Rational Construction of Borromean Linked Crystalline Organic Polymers

Article abstract of DOI:10.1002/anie.202012504

Attributed to the unique topological complexity and elegant beauty, Borromean systems are attracting intense attention. However, at present, the construction of Borromean linked organic polymers remains a challenge. To address this formidable challenge, we developed a supramolecular-synthon-driven approach to fabricate Borromean linked organic polymer. The solvothermal condensation reaction of a judiciously selected trigonal pyramidal building block, 1,3,5-Tris(4-aminophenyl)adamantane, with linear dialdehyde building blocks allowed the construction of two rare covalent organic frameworks (COFs) with high crystallinity and robustness. Structure refinement unveiled the successful formation of entangled 2D→2D Borromean arrayed structures. Both the two COFs were of microporosity and thus demonstrated the potentials for gas separation. The successful synthesis of the first two Borromean linked organic polymers paves the avenue to expand the supramolecular-synthon-driven approach to other building blocks and topologies, and broadens the family and scope of COFs.

Full text of DOI:10.1002/anie.202012504

A Journal of the Gesellschaft Deutscher Chemiker
Angewandte
International Edition Chemie
www.angewandte.org
Accepted Article
Title: Rational Construction of Borromean Linked Crystalline Organic
Polymers
Authors: Xiuxiu Guo, En Lin, Jia Gao, Tianhui Mao, Dong Yan, Peng
Cheng, Yao Chen, Shengqian Ma, and Zhenjie Zhang
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.202012504
Link to VoR: https://doi.org/10.1002/anie.202012504

Angewandte Chemie International Edition
10.1002/anie.202012504
RESEARCH ARTICLE
Rational Construction of Borromean Linked Crystalline Organic
§
Polymers
Xiuxiu Guo,+,[a],[b] En Lin,+,[a],[b] Jia Gao,[a],[b] Tianhui Mao,[a],[b] Dong Yan,[a],[b] Peng Cheng,[a],[b],[c]
[
d]
[a]
,[a],[b],[c]
Shengqian Ma, Yao Chen and Zhenjie Zhang*
Abstract: Attributed to the unique topological complexity and elegant
However, the design, prediction, and rationalization of CPMs’
beauty, Borromean systems are attracting intense attention. However, structures are always of great challenge. Thanks to the pioneering
works by Robson,[ Yaghi, O'Keeffe, et al., the design and
construction of desired CPM structures may be realized using the
"node and linker" approach, and the reticular chemistry synthesis
approach. However, obtaining the desired CPM structures is not
always guaranteed.[
21]
[22]
[23]
[24]
at present, the construction of Borromean linked organic polymers
remains a challenge. To address this formidable challenge, we
developed a supramolecular-synthon-driven approach to fabricate
Borromean linked organic polymer. The solvothermal condensation
reaction of a judiciously selected trigonal pyramidal building block,
25]
1
,3,5-Tris(4-aminophenyl)adamantane, with linear dialdehyde
The Borromean links, in which three rings are interlocked and
no two are interlinked, constitute topologically intriguing
entanglement. Attributed to their unique topological complexity,
structural integrity, and elegant beauty, the Borromean systems
have attracted the attention of scientists from various
building blocks allowed the construction of two rare covalent organic
frameworks (COFs) with high crystallinity and robustness. Structure
refinement unveiled the successful formation of entangled 2D➙2D
Borromean arrayed structures. Both the two COFs were of
[26]
microporosity and thus demonstrated the potentials for gas separation. backgrounds.[27-29] The earliest example of molecular Borromean
[
30-
The successful synthesis of the first two Borromean linked organic
polymers paves the avenue to expand the supramolecular-synthon-
driven approach to other building blocks and topologies, and
broadens the family and scope of COFs.
rings was reported in 1997 via manipulating DNA sequences.
3
1]
In 2004, Stoddart and collaborators reported the first molecular
Borromean links achieved by a coordination-driven assembly
strategy.[32] Since Stoddart’s pioneering work, coordination
chemistry has been frequently used to drive the formation of
Borromean arrayed structures. For example, Lu group
synthesized a 2D➙2D entangled coordination polymer with a
Borromean structure.[33] Besides, Zheng and co-workers first
reported the rational construction of HOFs with Borromean 3-fold
2D➙2D entangled layers, and n-Borromean 2D➙3D entangled
infinite layers based on hydrogen-bond-driven self-assembly of
Introduction
In the past three decades, crystalline porous materials
CPMs)[1,2] including metal-organic frameworks (MOFs),[3]-[4]
(
covalent organic frameworks (COFs),[5-9] hydrogen-bonded
organic frameworks (HOFs),[10] zeolites,[11] metal-organic
1,3,5-tris(4-carboxy-phenyl)adamantane (TCA).[34]
Overall, the
polyhedra (MOPs),[12-13] and porous organic cage (POC),[14] have
development of Borromean systems is still underexplored, and
creating advanced materials with desired Borromean structures is
urgently demanded.
Since the pioneering work by Yaghi in 2005,[35] COFs have
emerged a new class of CPMs with periodic networks linked by
covalent bonds. However, up to now, the construction of COFs
with Borromean links remains a formidable challenge. In order to
achieved terrific progress in many research fields such as
catalysis,[15] gas storage and separation,[16] electrochemistry,[17]
drug delivery,[18] sensing[19] and fluorescence imaging,[20]
attributed to their high crystallinity and regular porous structures.
The outstanding properties of CPMs depend on their structures.
design and synthesize Borromean arrayed COFs, three factors
are essential: i) the 63 honeycomb net with large enough
[
[
a]
b]
X. Guo, E. Lin, J. Gao, T. Mao, D. Yan, Prof. P. Cheng, Prof. Y.
Chen, Prof. Z. Zhang
State Key Laboratory of Medicine Chemistry Biology, College of
Chemistry, Nankai University
hexagonal cavities, which ensure the accommodation for other
two nets; ii) the chair conformation of the hexagonal rings; iii)
appropriate interactions between the modules at each
Tianjin 300071, China
E-mail: zhangzhenjie@nankai.edu.cn
X. Guo, E. Lin, J. Gao, T. Mao, D. Yan, Prof. P. Cheng, Prof. Z.
Zhang
Renewable Energy Conversion and Storage Center, College of
Chemistry, Nankai University
Tianjin 300071, China
Prof. P. Cheng, Prof. Z. Zhang
Key Laboratory of Advanced Energy Materials Chemistry
Ministry of Education, Nankai University
Tianjin 300071, China
[36]
intersection that can control the direction of interpenetration.
Based on the above considerations, we first created
a
supramolecular-synthon-driven approach to construct COFs with
Borromean links (Scheme 1a). According to the literature
survey,[34,36] 1,3,5-triphenyl-adamantane is a perfect module to
[
[
c]
d]
build Borromean structures because it can form an ‘up-down’
dimeric supramolecular synthon stabilized by C―H···π
interactions to direct the interweaving and the packing of
structures (Scheme 1b). Thereupon, to demonstrate the proof of
concept, we judiciously chose a rigid and trigonal pyramidal
molecule, 1,3,5-Tris(4-aminophenyl)adamantane (TAA), as the
main building blocks for the construction of Borromean linked
COFs. Furthermore, linear linkers such as terephthalaldehyde
Prof. S. Ma
Department of Chemistry
University of North Texas
1508 W Mulberry St, Denton, TX 76201, USA
[+
§]
]
These authors contributed equally to this work.
th
[
Dedicated to the 100 anniversary of Chemistry at Nankai University
(
TP) and its extended variant (4,4'-biphenyldicarboxaldehyde,
Supporting information for this article is given via a link at the end of
the document.
BPDA) were chosen as the guiding skeletons for the formation of
This article is protected by copyright. All rights reserved.

Angewandte Chemie International Edition
10.1002/anie.202012504
RESEARCH ARTICLE
two entangled 2D➙2D Borromean layered structures, NKCOF-6
and -7 (NKCOF
= Nankai University Covalent Organic
Framework).
Scheme 1. a) Illustration of the approach to build Borromean arrayed networks.
b) The stable ‘up-down’ dimeric supramolecular synthon formed by 1,3,5,-
triphenyl-adamantane moieties.
Figure 2. a) FT-IR spectra of NKCOF-6 and corresponding monomers. b) 13
CP/MAS solid-state NMR spectra of NKCOF-6. c) SEM image of NKCOF-6.
d) AFM image and the height profile of NKCOF-6.
C
Results and Discussion
The as-prepared NKCOF-6 was then submitted to the powder
X-ray diffraction (PXRD) analysis to determine its crystal structure
by comparing the experimental PXRD pattern with the
On this basis of the above design (Figure 1), the solvothermal
reaction of TAA and TP in the mixed solvent of 1,2-
dichlorobenzene, 1-butanol, and acetic acid at 120 °C for three
days afforded a crystalline powder of NKCOF-6 with a yield of
theoretically simulated model,[
37-38]
which was conducted with the
Materials Studio Software package. As shown in Figure 3, the two
most intense diffraction peaks in the PXRD profile of NKCOF-6
appeared at 4.26° and 5.82° (2θ). They exhibited strong diffraction
intensity together with narrow Full width at half maximum (FWHM),
indicating a high crystallinity of NKCOF-6. To solve the structure
of NKCOF-6, we referred to the real crystal structures of
Borromean linked HOFs reported by Zheng and co-workers. In
these HOFs, the TCA dimers inside layered Borromean weaves
were hydrogen-bonded with each other through –COOH groups
in TCA. The hydrogen bonds between carboxylic acid dimer
synthon were linear and coplanar. Therefore, these HOF
structures can be treated as perfect models to solve the structure
of NKCOF-6, via replacing the carboxylic acid dimer synthon by
linear linkers such as p-phenyl diimine moieties (Figure S3). On
the basis of this concept, we assumed the possible crystal
structure of NKCOF-6 was assembled with paralleled 2D
honeycomb sheets, i.e., 3-fold interwoven structures with
entangled ABC stacking analogous to the layered Borromean
~
60%. Subsequently, the as-prepared yellow powder was
collected by filtration and washed by Soxhlet extraction. A variety
of methods were employed for structural characterizations of
NKCOF-6. The formation of NKCOF-6 was assessed by the
Fourier transform infrared (FT-IR) spectrum and 13C cross-
polarization magic-angle spinning (CP/MAS) NMR spectroscopy.
Compared with the corresponding TAA and aldehydes monomer,
the FT-IR spectrum revealed a new peak at 1621 cm-1 for
NKCOF-6 (Figure 2a), which is a typical characteristic of the C=N
stretching vibrations. Meanwhile, the disappearance of the C=O
stretching vibrations (1682 cm-1 for TP) and the N-H stretching
vibrations (3441 cm-1 and 3363 cm-1 for TAA) indicated the
complete transformation of aldehyde- and amine-containing
1
3
reactants. The C NMR spectroscopy further confirmed the
successful formation of imine groups by the peak at 158.3 ppm
for NKCOF-6 (Figure 2b). Scanning electron microscopy (SEM)
3
weaves. In the ideal case, TAA is considered as a C -symmetry
images revealed that NKCOF-6 exhibited
a
distinctive
molecule that possesses identical tetrahedral angles without
distortion. However, in the real CPM networks, the tetrahedral
angles are always distorted that break the intrinsic symmetry of
TAA, hence leading to desymmetrize the network and lattice. This
kind of phenomenon has been observed in the HOFs reported by
Zheng and co-workers.[31] Based on this hypothesis, we
discovered a set of unit cell parameters (a = b= 22.5 Å, c = 9.0 Å,
α = β = 100°, γ = 133°) that matched the experimental PXRD
pattern from both the positions and the intensities very well. All
the observed diffraction peaks at d-spacing (2θ) 20.61 Å (4.27°),
homogeneous spheric morphology with approximately 2.1 µm
diameter particles (Figure 2c). In addition, the successful
synthesis of NKCOF-6 was verified by the synthesis of a model
compound by a reaction of TAA with benzaldehyde (Figure S1
and S2).
1
5
0
5.15 Å (5.81°), 8.07 Å (10.90°), 6.85 Å (12.85°), 5.30 Å (16.6°),
.00 Å (17.6°), can be assigned to (1 0 0), (1 -1 0), (0 1 -1), (3 0
), (1 -3 0), and (3 -3 0) facets, respectively. Pawley refinement
gave the unit-cell parameters of a = 22.6 Å, b = 16.2 Å, c = 9.0 Å,
α = 94.2°, β = 100.3° and γ = 110.6°, with Rwp = 6.93% and R
.38%. In the layer stacking model of NKCOF-6 frameworks,
adjacent adamantane vertices demonstrated a small ateral offset
between adjacent COF layers (Figure 3c).
p
=
5
Figure 1. Illustration of the synthetic route of NKCOF-6.
This article is protected by copyright. All rights reserved.

Angewandte Chemie International Edition
10.1002/anie.202012504
RESEARCH ARTICLE
experimental PXRD with the theoretically simulated ones. A
series of peaks at d-spacing (2θ) 24.7 Å (3.56°), 18.0 Å (4.89°),
and 8.97 Å (9.81°) are observed for NKCOF-7 (Figure 4). We
noted that the d-spacing of NKCOF-7 diffraction peaks present
equal proportion compared with that of NKCOF-6, and the scale
factor is 1.1 approximately, which meant that NKCOF-7 shared
the identical structural feature with NKCOF-6 and adapted the
same stacking mode. The refined PXRD profile matched the
experimental pattern quite well, giving unit cell parameters of a =
2
7.1 Å, b = 19.3 Å, c = 9.0 Å, α = 88.7°, β = 81.2° and γ = 110.6°,
with Rwp = 3.25% and R = 2.21%, respectively. In addition, the
successful synthesis of NKCOF-7 was verified by the synthesis of
model compound by reaction of TAA with 4-
p
a
a
Figure 3. a) PXRD patterns of NKCOF-6. b) Space-filling model of Borromean
weaves of NKCOF-6. Paralleled honeycomb sheets in layered Borromean
weaves are shown as red, blue, gold. c) Separable Borromean weaves in
NKCOF-6.
Phenylbenzaldehyde (Figure S10 and S11).
The structures of CPMs are categorized based on their
underlying topologies, which can be described based on the
number of vertices, edges, rings, and tiles. At present, the vast
majority of reported COFs possess topologies with only one or
two kinds of vertices and one kind of edge. For instance, the
entangled ABC stacking models proposed above can be
considered as the derivates of dia-z topology, with one kind of
vertices and edges. Paralleled 2D honeycomb sheets with other
stacking modes such as eclipsed AA stacking and AB stacking
without entanglement, were also constructed as comparisons.
However, both of them demonstrated a largely deviate from the
experimental PXRD patterns (Figure S4). To further verify the
correctness of Borromean linked ABC stacking model, we
screened all the possible topologies that have one or two kinds of
Figure 4. a) PXRD patterns of NKCOF-7. b) The linear linker of NKCOF-7. c)
The hexagonal rings with chair conformation of NKCOF-7.
The entangled Borromean networks usually exhibit higher
stability than the structures without entanglement. NKCOFs was
activated under vacuum at 120 °C for 12 h before characterization.
Thermal gravimetric analysis (TGA) measurement revealed
NKCOF-6 and -7 could be thermally stable up to 450 °C under N2
without weight loss (Figure S12 and S13). The decomposition
temperature is higher than some traditional imine-based COFs
without entanglement (Table S3).[40-47] In addition, NKCOF-6 and
-7 exhibited excellent chemical stability in various solvents, such
as water, tetrahydrofuran (THF), N,N-dimethylformamide (DMF),
acetone, acetonitrile and methanol (MeOH). Moreover, NKCOF-
6 and -7 also exhibited good chemical stability under harsh
conditions such as aqueous NaOH (1 M) and HCl (pH = 2). PXRD
data revealed that NKCOF-6 and -7 retained their crystalline
structures after treatments under these conditions (Figure S14
and S15). The static water contact angle of the surface was
measured to investigate the hydrophilic-hydrophobic property of
COFs, that revealed a static water contact angles 95° for NKCOF-
6 and 101° for NKCOF-7 (Figure S16). According to literature,[
the hydrophobic property of NKCOFs could contribute to their high
water stability.
3
-connected vertices in the Reticular Chemistry Structure
[39]
Resource (RCSR)
database. Totally, 193 topologies were
identified and screened, and only two of them (srs-c8, ths-c3)
were promising, in terms of their diffraction peak positions and
relative intensity (Figure S4). However, these two networks depict
3
3
much lower densities (srs-c8: 0.252 g/cm , ths-c3: 0.114 g/cm )
3
than the experimental density (0.681 g/cm ) measured for
NKCOF-6. By contrast, the experimental density of NKCOF-6
matched well with that of the Borromean layered structure (0.618
3
g/cm ). The transmission electron microscopy (TEM) analyses
revealed that NKCOF-6 can be exfoliated into 2D nanosheets,
consistent with the simulated layered structure (Figure S5).
Atomic force microscopy (AFM) experiments were carried out to
measure the thickness of the exfoliated nanosheets of NKCOF-6
(
Figure 2d and S6). The thickness of the thinnest nanosheet was
measured to be about 1.6 nm, which was close to the monolayer
thickness of proposed structure (1.4 nm). This result indicated that
NKCOF-6 possessed the predicted 2D layered structure.
48]
To explore the generality of the supramolecular-synthon-driven
approach to construct COFs with Borromean moieties, we used
an extended variant of TP, i.e., BPDA, as the linear linker. The
solvothermal reaction of TAA and BPDA afforded a pale yellow
powder of NKCOF-7 with a high yield of ~83%. FI-IR spectra and
solid-phase 13C NMR further confirmed the existence of imine
linkages in NKCOF-7 (Figure S7 and S8). SEM analyses showed
NKCOF-7 exhibited a homogeneous spheric morphology with
The porosity and specific surface areas of NKCOF-6 and -7
were characterized by N
5). The adsorption isotherms of NKCOFs showed a sharp uptake
at a low-pressure of P/P range (P/P = 0-0.05), which was a
2
adsorption-desorption at 77 K (Figure
0
0
typical characteristic of microporous materials exhibited a classic
type  isotherm. The Langmuir surface area of NKCOF-6 and -7
2
-1
2
-1
was calculated to be 328 m g and 1052 m g , respectively.
Pore size distributions calculated based on the nonlocal density
functional theory (NLDFT) demonstrated an average pore size of
~
1.3 µm particle size (Figure S9). Similar to NKCOF-6, the crystal
structure of NKCOF-7 was also elucidated by comparing the
This article is protected by copyright. All rights reserved.

Angewandte Chemie International Edition
10.1002/anie.202012504
RESEARCH ARTICLE
1
.1 nm and 1.3 nm for NKCOF-6 and -7, respectively, which are
In summary, we, for the first time, developed an efficient and
versatile supramolecular-synthon-driven approach to construct
COFs with Borromean links, which have not been achieved yet in
in good agreement with the simulated values (1.0 nm and 1.2 nm
for NKCOF-6, and -7, respectively, obtained from the Poreblazer
software[49]).
the literature.
judiciously selected trigonal pyramidal building block (1,3,5-
Tris(4-aminophenyl)adamantane) with the linear
A solvothermal condensation reaction of a
terephthalaldehyde building block allowed the construction of a
rare 2D imine-based COF (NKCOF-6) with high crystallinity and
robustness. In order to determine the COF structure, we
developed a novel strategy: using the real single-crystal structure
of reported HOFs as the structure model and substituting the
planar carboxylic acid dimer synthon in HOFs by p-phenyl diimine
linear linker in COFs. Structure refinement unveiled that this COF
possessed a twisted hexagonal crystal lattice and entangled 2D
2
Figure 5. a) N adsorption−desorption isotherms of NKCOF-6 and NKCOF-7
collected at 77 K. b) Pore size distributions of NKCOF-6 and NKCOF-7.
➙2D Borromean layered structure. Furthermore, we proved the
generality of the supramolecular-synthon-driven approach and
successfully fabricated another Borromean linked COF, NKCOF-
Given the microporous nature of NKCOF-6 and -7, we
investigated their potential application for gas separation.
7
, via extending the length of the dialdehyde linker. Moreover,
both the two COFs were of microporosity and thus can be used
to separate C over CO . This work not only enriched the family
Currently, one of the urgent challenges in acetylene (C
production is the removal of the co-existence of carbon dioxide
CO and CO is of
) impurities.[50] However, separation of C
2 2
H )
2
H
2
2
(
2
2
H
2
2
and scope of COFs, but also realized a new powerful strategy to
fabricate Borromean linked materials.
the paramount challenge because they possess very similar
3
molecule shapes/sizes (3.32 × 3.34 × 5.70 Å for C
2
H
2
and 3.18
3
×
3.33 × 5.36 Å for CO
2
), and similar physical properties (boiling
[
51]
points of 189.3 K and 194.7 K, respectively). To address this
challenge, we collected the single-component gas adsorption
Acknowledgements
2 2 2
isotherms for C H and CO at 273 K and 298 K at 1 bar,
respectively. As shown in Figure S17 and S18, the uptakes of
NKCOF-6 at 1 bar and 298 K were up to 30.9 cm³/g and 15.6
The authors acknowledge the National Natural Science
Foundation of China (21971126) and 111 Project (B12015). We
also thank Dr. Kai Zhang and Haixia Li from Nankai University for
the assistance of TEM and AFM tests.
cm³/g for C
those of NKCOF-7 (30.2 cm³/g for C
2
H
2
and CO
2
, respectively, which were higher than
, 13.8 cm³/g for CO ). The
2
H
2
2
isosteric enthalpy (Qst) can quantitatively evaluate the affinity of
adsorbent toward adsorbate. Thus, we calculated the Qst from the
adsorption isotherms at 273 K and 298 K (Figure S19-S21). The
Keywords: Covalent organic frameworks
Entanglement • Microporous • Rational design
• Borromean •
-1
-1
initial Qst are 27.1 kJ mol and 25.1 kJ mol of NKCOF-6 for C
and CO
, respectively. The initial Qst are 25.6 kJ mol-1 and 20.4
kJ mol-1 of NKCOF-7 for C
and CO , respectively. The higher
st of NKCOF-6 agreed with the literature results that narrower
2 2
H
2
[1]
[2]
J. Zhou, B. Wang, Chem. Soc. Rev. 2017, 46, 6927-6945.
J. Jiao, W. Gong, X. Wu, S. Yang, Y. Cui, Coord. Chem. Rev. 2019, 385,
74-190.
2
H
2
2
1
Q
[52]
[3]
T. R. Cook, Y. R. Zheng, P. J. Stang, Chem. Rev. 2013, 113, 734-777.
M. Bosch, S. Yuan, W. Rutledge, H. C. Zhou, Acc. Chem. Res. 2017, 50,
pores usually led to stronger interaction for gas molecules.
Because the uptake and binding energy for C are larger than
those for CO , NKCOFs have the potential for C /CO
separation. To further examine this potential, we calculated
/CO selectivity (2:1) at 298 K and 1 bar using the ideal
adsorption solution theory (IAST) (Figure S22).
revealed that NKCOF-6 showed a higher C /CO
than that for NKCOF-7. Breakthrough experiments for C
2:1) at 298 K were also performed to evaluate the gas separation
performance of these COFs (Figure S22). As expected,
breakthrough experiments revealed that CO was firstly eluted
through the packed column, while C was still kept. Notably, the
[
4]
2
H
2
857-865.
2
2
H
2
2
[5]
K. Geng, T. He, R. Liu, S. Dalapati, K. T. Tan, Z. Li, S. Tao, Y. Gong, Q.
Jiang, D. Jiang, Chem. Rev. 2020, 120, 8814-8933.
C
2
H
2
2
[6]
[7]
M. S. Lohse, T. Bein, Adv. Funct. Mater. 2018, 28, 1705553.
S. -Y. Ding, W. Wang, Chem. Soc. Rev. 2013, 42, 548-568.
Y. Jin, Y. Hu, W. Zhang, Nature Reviews Chemistry 2017, 1, 0056.
X. Guan, F. Chen, Q. Fang, S. Qiu, Chem. Soc. Rev. 2020, 49, 1357-
[53]
The results
selectivity
/CO
2
[
[
8]
9]
2
H
2
2
2
H
2
1
384.
10] R. -B. Lin, Y. He, P. Li, H. Wang, W. Zhou, B. Chen, Chem. Soc. Rev.
019, 48, 1362-1389.
(
[
2
2
[
[
11] C. S. Cundy, P. A. Cox, Chem. Rev. 2003, 103, 663-702.
2
H
2
12] D. J. Tranchemontagne, Z. Ni, M. O'Keeffe, O. M. Yaghi, Angew. Chem.
2008, 120, 5214-5225; Angew. Chem. Int. Ed. 2008, 47, 5136-5147.
separation performance of NKCOF-6 was better than that of
NKCOF-7, consistent with the trend of the IAST result. To the best
of our knowledge, we demonstrated the first two COFs, which
achieved the real C H /CO gas mixture separation in the COF
2 2 2
field.[54]
[13] E. J. Gosselin, C. A. Rowland, E. D. Bloch, Chem. Rev. 2020, 120, 8987-
014
14] T. Hasell, A. I. Cooper, Nature Reviews Materials 2016, 1, 16053.
[15] Y. -B. Huang, J. Liang, X. -S. Wang, R. Cao, Chem. Soc. Rev. 2017, 46,
26-157.
16] Z. Wang, S. Zhang, Y. Chen, Z. Zhang, S. Ma, Chem. Soc. Rev. 2020,
9, 708-735.
[17] J. Li, X. Jing, Q. Li, S. Li, X. Gao, X. Feng, B. Wang, Chem. Soc. Rev.
020, 49, 3565-3604.
9
[
1
[
4
Conclusion
2
This article is protected by copyright. All rights reserved.

Angewandte Chemie International Edition
10.1002/anie.202012504
RESEARCH ARTICLE
[
18] V. S. Vyas, M. Vishwakarma, I. Moudrakovski, F. Haase, G. Savasci, C.
Ochsenfeld, J. P. Spatz, B. V. Lotsch, Adv. Mater. 2016, 28, 8749-8754.
19] X. Liu, D. Huang, C. Lai, G. Zeng, L. Qin, H. Wang, H. Yi, B. Li, S. Liu,
M. Zhang, R. Deng, Y. Fu, L. Li, W. Xue, S. Chen, Chem. Soc. Rev. 2019,
[53] D. DeSantis, J. A. Mason, B. James, J. R. Long, M. Veenstra, Energy.
Fuels. 2017, 31, 2024-2032.
[
[54] Z. Wang, S. Zhang, Y. Chen, Z. Zhang, S. Ma, Chem. Soc. Rev. 2020,
49, 708-735.
48, 5266-5302.
[
[
[
[
[
20] L. He, T; Wang, J. An, X. Li, L. Zhang, L. Li, G. Li, X. Wu, Z. Su, C. Wang,
CrystEngComm. 2014, 16, 3259-3263.
21] R. W. Gable, B. F. Hoskins, R. Robson, J. Chem. Soc., Chem. Commun.
1
990, 1677-1678.
22] H. Li, M. Eddaoudi, M. O'Keeffe, O. M. Yaghi, Nature 1999, 402, 276-
79.
2
23] O. M. Yaghi, M. O'Keeffe, N. W. Ockwig, H. K. Chae, M. Eddaoudi, J.
Kim, Nature 2003, 423, 705-714.
24] X. Cui, K. Chen, H. Xing, Q. Yang, R. Krishna, Z. Bao, H. Wu, W. Zhou,
X. Dong, Y. Han, B. Li, Q. Ren, M. J. Zaworotko, B. Chen, Science 2016,
353, 141.
[
[
25] G. R. Desiraju, Angew. Chem. Int. Ed. 2007, 46, 8342-8356.
26] L. Carlucci, G. Ciani, D. M. Proserpio, Coord. Chem. Rev. 2003, 246,
247-289.
[27] Y. Wang, J. F. Stoddart, Chem. 2017, 3, 17-18.
[28] Y. Lu, Y.-X. Deng, Y.-J. Lin, Y.-F. Han, L.-H. Weng, Z.-H. Li, G.-X. Jin,
Chem. 2017, 3, 110-121.
[
[
[
[
29] A. P. O. Chan, P. Ye, S. Ryu, Phys. Rev. Lett. 2018, 121, 061601.
30] C. Mao, W. Sun, N. C. Seeman, Nature 1997, 386, 137-138.
31] N. C. Seeman, Acc. Chem. Res. 1997, 30, 357-363.
32] K. S. Chichak, S. J. Cantrill, A. R. Pease, S. -H. Chiu, G. W. V. Cave, J.
L. Atwood, J. F. Stoddart, Science 2004, 304, 1308-1312.
33] L. Jiang, X. -R. Meng, H. Xiang, P. Ju, D. -C. Zhong, T. -B. Lu, Inorg.
Chem. 2012, 51, 1874-1880.
[
[
[
[
[
[
[
[
[
[
34] Y. -B. Men, J. Sun, Z. -T. Huang, Q. -Y. Zheng, Angew. Chem. 2009, 121,
2917-2920; Angew. Chem. Int. Ed. 2009, 48, 2873-2876.
35] A. P. Côté, A. I. Benin, N. W. Ockwig, M. Keeffe, A. J. Matzger, O. M.
Yaghi, Science 2005, 310, 1166-1170.
36] Y. -B. Men, J. Sun, Z. -T. Huang, Q. -Y. Zheng, Chem. Commun. 2010,
4
6, 6299-6301.
37] C. Gao, J. Li, S. Yin, J. Sun, C. Wang, J. Am. Chem. Soc. 2020, 142,
718-3723.
38] T. -Y. Zhou, S. -Q. Xu, Q. Wen, Z. -F. Pang, X. Zhao, J. Am. Chem. Soc.
014, 136, 15885-15888.
39] M. O’Keeffe, M. A. Peskov, S. J. Ramsden, O. M. Yaghi, Acc. Chem. Res.
008, 41, 1782-1789.
3
2
2
40] P. J. Waller, S. J. Lyle, T. M. Osborn Popp, C. S. Diercks, J. A. Reimer,
O. M. Yaghi, J. Am. Chem. Soc. 2016, 138, 15519-15522.
41] Q. Sun, B. Aguila, J. A. Perman, T. Butts, F. -S. Xiao, S. Ma, Chem. 2018,
4, 1726-1739.
42] Y. Yang, X. He, P. Zhang, Y. H. Andaloussi, H. Zhang, Z. Jiang, Y. Chen,
S. Ma, P. Cheng, Z. Zhang, Angew. Chem. 2020, 132, 3707-3713;
Angew. Chem. Int. Ed. 2020, 59, 3678-3684.
[
[
[
[
[
[
43] Y. Yusran, H. Li, X. Guan, D. Li, L. Tang, M. Xue, Z. Zhuang, Y. Yan, V.
Valtchev, S. Qiu, Q. Fang, Adv. Mater. 2020, 32, 1907289.
44] F. J. Uribe-Romo, C. J. Doonan, H. Furukawa, K. Oisaki, O. M. Yaghi, J.
Am. Chem. Soc. 2011, 133, 11478-11481.
45] H. -C. Ma, G. -J. Chen, F. Huang, Y. -B. Dong, J. Am. Chem. Soc. 2020,
1
42, 12574-12578.
46] X. Han, Q. Xia, J. Huang, Y. Liu, C. Tan, Y. Cui, J. Am. Chem. Soc. 2017,
39, 8693-8697.
1
47] S. Chandra, T. Kundu, S. Kandambeth, R. Babarao, Y. Marathe, S. M.
Kunjir, R. Banerjee, J. Am. Chem. Soc. 2014, 136, 6570-6573.
48] N. C. Burtch, H. Jasuja, K. S. Walton, Chem. Rev. 2014, 114, 10575-
10612.
[
49] L. Sarkisov, A. Harrison, Molecular Simulation 2011, 37, 1248-1257.
50] R. Matsuda, R. Kitaura, S. Kitagawa, Y. Kubota, R. V. Belosludov, T. C.
Kobayashi, H. Sakamoto, T. Chiba, M. Takata, Y. Kawazoe, Y. Mita,
Nature 2005, 436, 238-241.
[
[
51] C. R. Reid, K. M. Thomas, J. Phys. Chem. B, 2001, 105, 10619-10629.
52] R. -B. Lin, S. Xiang, W. Zhou, B. Chen, Chem. 2020, 6, 337-363
[
This article is protected by copyright. All rights reserved.

Angewandte Chemie International Edition
10.1002/anie.202012504
RESEARCH ARTICLE
RESEARCH ARTICLE
+
+
Herein, we, for the first time,
developed an efficient and
Xiuxiu Guo, En Lin, Jia Gao,
Tianhui Mao, Dong Yan,
Peng Cheng, Shengqian Ma,
Yao Chen and Zhenjie
Zhang*
versatile
synthon-driven approach to
construct COFs with
supramolecular-
Borromean links, which have
not been achieved yet in the
literature.
Page No. 1– Page No. 5
Rational Construction of
Borromean
Crystalline
Polymers
Linked
Organic
This article is protected by copyright. All rights reserved.