Benzotrithiophene-Based Covalent Organic Frameworks: Construction and Structure Transformation under Ionothermal Condition

Article abstract of DOI:10.1021/jacs.8b08282

A C₃-symmetric benzotrithiophene tricarbaldehyde (BTT) is synthesized for the first time with a facile method, which is used to construct BTT-based covalent organic frameworks (COFs) with different pore sizes. Meanwhile, the structure transform

Full text of DOI:10.1021/jacs.8b08282

Subscriber access provided by University of South Dakota
Communication
Benzotrithiophene-based Covalent Organic Frameworks: Construction
and Structure Transformation under Ionothermal Condition
Hongtao Wei, Jing Ning, Xingdi Cao, Xuehui Li, and Long Hao
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b08282 • Publication Date (Web): 04 Sep 2018
Downloaded from http://pubs.acs.org on September 4, 2018
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 9
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
Benzotrithiophene-based Covalent Organic Frameworks:
Construction and Structure Transformation under Ionothermal
Condition
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
Hongtao Wei,†,§ Jing Ning,†,§ Xingdi Cao,†,§ Xuehui Li,† Long Hao*,†
†College of Chemistry and Pharmaceutical Sciences, Qingdao Agricultural University, No.700 Changcheng Road, Qingdao
266109, China
Supporting Information Placeholder
controlling of pore sizes,4ꢀ7 surface functionalities,8ꢀ11 skeleton
ABSTRACT:
A
C3ꢀsymmetric
benzotrithiophene
structures,12ꢀ15 heteroatom doping,16ꢀ19 and structure defects.20ꢀ23
These unique advantages of COFs make their applications
gradually expanding into numerous fields over the past
decade.24ꢀ26
tricarbaldehyde (BTT) is synthesized for the first time with a
facile method, which is used to construct BTTꢀbased covalent
organic frameworks (COFs) with different pore sizes. Meanwhile,
the structure transformations of the COFs under highꢀtemperature
ionothermal condition are studied systematically, and the
relationships between the regularly changed structures of the
furtherꢀcrosslinked COFs and their supercapacitor performances
are investigated. It turns out that dealing COFs of designated
structures under ionothermal condition is a great method to build
In the electrochemical fields, such as lithium ion battery,27ꢀ29
lithiumꢀsulfur
battery,30,31
supercapacitor,32,33
or
electrocatalysis,34,35 COFs have also shown their significant value.
Their porous structures with ultrahigh surface areas and intrinsic
heteroatom doping are extremely favorable for enhancing the
electrochemical performances. Their controllable structures also
make it possible to deeply study the mechanism and
structureꢀperformance relationships in electrochemistry. However
the relatively poor conductivities of COFs always hinder their
broader applications. The usual improving method is adding
plenty of conductive addictives (e.g. carbon nanotube or
conductive carbon), which sometimes still can’t fulfill the
highꢀconductivity demand of some areas including supercapacitor
and electrocatalysis. Consequently, the highꢀtemperature
treatment of the materials is essential.36,37 Our previous works
highꢀconductive
electrochemical applications.
structureꢀcontrollable
materials
for
Covalent organic Frameworks (COFs) are crystalline reticular
materials constructed through the strong covalent bonds of
symmetric organic molecules. The appear of COFs extends the
organic reactions beyond small molecules.1 The diversities of
organic species and reaction types for building COFs also open up
a new direction in the molecular level to precisely control the
structures of lightꢀelementꢀconstituted materials,2,3 including the
Figure 1. (a) Key reaction for synthesizing the C3ꢀsymmetric benzotrithiophene tricarbaldehyde, BTT. (b) Construction of the model
compound, MC with the Schiffꢀbase reaction. (c) Schematic representation of the syntheses of BTTꢀbased COFs with different pore sizes.
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 2 of 9
with
1,3,5ꢀtrichloroꢀ2,4,6ꢀtris(dichloromethyl)benzene (Figure 1a,
Figure S1).45,46 The supposed mechanism may include
the
reaction
between
pꢀdithianeꢀ2,5ꢀdiol
and
have shown that dealing the covalent triazineꢀbased materials
(CTFs) with ionothermal method can enhance their conductivity
and maintain parts of their inherent structures as well.33,38,39 The
1
2
3
4
5
6
7
8
a
Et3Nꢀcatalytic nucleophilic substitution (SNAr) reaction followed
by an intramolecular Adol reaction (Figure S2).47 The asꢀprepared
BTT was first reacted with 4ꢀtertꢀButyl benzenamine to test the
reactivity of its aldehyde groups (Figure 1b), which revealed that
the Schiffꢀbase reaction happened quickly to get the model
compound (MC). Then, three aminobenzene derivatives (DADP,
DAB and TAB) were selected to react with BTT, aiming to get
Schiffꢀbase BTTꢀCOFs with different pore sizes (BTTꢀDADP
COF, BTTꢀDAB COF and BTTꢀTAB COF, Figure 1c). All the
reaction details are listed in Supporting Information.
structure
transformations
of
heteroatomꢀcontained
Schiffꢀbase/imine COFs under ionothermal condition still need to
be studied.
In all the COFꢀrelated researches, designs and syntheses of the
symmetric molecular building blocks usually play the most
important role. Benzotrithiophene is a classic C3ꢀsymmetric
construction unit for solar cells,40,41 selfꢀassemblies,42,43 and metal
9
organic frameworks.44 Herein,
a
new benzotrithiophene
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
tricarbaldehyde (BTT) was synthesized through a facile method
Figure 2. Characterizations of the BTTꢀbased COFs. (a) Experimental and simulated XRD patterns with the corresponding structural
schemes, stacking ways, lattice parameters and space groups inserted. (b) Typical TEM image of BTTꢀbased COFs (from BTTꢀDAB COF).
(c) Nitrogen adsorptionꢀdesorption isotherms with pore size distribution profiles inserted. (d) FTꢀIR spectra compared with BTT and MC.
(e) UV/Vis DRS spectra with KubelkaꢀMunkꢀtransformed reflectance spectra inserted.
The crystalline structures of BTTꢀbased COFs were first
characterized by the Xꢀray diffraction (XRD) measurements.
Through comparing the experimental XRD patterns with the
simulated ones, it can be seen that the COFs are all of layered
structures with eclipsed stacking ways (Figure 2a, the fractional
atomic coordinates in Table S1-S3, schematic for the staggered
structures in Figure S3). The layered structures of COFs can
also be revealed by the typical transmission electron microscope
(TEM) image (Figure 2b). The space groups of BTTꢀDADP COF
and BTTꢀDAB COF belong to P6/m symmetry, and the space
group of BTTꢀTAB COF belongs to Pꢀ6 symmetry. From
BTTꢀDADP COF, BTTꢀDAB COF to BTTꢀTAB COF, the
diffraction angles of the (100) planes gradually get bigger,
suggesting that the pore sizes of the COFs gradually become
smaller, which is in correspondence with the decreasing simulated
lattice parameters (a and b, Figure 2a). This can also be testified
by the results of pore size distribution analyses, which are
calculated based on the nitrogen adsorptionꢀdesorption
measurements at 77K (Figure 2c, average pore sizes in Table S4).
Besides, the BrunauerꢀEmmettꢀTeller (BET) specific surface areas
(SSAs) of the COFs also become smaller along with the
decreasing pore sizes (insertion in Figure 2c).
The Fourier transform infrared (FTꢀIR) spectra of the COFs and
the MC show that the C=N stretching for imines at 1600 cmꢀ1
emerges, and the C=O stretching for aldehyde groups at 1670
cmꢀ1 disappears compared with BTT (Figure 2d), proving that the
COFs are indeed constructed through the Schiffꢀbase reactions.
The ultraviolet–visible diffuse reflectance spectra (UV/vis DRS)
were also used to test these colored COF powders. From
BTTꢀTAB COF (yellow), BTTꢀDADP COF (light orange) to
BTTꢀDAB COF (dark red), an obvious redꢀshift of the optical
absorption edge can be observed, and the corresponding optical
band gaps decrease from 2.38, 2.25 to 2.04 eV (Figure 2e, digital
photographs in Figure S4). The variation tendency of the band
gaps is obviously not consistent with the pore size changes of the
COFs, they may also be influenced by the different space groups
of the COFs (Figure 2a), which is still under study. Nevertheless,
the test results of UV/vis DRS here still make BTTꢀbased COFs
good candidates for the visibleꢀlight photocatalysis.
ACS Paragon Plus Environment

Page 3 of 9
Journal of the American Chemical Society
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
Figure 3. Structural characterizations and electrochemical performances of COFꢀ700s. (a) XRD patterns with the JCPDS card of ZnS2
(No. 36ꢀ1450) inserted (BTTꢀTAB COFꢀ700ꢀuntreated was derived from BTTꢀTAB COFꢀ700 untreated with hot HCl solution during
workup). (b) Nitrogen adsorptionꢀdesorption isotherms with pore size distribution profiles inserted. (c) Nitrogen contents in COFꢀ700s
(from XPS analyses) compared with COFs (calculated). (d) The ratios of sp2 hybridized carbon in COFꢀ700s (from XPS analyses)
compared with the calculated carbon contents in COFs. (e) the specific capacitances at different current densities with the typical GC
curves inserted. (f) Cumulative specific surface area (SSA) with pore size larger than the ion diameter of the electrolyte (effective SSA,
EꢀSSA); the insertion is the specific capacitance at 0.5 A/g versus the EꢀSSA, and slopes of the lines are proportional to the permittivity, ε
in the formula for supercapacitors: C=εS/d.
To enhance the conductivity of the COFs for electrochemical
applications, the COFs were treated under ionothermal condition
with five times mass of ZnCl2 at 700℃ for 20h (see details in
Supporting Information). The further crossꢀlinked COFs are
named as COFꢀ700s: BTTꢀDADP COFꢀ700, BTTꢀDAB COFꢀ700
and BTTꢀTAB COFꢀ700, respectively. Notably, if ZnCl2 was not
added, the prepared sample would have very low BET SSA and
irregular pore size distribution (e.g. 15.6 m2/g for the 700℃
ꢀtreated BTTꢀDAB COF without ZnCl2, Figure S5). Here, the
ZnCl2 might have the function of padding and supporting the pore
structures of the materials during the highꢀtemperature treatment.
the carbon contents in the corresponding COFs (Figure 3d and
Figure S7),48 which means COFs with higher carbon contents
finally transform to COFꢀ700s with higher ratios of sp2 carbon.
These test results indicate that the structure characteristics of
COFꢀ700s are all transformed regularly according to the original
COFs.
The electrochemical performances of COFꢀ700s were
characterized by a symmetric supercapacitor system (a CR2032
coinꢀtype cell) with an ionic liquid, 1ꢀethylꢀ3ꢀmethylimidazolium
tetrafluoroborate (EMIMBF4) as the electrolyte (details in
Supporting Information). The quasiꢀrectangular cyclic
voltammetry (CV) curves (Figure S8) and triangularꢀshape
galvanostatic chargeꢀdischarge (GC) curves (Figure S9, typically
in Figure 3e) show the typical doubleꢀlayer supercapacitor
characteristics of COFꢀ700ꢀbased supercapacitors. The specific
capacitances caculated based on the discharge slopes of GC
curves become smaller from BTTꢀDADP COFꢀ700, BTTꢀTAB
COFꢀ700 to BTTꢀDAB COFꢀ700 (Figure 3e). The rate capacity of
BTTꢀTAB COFꢀ700 is worse than that of BTTꢀDADP COFꢀ700
and BTTꢀDAB COFꢀ700, which is because of its relatively bigger
equivalent series resistance (results of AC impedence in Figure
S10).49 The typical cycling perfomance test of BTTꢀDADP
COFꢀ700 at current density of 10 A/g shows that the specific
capacitance still remain 77.5% after 10 000 cycles (Figure S11).
Compared with the crystalline structures of COFs, COFꢀ700s
all change to amorphous (XRD patterns in Figure 3a), which can
also be testified by the typical TEM image in Figure S6. If the
samples were not washed adequately with hot HCl solution during
workup, the XRD peaks indexed to ZnS2 could be observed
(Figure 2a), which suggested that the sulfur atoms in the BTT
were reacted with ZnCl2 to form ZnS2 under the ionothermal
condition. This can also explain why the sulfur contents in
COFꢀ700s are all lower than 1 wt.% (XPS results in Table S5).
The results of nitrogen adsorptionꢀdesorption measurements
reveal that the BET SSAs and average pore sizes of COFꢀ700s all
become larger in contrast with that of the COFs (Figure 3b, Table
S4). Besides, the SSAs and pore sizes gradually become smaller
from BTTꢀDADP COFꢀ700, BTTꢀDAB COFꢀ700 to BTTꢀTAB
COFꢀ700 (Figure 3b), which have the same variation tendency
compared with that of the COFs (Figure 2c). The nitrogen
contents in COFꢀ700s and the corresponding COFs maintain
almost the same change regularity (Figure 3c). More interestingly,
the ratios of sp2 hybridized carbon in COFꢀ700s vary along with
To further investigate the relationships between the structures
of COFꢀ700s and their supercapacitor performances, the
cumulative surface areas of the pores bigger than the diameter of
the electrolyte (0.75nm for EMIM+) were extracted (Figure 3f),
which could be treated as the effective SSA (EꢀSSA) for the
supercapacitors.33,50 According to the fundamental formula for
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 4 of 9
supercapacitors: C=εS/d, d is the thickness of the electric double
Science and Engineering, Ocean University of China for the
support in XRD simulations.
layer, which is a constant when the electrolyte and testing
conditions are fixed. Consequently, the permittivity (ε), which
represents the interaction between the electrolyte and electrode
material is proportional to the C/S (specific capacitance/EꢀSSA,
slopes of the lines in the inserted figure of Figure 3f). Through
comparing the slopes, it can be concluded that the interactions
between the COFꢀ700s and the electrolyte gradually become
weaker form BTTꢀTAB COFꢀ700, BTTꢀDADP COFꢀ700 to
BTTꢀDAB COFꢀ700. This variation tendency is inconsonant with
the changes of pore sizes and nitrogen contents of COFꢀ700s
(Figure 3b and 3c), but is accordant with the change of the ratios
of sp2 carbon in COFꢀ700s (Figure 3d), which means COFꢀ700
with the higher ratio of sp2 carbon has the stronger interaction
with the electrolyte. This also indicates that the EꢀSSA and the
interaction between electrode materials and the electrolyte (ε)
should be carefully balanced, and besides the pore sizes and
heteroatomꢀdoping, the ratio of sp2 carbon in the materials should
also be concerned when designing and synthesizing the materials
for supercapacitors.
1
2
3
4
5
6
7
8
REFERENCES
(1) Diercks, C. S.; Yaghi, O. M. Science 2017, 355.
(2) Huang, N.; Wang, P.; Jiang, D. Nat. Rev. Mater. 2016, 1, 16068.
(3) Das, S.; Heasman, P.; Ben, T.; Qiu, S. Chem. Rev. 2017, 117, 1515.
(4) Guan, X.; Ma, Y.; Li, H.; Yusran, Y.; Xue, M.; Fang, Q.; Yan, Y.;
Valtchev, V.; Qiu, S. J. Am. Chem. Soc. 2018, 140, 4494.
(5) Zhai, L.; Huang, N.; Xu, H.; Chen, Q.; Jiang, D. Chem. Commun.
2017, 53, 4242.
(6) Pang, Z.ꢀF.; Xu, S.ꢀQ.; Zhou, T.ꢀY.; Liang, R.ꢀR.; Zhan, T.ꢀG.; Zhao,
X. J. Am. Chem. Soc. 2016, 138, 4710.
(7) Fang, Q.; Zhuang, Z.; Gu, S.; Kaspar, R. B.; Zheng, J.; Wang, J.;
Qiu, S.; Yan, Y. Nat. Commun. 2014, 5, 4503.
(8)Lu, Q.; Ma, Y.; Li, H.; Guan, X.; Yusran, Y.; Xue, M.; Fang, Q.; Yan,
Y.; Qiu, S.; Valtchev, V. Angew. Chem. Int. Edit. 2018, 57, 6042.
(9) Diercks, C. S.; Lin, S.; Kornienko, N.; Kapustin, E. A.; Nichols, E.
M.; Zhu, C.; Zhao, Y.; Chang, C. J.; Yaghi, O. M. J. Am. Chem. Soc. 2018,
140, 1116.
(10) Lohse, M. S.; Stassin, T.; Naudin, G.; Wuttke, S.; Ameloot, R.; De
Vos, D.; Medina, D. D.; Bein, T. Chem. Mater. 2016, 28, 626.
(11) Ding, S.ꢀY.; Dong, M.; Wang, Y.ꢀW.; Chen, Y.ꢀT.; Wang, H.ꢀZ.; Su,
C.ꢀY.; Wang, W. J. Am. Chem. Soc. 2016, 138, 3031.
(12) Pachfule, P.; Acharjya, A.; Roeser, J.; Langenhahn, T.; Schwarze,
M.; Schomäcker, R.; Thomas, A.; Schmidt, J. J. Am. Chem. Soc. 2018, 140,
1423.
(13) Waller, P. J.; Lyle, S. J.; Osborn Popp, T. M.; Diercks, C. S.;
Reimer, J. A.; Yaghi, O. M. J. Am. Chem. Soc. 2016, 138, 15519.
(14) Ascherl, L.; Sick, T.; Margraf, J. T.; Lapidus, S. H.; Calik, M.;
Hettstedt, C.; Karaghiosoff, K.; Döblinger, M.; Clark, T.; Chapman, K. W.;
Auras, F.; Bein, T. Nat. Chem. 2016, 8, 310.
(15) Vyas, V. S.; Haase, F.; Stegbauer, L.; Savasci, G.; Podjaski, F.;
Ochsenfeld, C.; Lotsch, B. V. Nat. Commun. 2015, 6, 8508.
(16) Huang, N.; Zhai, L.; Xu, H.; Jiang, D. J. Am. Chem. Soc. 2017,
139, 2428.
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
In summary,
a
new C3ꢀsymmetric benzotrithiophene
tricarbaldehyde (BTT) and a series of BTTꢀbased COFs have been
constructed for the first time. These COFs display gradually
increased pore sizes and SSAs, and also show good potential for
visibleꢀlight photocatalysis with optical band gaps of 2.04ꢀ2.08
eV. More importantly, the furtherꢀcrosslinked COFs under
ionothermal condition (COFꢀ700s) reveal regularly changed pore
sizes, SSAs, nitrogen contents and ratios of sp2 carbon according
to the structures of the corresponding COFs. And the test results
of COFꢀ700ꢀbased supercapacitors show that the interaction
between COFꢀ700s and the electrolyte is related to the ratios of
sp2 carbon in COFꢀ700s. In short, dealing COFs of designated
structures under ionothermal condition is a great method to build
(17) Sun, Q.; Aguila, B.; Perman, J.; Nguyen, N.; Ma, S. J. Am. Chem.
Soc. 2016, 138, 15790.
(18) Medina, D. D.; Petrus, M. L.; Jumabekov, A. N.; Margraf, J. T.;
Weinberger, S.; Rotter, J. M.; Clark, T.; Bein, T. ACS Nano 2017, 11,
2706.
highꢀconductive
structureꢀcontrollable
materials
for
electrochemical applications. This method is extremely beneficial
for both the inꢀdepth study of the structureꢀperformance
relationships in electrochemistry and the further enhancement of
electrochemical performances.
(19) Zhang, D. S.; Chang, Z.; Lv, Y. B.; Hu, T. L.; Bu, X. H. Rsc Adv.
2012, 2, 408.
(20) Kissel, P.; Erni, R.; Schweizer, W. B.; Rossell, M. D.; King, B. T.;
Bauer, T.; Gotzinger, S.; Schluter, A. D.; Sakamoto, Nat. Chem. 2012, 4,
287.
(21) Evans, A. M.; Parent, L. R.; Flanders, N. C.; Bisbey, R. P.; Vitaku,
E.; Kirschner, M. S.; Schaller, R. D.; Chen, L. X.; Gianneschi, N. C.;
Dichtel, W. R. Science 2018, 361, 52.
(22) Ma, T.; Kapustin, E. A.; Yin, S. X.; Liang, L.; Zhou, Z.; Niu, J.; Li,
L.ꢀH.; Wang, Y.; Su, J.; Li, J.; Wang, X.; Wang, W. D.; Wang, W.; Sun, J.;
Yaghi, O. M. Science 2018, 361, 48.
(23) Auras, F.; Ascherl, L.; Haldmioun, A. H.; Margraf, J. T.; Hanusch,
F. C.; Reuter, S.; Bessinger, D.; Doblinger, M.; Hettstedt, C.; Karaghiosoff,
K.; Herbert, S.; Knochel, P.; Clark, T.; Bein, T. J. Am. Chem. Soc. 2016,
138, 16703.
(24) Slater, A. G.; Cooper, A. I. Science 2015, 348, 988.
(25) Ding, S. Y.; Wang, W. Chem. Soc. Rev. 2013, 42, 548.
(26) Xiang, Z.; Cao, D. J. Mater. Chem. A 2013, 1, 2691.
(27) Xu, F.; Jin, S.; Zhong, H.; Wu, D.; Yang, X.; Chen, X.; Wei, H.; Fu,
R.; Jiang, D. Sci. Rep. 2015, 5, 8225.
(28) Wang, S.; Wang, Q.; Shao, P.; Han, Y.; Gao, X.; Ma, L.; Yuan, S.;
Ma, X.; Zhou, J.; Feng, X.; Wang, B. J. Am. Chem. Soc. 2017, 139, 4258.
(29) Yang, D. H.; Yao, Z. Q.; Wu, D.; Zhang, Y. H.; Zhou, Z.; Bu, X. H.
J. Mater. Chem. A 2016, 4, 18621.
(30) Talapaneni, S. N.; Hwang, T. H.; Je, S. H.; Buyukcakir, O.; Choi, J.
W.; Coskun, A. Angew. Chem. Int. Edit. 2016, 55, 3106.
(31) Ghazi, Z. A.; Zhu, L. Y.; Wang, H.; Naeem, A.; Khattak, A. M.;
Liang, B.; Khan, N. A.; Wei, Z. X.; Li, L. S.; Tang, Z. Y. Adv. Energy
Mater. 2016, 6, 1601250.
ASSOCIATED CONTENT
Supporting Information
Supporting Information consists of experimental section, Figures
S1ꢀS11, and Tables S1ꢀS5. This material is available free of
charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
L.H., Eꢀmail: haol@qau.edu.cn
Author Contributions
§H.W., J.N. and X.C. contribute equally to this work.
Notes
The authors declare no competing financial interests.
ACKNOWLEDGMENT
This work was supported by National Natural Science Foundation
of China (51603114), Natural Science Foundation of Shandong
Province (ZR2016EMQ03), Science and Technology Foundation
of Qingdao City (16ꢀ5ꢀ1ꢀ43ꢀjch) and Doctorial Fund of Qingdao
Agriculture University (663ꢀ1115046, 663ꢀ1117016 and
663/1113309). The authors acknowledge School of Material
(32) Xu, F.; Xu, H.; Chen, X.; Wu, D.; Wu, Y.; Liu, H.; Gu, C.; Fu, R.;
Jiang, D. Angew. Chem. Int. Edit. 2015, 54, 6814.
4
ACS Paragon Plus Environment

Page 5 of 9
Journal of the American Chemical Society
(33) Hao, L.; Ning, J.; Luo, B.; Wang, B.; Zhang, Y.; Tang, Z.; Yang, J.;
(42) Xiao, Q.; Sakurai, T.; Fukino, T.; Akaike, K.; Honsho, Y.; Saeki, A.;
Seki, S.; Kato, K.; Takata, M.; Aida, T. J. Am. Chem. Soc. 2013, 135,
18268.
(43) Ikeda, T.; Adachi, H.; Fueno, H.; Tanaka, K.; Haino, T. J. Org.
Chem. 2017, 82, 10062.
Thomas, A.; Zhi, L. J. Am. Chem. Soc. 2015, 137, 219.
(34) 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.
Science 2015, 349, 1208.
1
2
3
4
5
6
7
8
9
(35) Nandi, S.; Singh, S. K.; Mullangi, D.; Illathvalappil, R.; George,
L.; Vinod, C. P.; Kurungot, S.; Vaidhyanathan, R. Adv. Energy Mater. 2016,
6, 1601189.
(36) Kou, Y.; Xu, Y.; Guo, Z.; Jiang, D. Angew. Chem. Int. Edit. 2011,
50, 8753.
(37) Zhang, J.; Zhao, Z.; Xia, Z.; Dai, L. Nat. Nanotechnol. 2015, 10,
444.
(38) Hao, L.; Luo, B.; Li, X.; Jin, M.; Fang, Y.; Tang, Z.; Jia, Y.; Liang,
M.; Thomas, A.; Yang, J.; Zhi, L. Energ. Environ. Sci. 2012, 5, 9747.
(39) Hao, L.; Zhang, S.; Liu, R.; Ning, J.; Zhang, G.; Zhi, L. Adv. Mater.
2015, 27, 3190.
(40) MolinaꢀOntoria, A.; Zimmermann, I.; GarciaꢀBenito, I.; Gratia, P.;
RoldánꢀCarmona, C.; Aghazada, S.; Graetzel, M.; Nazeeruddin, M. K.;
Martín, N. Angew. Chem. Int. Edit. 2016, 55, 6270.
(41) Gu, C.; Huang, N.; Chen, Y.; Qin, L.; Xu, H.; Zhang, S.; Li, F.; Ma,
Y.; Jiang, D. Angew. Chem. Int. Edit. 2015, 54, 13594.
(44) Feng, D.; Liu, T.ꢀF.; Su, J.; Bosch, M.; Wei, Z.; Wan, W.; Yuan, D.;
Chen, Y.ꢀP.; Wang, X.; Wang, K.; Lian, X.; Gu, Z.ꢀY.; Park, J.; Zou, X.;
Zhou, H.ꢀC. Nat. Commun. 2015, 6, 5979/1.
(45) Taerum, T.; Lukoyanova, O.; Wylie, R. G.; Perepichka, D. F. Org.
Lett. 2009, 11, 3230.
(46) Wei, H.; Sun, M.; Ji, M. J. Chem. Res. 2009, 2009, 359.
(47) Yang, L.ꢀL.; Hu, X.ꢀL.; Tang, Z.ꢀQ.; Li, X.ꢀF. Chem. Lett. 2015, 44,
1515.
(48) Zhang, C.; Fu, L.; Liu, N.; Liu, M.; Wang, Y.; Liu, Z. Adv. Mater.
2011, 23, 1020.
(49) Ra, E. J.; RaymundoꢀPiñero, E.; Lee, Y. H.; Béguin, F. Carbon
2009, 47, 2984.
(50) Zhang, L.; Yang, X.; Zhang, F.; Long, G.; Zhang, T.; Leng, K.;
Zhang, Y.; Huang, Y.; Ma, Y.; Zhang, M.; Chen, Y. J. Am. Chem. Soc.
2013, 135, 5921.
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
Table of Contents artwork
5
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 6 of 9
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
90x51mm (300 x 300 DPI)
ACS Paragon Plus Environment

Page 7 of 9
Journal of the American Chemical Society
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
83x47mm (300 x 300 DPI)
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 8 of 9
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
85x43mm (300 x 300 DPI)
ACS Paragon Plus Environment

Page 9 of 9
Journal of the American Chemical Society
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
A C3-symmetric benzotrithiophene tricarbaldehyde (BTT) and a series of BTT-based covalent organic
frameworks (BTT-COFs) are constructed for the first time. Meanwhile, structure transformations of the COFs
under high-temperature ionothermal condition are studied systematically. The BTT-COFs and ionothermal-
dealing method have shown great potential for photocatalysis and electrochemistry.
47x41mm (300 x 300 DPI)
ACS Paragon Plus Environment