kim, J.; Ihee, H.; Jiang, D. A Belt-Shaped, Blue
Luminescent, and Semiconducting Covalent Organic Framework.
Angew. Chem. Int. Ed. 2008, 47, 8826.
(11) Du, Y.; Yang, H.; Whiteley, J. M.; Wan, S.; Jin, Y.; Lee, S. H.; Zhang,
W. Ionic Covalent Organic Frameworks with Spiroborate Linkage.
Angew. Chem. Int. Ed. 2016, 55, 1737.
(12) 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.
(13) Li, L. H.; Feng, X. L.; Cui, X. H.; Ma, Y. X.; Ding, S. Y.; Wang, W.
Salen-Based Covalent Organic Framework. J. Am. Chem. Soc. 2017, 139,
6042.
(14) Han, X.; Xia, Q. C.; Huang, J. J.; Liu, Y.; Tan, C. X.; Cui, Y. Chiral
Covalent Organic Frameworks with High Chemical Stability for
Heterogeneous Asymmetric Catalysis. J. Am. Chem. Soc. 2017, 139,
8693.
(15) Kandambeth, S.; Mallick, A.; Lukose, B.; Mane, M. V.; Heine, T.;
Banerjee, R. Construction of Crystalline 2D Covalent Organic
Frameworks with Remarkable Chemical (Acid/Base) Stability via a
Combined Reversible and Irreversible Route. J. Am. Chem. Soc. 2012,
134, 19524.
(16) Calik, M.; Auras, F.; Salonen, L. M.; Bader, K.; Grill, I.; Handloser,
M.; Medina, D. D.; Dogru, M.; Löbermann, F.; Trauner, D.; Hartschuh, A.;
Bein, T. Extraction of Photogenerated Electrons and Holes from a
Covalent Organic Framework Integrated Heterojunction. J. Am. Chem.
Soc. 2014, 136, 17802.
(17) Zhou, T. Y.; Xu, S. Q.; Wen, Q.; Pang, Z. F.; Zhao, X. One-Step
Construction of Two Different Kinds of Pores in a 2D Covalent Organic
Framework. J. Am. Chem. Soc. 2014, 136, 15885.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
·-
evidence for the removal of O2 (Figure 4d and 4e), which
further demonstrated the critical role of redox-active metal
centers in antioxidant activity. ICP analysis of the filtrate after
the reaction revealed almost no leaching of metal ions (see
Section S1 in SI). PXRDs showed that the recovered solid
remained crystalline and structurally intact (Figures S24-26).
Most importantly, these M-Salphen COF catalysts can be readily
recycled and reused at least three times without obvious loss
of activity (Figure 4f). Compared with other common catalytic
antioxidants, 3D-M-Salphen-COFs need higher concentrations
to remove the oxygen radicals due to their high molecular
weight; however, these COFs as heterogeneous catalysts can be
easily recycled and reused, which is superior to most of
reported catalytic antioxidants.
In conclusion, we have for the first time designed and
synthesized 3D-Salphen-COFs and 3D-M-Salphen-COFs. These
Salphen-based COFs showed high crystallinity, BET surface
area, and chemical stability. Furthermore, the Cu(II)-Salphen
COF displayed high performance in the removal of superoxide
radicals and could be reused without significant activity loss.
3D Salphen-based COFs successfully prepared in this work may
not only open a new pathway to create 3D functionalized COFs,
but also expand the applications of COF materials in biology
and medicine.
ASSOCIATED CONTENT
Supporting Information
Synthetic procedures, SEM, TEM, FTIR, solid state 13C NMR,
TGA, and BET plots. This material is available free of charge via
the internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*qrfang@jlu.edu.cn
Notes
The authors declare no competing financial interests.
(18) Peng, Y. W.; Xu, G. D.; Hu, Z. G.; Cheng, Y. D.; Chi, C. L.; Yuan, D.
Q.; Cheng, H. S.; Zhao, D. Mechanoassisted Synthesis of Sulfonated
Covalent Organic Frameworks with High Intrinsic Proton Conductivity.
ACS Appl. Mater. Interfaces 2016, 8, 18505.
(19) Wang, S.; Wang, Q.; Shao, P.; Han, Y.; Gao, X.; Ma, L.; Yuan, S.; Ma,
X.; Zhou, J.; Feng, X.; Wang, B. Exfoliation of Covalent Organic
Frameworks into Few-layer Redox-Active Nanosheets as Cathode
Materials for Lithium-Ion Batteries. J. Am. Chem. Soc. 2017, 139, 4258.
ACKNOWLEDGMENT
This work was supported by National Natural Science
Foundation of China (21571079, 21621001, 21390394,
21571076, and 21571078), 111 project (B07016 and
B17020), Guangdong and Zhuhai Science and Technology
Department Project (2012D0501990028), and the program for
JLU Science and Technology Innovative Research Team. Q.F
ACS Paragon Plus Environment

Page 5 of 6
Journal of the American Chemical Society
(20) Sun, Q.; Aguila, B.; Perman, J.; Earl, L. D.; Abney, C. W.; Cheng, Y.;
(31) Guan, X. Y.; Ma, Y. C.; Li, H.; Yusran, Y.; Xue, M.; Fang, Q. R.; Yan,
Y. S.; Valtchev, V.; Qiu, S. L. Fast, Ambient Temperature and Pressure
Ionothermal Synthesis of Three-Dimensional Covalent Organic
Frameworks. J. Am. Chem. Soc. 2018, 140, 4494.
Wei, H.; Nguyen, N.; Wojtas, L.; Ma, S. Q. Postsynthetically Modified
Covalent Organic Frameworks for Efficient and Effective Mercury
Removal. J. Am. Chem. Soc. 2017, 139, 2786.
1
2
3
4
5
6
7
8
9
(21) Jin, E. Q.; Asada, M.; Xu, Q.; Dalapati, S.; Addicoat, M. A.; Brady,
M. A.; Xu H.; Nakamura, T., Heine, T.; Chen, Q. H.; Jiang, D. L. Two-
dimensional sp2 carbon-conjugated covalent organic frameworks.
Science 2017, 357, 673.
(22) Colson, J. W.; Dichtel, W. R. Rationally synthesized two-
dimensional polymers. Nat. Chem. 2013, 5, 453.
(23) Diercks, C. S.; Yaghi, O. M. The atom, the molecule, and the
covalent organic framework. Science 2017, 355, 923.
(24) El-Kaderi, H. M.; Hunt, J. R.; Mendoza-Cortés, J. L.; Côté, A. P.;
Taylor, R. E.; O'Keffe, M.; Yaghi, O. M. Designed Synthesis of 3D Covalent
Organic Frameworks. Science 2007, 316, 268.
(25) Zhang, Y. B.; Su, J.; Furukawa, H.; Yun, Y. F.; Gándara, F.; Duong,
A.; Zou, X. D.; Yaghi, O. M. Single-Crystal Structure of a Covalent Organic
Framework. J. Am. Chem. Soc. 2013, 135, 16336.
(26) Beaudoin, D.; Maris, T.; Wuest, J. D. Constructing
monocrystalline covalent organic networks by polymerization. Nat.
Chem. 2013, 5, 830.
(27) Lin, G. Q.; Ding, H. M.; Yuan, D. Q.; Wang, B. S.; Wang, C. A pyrene-
Based, Fluorescent Three-Dimensional Covalent Organic Framework. J.
Am. Chem. Soc. 2016, 138, 3302.
(28) Yahiaoui, O.; Fitch, A. N.; Hoffmann, F.; Fröba, M.; Thomas, A.;
Roeser, J. 3D Anionic Silicate Covalent Organic Framework with srs
Topology. J. Am. Chem. Soc. 2018, 140, 5330.
(32) Lu, Q. Y.; Ma, Y. C.; Li, H.; Guan, X. Y.; Yusran, Y.; Xue, M.; Fang, Q.
R.; Yan, Y. S.; Qiu, S. L.; Valtchev, V. Postsynthetic Functionalization of
Three-Dimensional Covalent Organic Framework for Selective
Extraction of Lanthanide Ions. Angew. Chem. Int. Ed. 2018, 57, 6042.
(33) Li, H.; Pan, Q. Y.; Ma, Y. C.; Guan, X. Y.; Xue, M.; Fang, Q. R.; Yan,
Y. S.; Valtchev, V.; Qiu, S. L. 3D Covalent Organic Frameworks with Dual
Linkages for Bifunctional Cascade Catalysis. J. Am. Chem. Soc. 2016, 138,
14783.
(34) Fang, Q. R.; Wang, J. H.; Gu, S.; Kaspar, R. B.; Zhuang, Z. B.; Zheng,
J.; Guo, H. X.; Qiu, S. L.; Yan, Y. S. 3D Porous Crystalline Polyimide
Covalent Organic Frameworks for Drug Delivery. J. Am. Chem. Soc. 2015,
137, 8352.
(35) Fang, Q. R.; Gu, S.; Zheng, J.; Zhuang, Z. B.; Qiu, S. L.; Yan, Y. S. 3D
Microporous Base-Functionalized Covalent Organic Frameworks for
Size-Selective Catalysis. Angew. Chem., Int. Ed. 2014, 53, 2878.
(36) Delgado-Friedrichs, O.; O'Keeffe, M.; Yaghi, O. M. Three-periodic
nets and tilings: edge-transitive binodal structures. Acta Crystallogr.
Sect. A 2006, 62, 350.
(37) Materials Studio ver. 7.0; Accelrys Inc.; San Diego, CA.
(38) Gilgun-Sherki, Y.; Melamed, E.; Offen, D. Oxidative stress
induced-neurodegenerative diseases:the need for antioxidants that
penetrate the blood brain barrier. Neuropharmacology 2001, 40, 959.
(39) Bian, H. D.; Wang, J.; Wei, Y.; Tang, J.; Huang, F. P.; Yao, D.; Yu, Q.;
Liang, H. Superoxide dismutase activity studies of Mn(III)/Cu(II)/Ni(II)
complexes with Schiff base ligands. Polyhedron 2015, 90, 147.
(40) Riley, D. P. Functional Mimics of Superoxide Dismutase
Enzymes as Therapeutic Agents. Chem. Rev. 1999, 99, 2573.
(41) Riley, D. P.; Weiss, R. H. Manganese Macrocyclic Ligand
Complexes as Mimics of Superoxide Dismutase. J. Am. Chem. Soc. 1994,
116, 387.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(29) Ma, T. Q.; Kapustin, E. A.; Yin, S. X.; Liang, L.; Zhou, Z. Y.; Niu, J.;
Li, L. H.; Wang, Y. Y.; Su, J.; Wang, X. G.; Wang, W. D.; Wang, W.; Sun, J. L.;
Yaghi, O. M. Single-crystal x-ray diffraction structures of covalent
organic frameworks. Science 2018, 361, 48.
(30) Li, Z. L.; Li, H.; Guan, X. Y.; Tang, J. J.; Yusran, Y.; Li, Z.; Xue, M.;
Fang, Q. R.; Yan, Y. S.; Valtchev, V.; Qiu, S. L. Three-Dimensional Ionic
Covalent Organic Frameworks for Rapid, Reversible and Selective Ion
Exchange. J. Am. Chem. Soc. 2017, 139, 17771.
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 6 of 6
TOC Graphic:
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
6
ACS Paragon Plus Environment