pubs.acs.

org/JACS Article

Isoreticular Series of Two-Dimensional Covalent Organic

Frameworks with the kgd Topology and Controllable Micropores
Liuxiao Li,◆ Qinbai Yun,◆ Chongzhi Zhu,◆ Guan Sheng, Jun Guo, Bo Chen, Meiting Zhao,
Zhicheng Zhang, Zhuangchai Lai, Xiao Zhang, Yongwu Peng,* Yihan Zhu,* and Hua Zhang*
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sı Supporting Information

ABSTRACT: Two-dimensional (2D) covalent organic frame-

works (COFs) possess designable pore architectures but limited
framework topologies. Until now, 2D COFs adopting the kgd
topology with ordered and rhombic pore geometry have rarely
been reported. Here, an isoreticular series of 2D COFs with the
kgd topology and controllable pore size is synthesized by
employing a C6-symmetric aldehyde, i.e., hexa(4-formylphenyl)-
benzene (HFPB), and C 3 -symmetric amines i.e., tris(4-
aminophenyl)amine (TAPA), tris(4-aminophenyl)trazine
(TAPT), and 1,3,5-tris[4-amino(1,1-biphenyl-4-yl)]benzene
(TABPB), as building units, referred to as HFPB−TAPA,
HFPB−TAPT, and HFPB−TABPB, respectively. The micropore
dimension down to 6.7 Å is achieved in HFPB−TAPA, which is
among the smallest pore size of reported 2D COFs. Impressively, both the in-plane network and stacking sequence of the 2D COFs
can be clearly observed by low-dose electron microscopy. Integrating the unique kgd topology with small rhombic micropores, these
2D COFs are endowed with both short molecular diffusion length and favorable host−guest interaction, exhibiting potential for drug
delivery with high loading and good release control of ibuprofen.

1. INTRODUCTION Here, we report the rational design and synthesis of a series

Covalent organic frameworks (COFs) are a kind of porous of microporous 2D COFs with the kgd topology using a C6-
symmetric aldehyde, i.e., hexa(4-formylphenyl)benzene
materials constructed from organic building blocks under
(HFPB), as vertices, and three different C3-symmetric amines,
reticular chemistry.1−9 These emerging types of materials with
i.e., tris(4-aminophenyl)amine (TAPA), tris(4-aminophenyl)-
high surface areas and good crystallinity have drawn great trazine (TAPT), and 1,3,5-tris[4-amino(1,1-biphenyl-4-yl)]-
attention in various applications including gas separation10,11 benzene (TABPB), as edges, referred to as HFPB−TAPA,
and storage,12,13 catalysis,14−18 biosensing,19 and optoelec- HFPB−TAPT, and HFPB−TABPB, respectively. Importantly,
tronics.20−22 The overall performance of COFs in these the utilization of the highest symmetric building units (i.e.,
applications is greatly determined by the interaction between HFPB) endows the 2D COFs with ultramicropores (∼6.7 Å,
the porous network and guest molecules. Two-dimensional which is among the smallest one of the reported 2D COFs).
(2D) COFs feature ultrathin thickness and thus short The in-plane molecular network and stacking sequence of
molecular diffusion length, which favor efficient mass transport these 2D COFs have been clearly observed by low-dose
and fast molecular adsorption/desorption.23,24 However, there electron microscopy. Impressively, taking advantage of the
are merely five topologies in which the vertices are connected rhombic ultramicropores of the obtained 2D COFs as drug
by one kind of edge (i.e., edge-transitive networks): hexagonal carriers, high drug loading (14, 2.5, and 4 wt % for HFPB−
tiling (hcb),25,26 tetragonal tiling (sql),27 kagome tiling TAPA, HFPB−TAPT, and HFPB−TABPB, respectively) and
(kgm),28−30 triangular tiling (hxl),31,32 and rhombille tiling controlled releasing of ibuprofen (IBU) have been achieved.
(kgd). In principle, COFs with target topology can be
rationally designed and synthesized based on the theory of Received: January 31, 2022
reticular chemistry.33 Nevertheless, 2D COFs with the kgd Published: April 4, 2022
topology and controllable pores have rarely been re-
ported.34−36 Importantly, 2D COFs with the kgd topology
are regarded as good candidates for drug delivery due to their
micropore sizes.

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Figure 1. Topology diagrams for the preparation of typical 2D COFs based on C3-symmetric building units.

Our reported microporous 2D COFs with the kgd topology respectively, indicating that they are all semiconductors
and unique pore geometries would not only enrich the COF (Figure S4). As implied by the thermogravimetric analysis
family but also broaden their application in highly efficient (TGA) results, these 2D COFs exhibit high thermal stability
drug delivery. up to ∼460 °C (Figure S5). As displayed in the scanning
electron microscopy (SEM) and transmission electron
2. RESULTS AND DISCUSSION microscopy (TEM) images, both the as-prepared HFPB−
2.1. Preparation of 2D COFs with the kgd Topology. TAPA and HFPB−TABPB possess nanoparticle morphologies
From the topological point of view, the combination of a six- (Figures S6 and S7), while HFPB−TAPT shows hollow
connected C6-symmetric building unit with a three-connected nanorod morphology (Figure S8).
C3-symmetric building unit could result in the construction of 2.2. Structural Characterization of 2D COFs with the
2D COFs with the kgd topology and microporous structures. kgd Topology. The crystalline structures and unit cell
As illustrated in Figure 1, the hexagonal topology with C3- and parameters of HFPB−TAPA, HFPB−TAPT, and HFPB−
C2-symmetric building units possess a pore size of 3√3 L, TABPB were characterized by the powder X-ray diffraction
while the hexagonal topology using C3- and C3-building units (PXRD) combined with structural simulations and Pawley
leads to a pore size of 2√3 L, where the length between two refinement (Figure 2 and Tables S1−S3). Considering the
vertices is defined as 3 and 2 L, respectively. By contrast, the geometry of molecular building blocks and their connectivity,
kgd topology constructed from C3- and C6-symmetric building the 2D structural models were proposed and constructed
units can form the smallest pore size of √3 L, indicating that (Figure 2a). The experimental PXRD profiles of these HFPB−
the micropores are easier to be formed when higher symmetric TAPA and HFPB−TABPB COFs can be well indexed by the
C6-building units are employed. Here, via the Schiff base hexagonal unit cells, while HFPB−TAPT is indexed by a
reaction between HFPB and TAPA (or TAPT, TABPB) at 393 trigonal unit cell (Figure 2b). HFPB−TAPA exhibits an
K for 72 h, microporous kgd topology 2D COF, namely, as intense peak at 7.66° and minor peaks at 4.40, 8.99, 15.95, and
HFPB−TAPA (or HFPB−TAPT, HFPB−TABPB) was 18.94°, which are assigned to the Bragg diffractions of the
successfully synthesized (Figure 2, see the detailed Exper- (110), (100), (200), (310), and (230) planes, respectively (red
imental Section in the Supporting Information). As indicated curve in the left panel of Figure 2b). HFPB−TAPT shows an
in the Fourier transform infrared (FT-IR) spectra (Figures intense (110) diffraction peak at 6.86° and other minor peaks
S1−S3), HFPB−TAPA, HFPB−TAPT, and HFPB−TABPB at 10.57, 12.01, and 13.91° corresponding to the (210), (300),
possess the characteristic CN stretching bands at 1622, and (220) planes, respectively (red curve in the middle panel
1631, and 1624 cm−1, respectively. In addition, the aldehyde of Figure 2b). As for HFPB−TABPB, the intense peak at 5.72°
stretching band of the starting material HFPB (1702 cm−1) is and minor peaks at 3.32, 8.57, and 11.30° can be observed,
greatly attenuated, suggesting that the condensation reaction which correspond to the Bragg diffractions of the (110), (100),
occurred and the formation of imine bonds (Figures S1−S3). (210), and (220) planes, respectively (red curve in the right
The UV−vis diffuse reflectance spectroscopy (UV-DRS) panel of Figure 2b). Moreover, the Pawley-refined PXRD
analyses reveal the absorbance bands at 433, 440, and 446 patterns (black curves in Figure 2b) match well with the
nm, corresponding to the band gaps of 2.86, 2.82, and 2.78 eV experimental PXRD results (red curves in Figure 2b),
for the HFPB−TAPA, HFPB−TAPT, and HFPB−TABPB, considering their negligible differences as displayed in the
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Figure 2. (a) Structures and (b) powder X-ray diffraction (PXRD) patterns of HFPB−TAPA (left), HFPB−TAPT (middle), and HFPB−TABPB
(right) obtained experimentally (red) and through Pawley refinement (black). The blue curves are the corresponding differences between the
experimental and Pawley-refined data.

blue curves in Figure 2b, with Rwp and Rp values converged to characterized by a higher degree of structural order (Figure 2b,
4.06 and 7.21% for HTPB−TAPA, 4.22 and 3.20% for HTPB− middle panel). Electron diffraction tomography (EDT) was
TAPT, and 5.63 and 8.99% for HTPB−TABPB. The refined conducted on HFPB−TAPT via electron diffraction tilt series
lattice parameters by Pawley methods are compiled in Tables collected from −70 to 70° (Figure 3a), confirming its
S1−S3, i.e., a = b = 23.1788 Å and c = 4.2425 Å for HFPB− hexagonal unit cell, 2D structure, and h − k ≠ 3n extinction
TAPA, a = b = 25.4941 Å and c = 12.5420 Å for HFPB− condition for hk0 reflections based on the in-plane diffuse
TAPT, and a = b = 31.8964 Å and c = 4.4028 Å for HFPB− diffraction rods in the three-dimensional (3D) reciprocal
TABPB. space. The extinction rules observed for the in-plane reflections
The aforementioned results indicate that these 2D networks coincide with the disappearance of the 100 reflection in the
with the kgd topology have increased unit cell dimensions and PXRD pattern (Figure 2b, middle panel), most likely
pore openings at their basal planes but similar interlayer originating from the ordered stacking of 2D HFPB−TAPT
spacings along the stacking direction. Importantly, it is layers in the ABC stacking sequence. Such a stacking sequence
observed that the intensity ratios of I100/I110 reflections creates the R3/R3̅ symmetry of the stacked layers rather the P6
belonging to these 2D COFs are significantly decreased with symmetry of individual 2D layers (Figures 3b,c), and features
respect to their theoretical values (i.e., 0.24 vs 1.18 for HFPB− the 003 diffraction spot in the EDT data (Figure 3a),
TAPA, 0 vs 1.27 for HFPB−TAPT, and 0.62 vs 1.38 for corresponding to the ∼4.2 Å interlayer spacing due to the l
HFPB−TABPB). The 100 reflection even vanishes for the ≠ 3n extinction condition for hhl reflections. Furthermore,
HFPB−TAPT COF despite its much smaller peak width low-dose electron microscopy was employed to directly
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Figure 3. (a) 3D electron diffraction tomography tilt series collected on a representative HFPB−TAPT crystal. (b) [100] and (c) [001] structural
projections of the HFPB−TAPT crystal with ABC stacking sequence. The left and right panels of (c) refer to the single-layer and the ABC stacked
structural models, respectively. C, N, and H atoms and six rings are denoted by black, red, pink, and green colors, respectively. (d) Low-dose
HRTEM image taken along the [001] direction after correcting the contrast transfer function (CTF) effects at a defocus of 575 nm. Inset: the
corresponding FFT pattern (the white dashed circle refers to the 4 Å information transfer limit). (e, f) Enlarged image (e) from the yellow dashed
square in (d), and the corresponding simulated projected potential map with a point-spread-function (PSF) width of 4 Å (f). Red arrows in (e)
indicate the projected imine groups linking HFPB and TAPT molecules. Structural projection (g), low-dose HRTEM image collected near Scherzer
defocus (h), and simulated projected potential map with a PSF width of 3 Å (i) along the [11̅0] direction.

visualize the 2D network of HFPB−TAPT COFs with the from the synthesized hollow nanorods by sonication (Figure
underlying kgd topology (Figure 3d−f). As shown in the low- S10), the contrast becomes chemically interpretable after
magnification TEM image (Figure S9a) and the [11̅0] correcting the effects from the contrast transfer function
projection high-resolution transmission electron microscopy (CTF) of the objective lens (Figure 3d), similarly as reported
(HRTEM) image (Figure S9b), the HFPB−TAPT COFs previously.37,38 For the single-layer projected HFPB−TAPT
crystallize as hollow nanorods along the [001] direction and 2D COF with a P6 symmetry, an entangled honeycomb
exhibit fast Fourier transform (FFT) patterns with hhl (l = 3n) pattern is expected (Figure S11). However, the CTF-corrected
spots. The extinction rules arising from the ABC stacking HRTEM exhibits a simple P6 symmetric honeycomb pattern
sequence may locally be broken by exhibiting weak and diffuse characterized by the ABC stacked layers displaced along the
hhl (l ≠ 3n) spots in electron diffraction pattern collected from [11̅0] direction (Figure 3d−f). In the projected HRTEM
a large area of [11̅0] projected HFPB−TAPT hollow nanorod image (Figure 3d), each dark dot in the honeycomb pattern
(Figure S9c). originates from a pair of three-connected TAPT molecules
The presence of hhl (l ≠ 3n) diffraction spots may result superimposed with reversed orientation and another six-
from the local incoherent rippling of ABC stacked 2D COF connected HFPB molecule, which are located at different
layers that breaks the R3/R3̅ symmetry and validate the ABC stacked layers, respectively. The contrast for short dark
proposed stacking order of 2D HFPB−TAPT COFs that lines (marked by the red arrows in Figure 3e) that connect the
introduces out-of-plane reflections with tripled interlayer neighboring dark dots refers to projected imine groups that
spacings. As displayed in the HRTEM image taken along the link HFPB and TAPT molecules in the 2D kgd networks. The
[001] projection of an HFPB−TAPT COF fragment peeled off image also matches well with both the [001] structural
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Figure 4. (a) N2 sorption isotherms for HFPB−TAPA, HFPB−TAPT, and HFPB−TABPB measured at 77 K. (b) Pore size distributions of
HFPB−TAPA, HFPB−TAPT, and HFPB−TABPB. (c) UV−vis spectra of IBU in phosphate-buffered saline (PBS, pH 7.4) at various
concentrations. Inset: IBU calibration curve. (d) Release curve of IBU-loaded HFPB−TAPA. Inset: the structure of IBU.

Table 1. Comparison of the BET Surface Areas, Pore Sizes, and IBU Loading Amounts of HFPB−TAPA, HFPB−TAPT, and
HFPB−TABPB
BET surface area experimental main pore size theoretical main pore size theoretical pore architecture IBU loading amount
(m2 g−1) (Å) (Å) (Å × Å) (wt %)
HFPB−TAPA 852 6.7 6.5 8.22 × 13.76 14.0
HFPB−TAPT 531 7.3 7.0 8.09 × 15.65 2.5
HFPB− 960 12.0 11.0 7.80 × 22.39 4.0
TABPB

projection and the corresponding simulated projected potential HFPB−TAPA, HFPB−TAPT, and HFPB−TABPB are calcu-
map of the optimized HFPB−TAPT structural model with lated to be 852, 531, and 960 m2 g−1, respectively (Figure 4a).
either R3 or R3̅ symmetry (Figures 3c,f and S11). Despite the Pore size distributions calculated based on the nonlocal density
fact that the former adopts a slightly lower P3 projection functional theory (NLDFT) method show the main pore
symmetry along the [001] direction, the geometry is distributions of ca. 6.7, 7.3, and 12.0 Å for HFPB−TAPA,
energetically more favorable. Accordingly, the above observa- HFPB−TAPT, and HFPB−TABPB, respectively (Figure 4b),
tions confirm that the HFPB−TAPT hollow nanorods are which coincide with the theoretical values obtained from their
composed of ABC stacked 2D kgd networks that adopt an R3 crystal structures, i.e., 6.5, 7.0, and 11.0 Å for HFPB−TAPA,
symmetry. The proposed structural model is further supported HFPB−TAPT, and HFPB−TABPB, respectively (Figure 2a).
by another HRTEM image taken along the [11̅0] direction 2.3. Application of 2D COFs with the kgd Topology
(Figure 3g−i), which also matches well with the corresponding as Drug Carriers. Recent reports have demonstrated that 2D
structural projection (Figure 3g) and the potential map (Figure COFs with large specific surface area, high pore volume, and
3i). As reported previously, low-dose electron microscopy can high structure and function tunability are potential candidates
elucidate structural ambiguities introduced by conventional as drug carriers.41−45 As a proof-of-concept application, the
structural elucidation techniques and allows the construction obtained microporous kgd-structured 2D COFs were
of molecularly precise structural models for a wide range of employed as drug carriers for loading and releasing of IBU
COFs.19,39,40 with the molecular size of 6.0 Å × 13.0 Å. Briefly, the IBU was
The topologies and structural models for HFPB−TAPA, loaded by immersing solvent-free COFs in the hexane solution
HFPB−TAPT, and HFPB−TABPB were further confirmed by of IBU, which was kept unstirred for 12 h to achieve an
N2 sorption isotherms measured at 77 K. Figure 4a shows that adsorption−desorption equilibrium. Then, the IBU-loaded
all three COFs adopt reversible type I isotherms, demonstrat- COFs were separated from the solution by filtration, washed
ing their microporous structures with a pore size less than 2 with hexane, and dried at room temperature. As revealed by
nm. The Brunauer−Emmett−Teller (BET) surface areas for the TGA analyses, the loading amount of IBU in HFPB−
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TAPA (14.0 wt %) is higher than that in HFPB−TAPT (2.5 wt Cambridge Crystallographic Data Centre, 12 Union Road,
%) and HFPB−TABPB (4.0 wt %) (Figures S12−S14, Table Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

■
1). This could be attributed to the unique pore size of HFPB−
TAPA (8.22 Å × 13.76 Å, Figure S15, Table 1), which is
comparable with the molecular size of IBU (6.0 Å × 13.0 Å), AUTHOR INFORMATION
as compared to HFPB−TAPT (8.09 Å × 15.65 Å, Figure S16) Corresponding Authors
and HFPB−TABPB (7.80 Å × 22.39 Å, Figure S17). The Yongwu Peng − Center for Electron Microscopy, State Key
more suitable pore size of HFPB−TABA leads to the more Laboratory Breeding Base of Green Chemistry Synthesis
intimate encapsulation of IBU molecules and stronger Technology, College of Materials Science and Engineering and
chemical bonding between the functional groups of IBU College of Chemical Engineering, Zhejiang University of
molecules and COF, favoring the efficient chemisorption of Technology, Hangzhou 310014, China; orcid.org/0000-
IBU. In addition, the higher BET surface area of HFPB−TAPA 0003-4760-5173; Email: [email protected]
(852 m2 g−1), as compared to HFPB−TAPT (531 m2 g−1), Yihan Zhu − Center for Electron Microscopy, State Key
also contributes to the higher physisorption of IBU in HFPB− Laboratory Breeding Base of Green Chemistry Synthesis
TAPA. Furthermore, the PXRD peaks (Figure S18a) and FT- Technology, College of Materials Science and Engineering and
IR spectra (Figure S18b) of IBU-loaded HFPB−TAPA are in College of Chemical Engineering, Zhejiang University of
accordance with those of the original HFPB−TAPA, Technology, Hangzhou 310014, China; Email: yihanzhu@
suggesting that the structure of HFPB−TAPA was well zjut.edu.cn
maintained after IBU loading. In a typical experiment for Hua Zhang − Department of Chemistry, City University of
releasing IBU from COFs, the IBU-loaded COFs were placed Hong Kong, Hong Kong, China; Hong Kong Branch of
in a vial and immersed in phosphate-buffered saline (PBS, pH National Precious Metals Material Engineering Research
= 7.4) at 310 K. The mixture was replaced with fresh PBS, and Center (NPMM), City University of Hong Kong, Hong Kong,
the withdrawn samples were taken for the UV−vis absorption China; Shenzhen Research Institute, City University of Hong
analysis using a calibration curve for IBU to determine the Kong, Shenzhen 518057, China; orcid.org/0000-0001-
drug concentration (Figures 4c,d). For HFPB−TAPA, the 9518-740X; Email: [email protected]
majority of the IBU can be released after about 5 days and total
delivery can achieve ∼99% of the initial IBU loading. In Authors
addition, to assessing the toxicity of HFPB−TAPA to cells, Liuxiao Li − Department of Chemistry, City University of
MTT cell viability assays were conducted using rat-derived Hong Kong, Hong Kong, China; Center for Programmable
H9C2 cardiomyocytes. As shown in Figure S19, the relative Materials, School of Materials Science and Engineering,
cell viabilities of H9C2 cells treated with different doses of Nanyang Technological University, Singapore 639798,
HFPB−TAPA are almost the same, indicating the low Singapore
cytotoxicity of HFPB−TAPA and its great potential in Qinbai Yun − Department of Chemistry, City University of
biomedical applications. Hong Kong, Hong Kong, China
Chongzhi Zhu − Center for Electron Microscopy, State Key
3. CONCLUSIONS Laboratory Breeding Base of Green Chemistry Synthesis
In summary, a series of 2D COFs with the kgd topology has Technology, College of Materials Science and Engineering and
been successfully prepared by the co-condensation of C6- College of Chemical Engineering, Zhejiang University of
symmetric building units with C3-symmetric building units. Technology, Hangzhou 310014, China
These highly crystalline and microporous 2D COF structures Guan Sheng − Center for Electron Microscopy, State Key
are clearly observed by low-dose electron microscopy. In Laboratory Breeding Base of Green Chemistry Synthesis
particular, the unique framework and the host−guest Technology, College of Materials Science and Engineering and
interaction endow the HFPB−TAPA with both high loadings College of Chemical Engineering, Zhejiang University of
and good release properties of IBU when used as the drug Technology, Hangzhou 310014, China
carrier. Our strategy greatly enriches the reticular chemistry Jun Guo − Department of Chemistry, City University of Hong
repertoire for 2D COFs with the kgd topology and Kong, Hong Kong, China; orcid.org/0000-0001-6277-
controllable micropore architectures toward both facilitated 3947
mass transport and effective host−guest interaction. Bo Chen − Department of Chemistry, City University of Hong

■ ASSOCIATED CONTENT
* Supporting Information
sı
Kong, Hong Kong, China; orcid.org/0000-0001-6743-
9251
Meiting Zhao − Tianjin Key Laboratory of Molecular
The Supporting Information is available free of charge at Optoelectronic Sciences, Department of Chemistry, Institute of
https://pubs.acs.org/doi/10.1021/jacs.2c01199. Molecular Aggregation Science, Tianjin University, Tianjin
Experimental procedures, FT-IR spectra, UV−vis DRS 300072, China; orcid.org/0000-0002-0776-5626
spectra, TGA curves, figures of SEM and TEM images, Zhicheng Zhang − Tianjin Key Laboratory of Molecular
cell viability assays, and crystallographic information Optoelectronic Sciences, Department of Chemistry, School of
(PDF) Science, Tianjin University & Collaborative Innovation
Center of Chemical Science and Engineering (Tianjin),
Accession Codes Tianjin 300072, China; orcid.org/0000-0002-2487-
CCDC 2150492−2150494 contain the supplementary crys- 4250
tallographic data for this paper. These data can be obtained Zhuangchai Lai − Department of Chemistry, City University of
free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by Hong Kong, Hong Kong, China; orcid.org/0000-0001-
emailing [email protected], or by contacting The 8743-6568
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■ ACKNOWLEDGMENTS
H.Z. acknowledges support from ITC via the Hong Kong
Chem. 2015, 7, 905−912.
(17) 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.
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Research Center (NPMM), the Start-Up Grant (project no. (18) Wang, X.; Han, X.; Zhang, J.; Wu, X.; Liu, Y.; Cui, Y.
9380100), and grants (project nos. 7020013, 9678272, and Homochiral 2D porous covalent organic frameworks for heteroge-
1886921) from the City University of Hong Kong. Y.Z. neous asymmetric catalysis. J. Am. Chem. Soc. 2016, 138, 12332−
acknowledges financial support from the National Natural 12335.
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22122505, and 22075250). Y.P. thanks the financial support Zhang, Z.; Zhao, M.; Tan, C.; Yang, N.; Shao, F.; Han, Y.; Zhang, H.
from the funding of the “Leading Innovative and Entrepreneur Ultrathin Two-Dimensional Covalent Organic Framework Nano-
Team Introduction Program of Zhejiang” (2020R01002) and sheets: Preparation and Application in Highly Sensitive and Selective
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Zhejiang University of Technology for assistance in some (21) Huang, N.; Ding, X.; Kim, J.; Ihee, H.; Jiang, D. A
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