2D and 3D Porphyrinic Covalent Organic Frameworks: The Influence of Dimensionality on Functionality

Article abstract of DOI:10.1002/anie.201913091

The construction of 2D and 3D covalent organic frameworks (COFs) from functional moieties for desired properties has gained much attention. However, the influence of COFs dimensionality on their functionalities, which can further assist in COF design, has

Full text of DOI:10.1002/anie.201913091

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Accepted Article
Title: 2D and 3D Porphyrinic Covalent Organic Frameworks: The
Influence of Dimensionality on Functionality
Authors: Cheng Wang, Yi Meng, Yi Luo, Ji-Long Shi, Huimin Ding,
Xianjun Lang, Wei Chen, Anmin Zheng, and Junliang Sun
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10.1002/anie.201913091
Angewandte Chemie International Edition
RESEARCH ARTICLE
2D and 3D Porphyrinic Covalent Organic Frameworks: The
Influence of Dimensionality on Functionality
Yi Meng, [a]† Yi Luo, [b], [c]† Ji-Long Shi, [a]† Huimin Ding, [a] Xianjun Lang, [a] Wei Chen,[d] Anmin Zheng, [d]
Junliang Sun*[b], [c] and Cheng Wang*[a]
Dedicated to Professor Jean-Pierre Sauvage on occasion of his 75th birthday
Abstract: The construction of 2D and 3D covalent organic
frameworks (COFs) from functional moieties for desired properties
has gained intensive attention. However, the influence of COFs
dimensionality on their functionalities, which can further assist in
COF design, has never been explored. Herein, by selecting
designed precursors and topology diagrams, we reported the
synthesis of 2D and 3D porphyrinic COFs (2D-PdPor-COF and 3D-
PdPor-COF). By model building and Rietveld refinement of powder
X-ray diffraction, 2D-PdPor-COF crystallizes as 2D sheets while 3D-
many groups, a large number of functional COFs have been
reported over the past decade, which have found interesting
applications in gas adsorption and separation,[3] heterogeneous
catalysis,[4] molecular sensing,[5] energy storage,[6] proton
conductivity,[7] optoelectronics,[8] etc.
In order to construct COFs with desired functionalities, a
facile way is incorporating specific functional moieties during
their synthesis process. From a structural viewpoint, these
functional moieties can be integrated into either two-dimensional
[9]
PdPor-COF adopts
a
five-fold interpenetrated pts topology.
(2D) layered structures
or three-dimensional (3D) extended
Interestingly, compared with 2D-PdPor-COF, 3D-PdPor-COF
showed interesting properties, including 1) higher CO2 adsorption
capacity; 2) better photocatalytic performance; 3) size-selective
photocatalysis. Based on this study, we believe that with the
incorporation of functional moieties, the dimensionality of COFs can
definitely influence their functionalities.
networks [10], depending on the geometry and connectivity of the
precursors. For 2D COFs, the 2D flat sheets usually stack in a
face-to-face mode, and the functional moieties in the adjacent
layers have strong π-π interactions that could be beneficial for
the charge mobility. In contrast, 3D COFs will allow the
functional moieties to be three-dimensionally organized into the
framework and thus feature open sites. In principle, the
alignment and interaction of these functional moieties in 2D and
3D COFs are different, which may affect the properties of the
resulting materials. Therefore, it will be very interesting to
construct 2D and 3D COFs from the same functional moieties
and then investigate the influence of dimensionality on their
properties. However, to the best of our knowledge, no related
work has been reported yet.
Introduction
Covalent organic frameworks (COFs) are an emerging class of
porous crystalline polymers built from molecular building blocks
linked via strong covalent bonds.[1] In comparison with
amorphous organic polymers, COFs can precisely assemble
molecular building blocks into extended order structures through
the principles of reticular chemistry. Owning to their periodic
architectures, low densities, high surface areas and robust
stability, COFs are considered as a highly designable and
functionalized materials platform with various potential
applications. Since first discovered by Yaghi and co-workers in
2005,[2] intensive attentions have been devoted to constructing
functional COFs with desired properties. Thanks to the efforts of
TAPM
o-DCB/n-BuOH/AcOH (6M. aq.)
(9/1/1 v/v/v), 120 ℃, 7d
OHC
CHO
[a]
[b]
Y. Meng, J. Shi, Dr. H. Ding, Prof. Dr. X. Lang, Prof. Dr. C. Wang
Sauvage Center for Molecular Sciences and Hubei Key Lab on
Organic and Polymeric Optoelectronic Materials
College of Chemistry and Molecular Sciences
Wuhan University, Wuhan 430072, China
3D-PdPor-COF
N
Pd
N
N
N
E-mail: chengwang@whu.edu.cn
Dr. Y. Luo, Prof. Dr. J. Sun
OHC
CHO
p-PdPor-CHO
College of Chemistry and Molecular Engineering
Beijing National Laboratory for Molecular Sciences
Peking University, Beijing 100871, China
E-mail: junliang.sun@pku.edu.cn
Dr. Y. Luo, Prof. Dr. J. Sun
o-DCB/n-BuOH/AcOH (3M aq.)
(5/5/1 v/v/v), 120 ℃, 3d
[c]
[d]
Department of Materials and Environmental Chemistry
Stockholm University, Stockholm 10691, Sweden
Dr. W. Chen, Prof. Dr. A. Zheng
State Key Laboratory of Magnetic Resonance and Atomic and
Molecular Physics, Wuhan Institute of Physics and Mathematics
Chinese Academy of Sciences, Wuhan 430071, China
These authors contributed equally to this work.
PPDA
2D-PdPor-COF
Scheme 1. Schematic Representation of the Synthesis of 2D-PdPor-COF and
†
3D-PdPor-COF
Supporting information for this article is given via a link at the end of
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10.1002/anie.201913091
Angewandte Chemie International Edition
RESEARCH ARTICLE
2D COFs,[1b] whereas for 3D COFs we used our reported
topology strategy starting from tetrahedral (Td) and quadrilateral
(C2 or C4) building blocks.[13] Since we aimed to construct
porphyrinic COFs, we accordingly designed and synthesized the
Porphyrins and its derivatives are unique chromophores with
interesting photophysical properties that have found great
potentials in photocatalytic applications.[11] A unique feature of
porphyrins is that their photocatalytic activity is strongly
dependent on their aggregation state. With this consideration in
mind, we decided to construct 2D and 3D porphyrinic COFs and
then investigate their different properties to explore the
dimensionality effect on COFs functionality. Herein, we report
the designed synthesis and characterization of 2D and 3D
palladium porphyrin-based COFs (2D-PdPor-COF and 3D-
PdPor-COF) (Scheme 1), which have high crystallinity and large
surface area. Interestingly, compared with 2D-PdPor-COF, 3D-
PdPor-COF exhibited higher CO2 adsorption capacity. In
addition, both COFs can be used as heterogeneous
photocatalysts for selective oxidation of sulfides to sulfoxides,
but 3D-PdPor-COF showed better photocatalytic performance
as well as size-selectivity.
functional
precursor,
[5,10,15,20-Tetrakis(4-
benzaldehyde)porphyrin]palladium (p-PdPor-CHO),[14] which can
form 2D or 3D COFs by condensation with p-phenylenediamine
(PPDA) or tetra(p-aminophenyl)methane (TAPM)[15], respectively.
As can be seen in Scheme 1, 2D-PdPor-COF and 3D-
PdPor-COF were synthesized under solvothermal conditions by
reacting p-PdPor-CHO with PPDA and TAPM in a mixture of o-
dichlorobenzene, n-butanol and aqueous acetic acid at 120 °C
for several days. After washed by the Soxhlet extraction method,
both COFs were isolated as powders insoluble in common
organic solvents and water. From the solid-state 13C NMR
spectra (Figure S1 and S2), 2D-PdPor-COF and 3D-PdPor-COF
showed a characteristic signal at ~158 ppm, which should be
assigned to the imine carbon atom and indicates the formation
of imine-linked materials. In addition, the Fourier transform
infrared (FT-IR) spectra of both COFs exhibited a stretching
vibration band at ~1626 cm-1 (Figure S3), confirming again the
existence of imine bonds. Furthermore, the thermogravimetric
analysis (TGA, Figure S4) revealed that both COFs have high
thermal stability up to 500 °C under nitrogen atmosphere.
According to the scanning electron microscopy (SEM) images
(Figure S5), 3D-PdPor-COF possesses an irregular polyhedral
morphology while 2D-PdPor-COF is plate-like.
Results and Discussion
In order to study the dimensionality effect, the major concern is
how to rationally select the proper topology diagram and then
design the functional precursors to construct the desired 2D and
3D COFs. However, unlike the well-established 2D COFs, the
construction of 3D COFs have been proved to be a big
challenge,[12] and only a few topology diagrams for 3D COFs has
been reported until now.[1b] After careful consideration, we
decided to choose the reported [C4 + C2] diagram to synthesize
Figure 1. PXRD patterns of 2D-PdPor-COF (a) and 3D-PdPor-COF (d) with the experimental profiles in black, Rietveld refinement in red, their difference in green,
and the Bragg position in blue. Structural representations of 2D-PdPor-COF (b) and 3D-PdPor-COF (e), in which the former has an eclipsed AA stacking 2D
structure and the latter adopts a five-fold interpenetrated pts topology. The schematic diagrams of stacking manners of palladium porphyrin units in 2D-PdPor-
COF (c) and 3D-PdPor-COF (f).
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10.1002/anie.201913091
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RESEARCH ARTICLE
The high crystallinity of 2D-PdPor-COF and 3D-PdPor-COF
was revealed by powder X-ray diffraction (PXRD) analysis
(Figure 1a and 1d). Their structures were then reliably solved
and confirmed based on PXRD data by a combination of real
space method (model building) and Rietveld refinement.[16] For
2D-PdPor-COF, from its PXRD pattern, a triclinic unit cell (a =
4.29 Å, b = 23.51 Å, c = 25.47 Å, α = 88.6°, β = 97.7°, γ = 87.9°,
space group P-1) could be indexed. With the determined unit
cell a topologically reasonable eclipsed AA stacking 2D structure
model (Figure 1b) was built straightforwardly by employing the
chemical information from real space such as basic building
blocks and connection manners (-C=N-). The simulated PXRD
pattern of the structure model fits well with the experimental
PXRD pattern of 2D-PdPor-COF in peak positions and
intensities (Figure S8), indicating the reliability of the structure
model. The structure model was then further validated by the
Rietveld refinement using the program Topas V6.[17] The final
The permanent porosities of 2D-PdPor-COF and 3D-PdPor-
COF were evaluated by nitrogen adsorption isotherms at 77 K.
As shown in Figure 2a and 2b, both COFs exhibited a typical I
isotherm, indicating micro-porosity. Accordingly, the Brunauer-
Emmett-Teller (BET) surface areas were calculated to be 1120
m2 g-1 for 2D-PdPor-COF and 1406 m2 g-1 for 3D-PdPor-COF.
From density functional theory calculations, both COFs showed
a narrow pore distribution with the peak at 1.9 nm for 2D-PdPor-
COF and 0.58 nm for 3D-PdPor-COF, which is in agreement
with the calculated pore size from crystal structures (1.87 nm for
2D-PdPor-COF and 0.63 nm for 3D-PdPor-COF, Figure S12).
Furthermore, we investigated their CO2 adsorption with
pressures up to 1 bar and at temperature of 273 K and 298 K
(Figure 2c and 2d). Interestingly, 3D-PdPor-COF exhibited a
capacity of 105.0 cm3 g-1 at 273 K and 47.7 cm3 g-1 at 298 K,
which is 3.1-fold and 2.4-fold greater than those of 2D-PdPor-
COF. Therefore, compared with 2D-PdPor-COF, 3D-PdPor-COF
has advantages in CO2 adsorption.
agreement residuals for the refinement were RI = 0.005, Rwp
=
0.076, and Rexp =0.028 (Figure 1a, Table S1). For 3D-PdPor-
COF, its PXRD pattern could be indexed by a C-centered
monoclinic unit cell (a = 28.37 Å, b = 7.50 Å, c = 39.9 Å, β =
99.75°, space group C2/c), which is highly consistent with the
one revealed by single-crystal electron diffraction data[18] (Figure
S9, Table S2). A structure model with a five-fold interpenetrated
pts topology (Figure 1e, Figure S11) was then established
indisputably using model building. The Rietveld refinement of
3D-PdPor-COF converged with agreement values RI= 0.007,
Rwp= 0.064, with Rexp= 0.030 (Figure 1d, Table S3). It should be
mentioned here, in the refined structures of 2D-PdPor-COF and
3D-PdPor-COF, all bond lengths and angles are consistent with
those expected for COF materials. Furthermore, according to
their crystal structures, the palladium porphyrin units in 2D-
PdPor-COF and 3D-PdPor-COF stack in totally different
manners (Figure 1c and 1f).
For exploring the dimensional effect of 2D-PdPor-COF and
3D-PdPor-COF, we decided to investigate their photocatalytic
activities as photocatalysts based on the following
considerations:
1)
palladium
porphyrins
are
good
photosensitizer; 2) from the crystal structures, the alignments of
palladium porphyrins in these two COFs are significantly
different, which can affect their photochemical properties; and 3)
the smaller pore size of 3D-PdPor-COF may show certain
selectivity. Their photocatalytic performances were then studied
by the visible-light-induced aerobic oxidation of sulfides to
sulfoxides, which plays a pivotal role in synthesizing a series of
important organic compounds.[19] As shown in Table 1, by using
Table 1. Photocatalytic seletive Oxidation of thioanisole to methyl phenyl
sulfoxide by both COFs [a]
a)
b)
Adsorption
Desorption
Adsorption
Desorption
400
300
200
100
0
400
300
200
100
0
Entry Light Photocatalyst Air
Additive
Yield (%)b
1
2
3
4
5
6
on
off
on
on
on
on
3D-PdPor-COF
3D-PdPor-COF
none
+
+
+
-
-
-
-
-
-
98
0
0.58 nm
1.9 nm
0.8
0.6
0.4
0.2
0.0
3
2
1
0
0
2
4
6
8
10
0
2
4
6
8
10
0
Pore Width (nm)
Pore Width (nm)
0.0
0.2
0.4
0.6
0.8
1.0
0.0
0.2
0.4
0.6
0.8
1.0
Relative pressure (P/P0)
Relative pressure (P/P0)
d)
3D-PdPor-COF
2D-PdPor-COF
3D-PdPor-COF
0
c)
35
30
25
20
15
10
5
ADS at 273K
DES at 273K
ADS at 298K
DES at 298K
ADS at 273K
DES at 273K
ADS at 298K
DES at 298K
100
80
60
40
20
0
+
+
48
Superoxide
scavenger c
13
7
Superoxide
scavenger c
7
8
on
on
2D-PdPor-COF
+
+
0
p-PdPor-CHO
-
23
0.0
0.2
0.4
0.6
0.8
1.0
0.0
0.2
0.4
0.6
0.8
1.0
Absolute pressure (bar)
Absolute Pressure (bar)
[a]
Conditions: thioanisole (0.2 mmol), photocatalyst (0.01 mmol), CF3CH2OH
Figure 2. N2 adsorption and desorption isotherms of 2D-PdPor-COF (a) and
3D-PdPor-COF (b) at 77K. The inset is their pore size distributions. CO2
adsorption and desorption isotherms of 2D-PdPor-COF (c) and 3D-PdPor-
COF (d) at 273K and 298K.
[b]
(1 mL), chlorobenzene (10 μL), irradiation with 3W blue LEDs, 0.4 h. Yield
determined by GC-FID with chlorobenzene as internal standard.
Benzoquinone as superoxide scavenger (1 mg).
[c]
p-
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10.1002/anie.201913091
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RESEARCH ARTICLE
3D-PdPor-COF as photocatalyst (entry 1), the photo-induced
oxidation of thioanisole to methyl phenyl sulfoxide can reach to a
yield of 98% in 0.4 h. This performance is comparable to many
reported heterogeneous photocatalysts (Table S7). In addition,
without any special treatment, 3D-PdPor-COF was still highly
active after 3 runs (Figure S17) with the framework retained
(Figure S18). We also evaluated the factors that may influence
the photocatalytic reaction. According to entries 2-4, it can be
concluded that the photocatalyst, light irradiation and oxygen
source are all indispensable.
presence of 3D-PdPor-COF, these tested substrates can be
efficiently converted to the desired products with high yields. As
usual,
3D-PdPor-COF
exhibited
better
photocatalytic
performance than 2D-PdPor-COF under same conditions, due to
its better photosensitizing activity mentioned above. However,
when substrates with larger sizes were used (entries 5-6), the
reaction yield of 3D-PdPor-COF decreased sharply while 2D-
PdPor-COF still showed reasonable yield. For example, by
changing the substrates from methyl p-tolyl sulfide (entry 2) to 4-
tert-butylphenyl methyl sulfide (entry 5), the yield of 3D-PdPor-
COF decreased from 99% to 48%, but for 2D-PdPor-COF, it is
almost the same. Accordingly, compared with 2D-PdPor-COF,
3D-PdPor-COF can exhibit certain size-selective photocatalysis.
This is reasonable, as the pore size of 3D-PdPor-COF is much
smaller than that of 2D-PdPor-COF.
However, when 2D-PdPor-COF was used as the
photocatalyst (entry 5) under same condition, the reaction yield
is only 48%, much lower than that of 3D-PdPor-COF. In order to
figure out the mechanism for this difference, we first performed
spin-trapping experiment by using electron spin resonance
(ESR) spectroscopy. After photoirradiation of the air saturated
CF3CH2OH solution containing 5,5-dimethyl-1-pyrroline N-oxide
(DMPO) and 2D-PdPor-COF or 3D-PdPor-COF, the signal for
the adduct of superoxide radical anion with DMPO was detected
(Figure S20) for both COFs, indicating the formation of the
superoxide radical anion. In addition, when the superoxide
scavenger p-benzoquinone was added into the reaction system
(entries 6 and 7), the conversion of thioanisole in the presence
of 3D-PdPor-COF and 2D-PdPor-COF reduced to 13% and 7%,
respectively. Therefore, the key oxidative intermediate in this
photocatalytic reaction is the superoxide radical anion, which is
generally accepted that it is formed through the electron transfer
of the excited triplet state of porphyrins to molecular oxygen.[20]
We then studied the triplet state lifetimes of these two COFs by
using transient absorption spectroscopy. As shown in Figure 3,
3D-PdPor-COF exhibited longer lifetime (26.34 μs) than that of
2D-PdPor-COF (0.41 μs). This difference can be explained from
their crystal structures (Figure 1), as the stacking mode of
palladium porphyrin units in 2D-PdPor-COF can efficiently
quench the triplet excited states. Consequently, compared with
2D-PdPor-COF, 3D-PdPor-COF has better photosensitizing
activity to produce superoxide radical anion, which results in
better photocatalytic performance.
Table 2. Substrate scope of the photocatalytic selective oxidation of sulfides to
sulfoxides by both COFs [a]
[a]
Conditions: sulfides (0.2 mmol), photocatalyst (0.01 mmol), CF3CH2OH (1
[b]
mL), chlorobenzene (10 μL), irradiation with 3W blue LEDs, 0.4 h.
Yield
a)
b)
determined by GC-FID with chlorobenzene as internal standard.
0.10
0.08
0.06
0.04
0.02
0.00
-0.02
0.8
0.6
0.4
0.2
0.0
-0.2
Conclusion
τT = 0.41 μs
τT = 26.34 μs
In conclusion, in order to demonstrate the influence of
dimensionality on COF functionality, we reported the designed
synthesis of 2D-PdPor-COF and 3D-PdPor-COF as well as their
properties characterization. Our results showed that, compared
with 2D-PdPor-COF, 3D-PdPor-COF can not only display higher
CO2 adsorption capacity, but also exhibit better photocatalytic
performance and size-selectivity. From this study, it can be
concluded that the incorporation of functional moieties into 2D or
3D COFs can definitely allow the resulting materials with
different properties, indicating the dimensionality of COFs can
influence the functionality through different arrangements of
0
10
20
30
40
0
50
100
150
200
Time (s)
Time (s)
Figure 3. Transient absorption decay curves of the triplet states of 2D-PdPor-
COF (a) and 3D-PdPor-COF (b) at 546 nm.
We further studied the applicability of both COFs as
photocatalysts, staring from substrates with different
substituents and sizes. As shown in Table 2 entries 1-4, in the
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Synthesis of 2D-PdPor-COF. A Pyrex tube was charged with p-
phenylenediamine (12.8 mg, 0.12 mmol), p-PdPor-CHO (50 mg, 0.06
mmol), 2 mL o-dichlorobenzene, 2 mL n-butanol, and 0.4 mL of 3 M
aqueous acetic acid. After being degassed by freeze-pump-thaw
technique for three times and then sealed under vacuum, the tube was
placed in an oven at 120 °C for 3 d. The resulting precipitate was filtered
off, exhaustively washed by Soxhlet extractions with tetrahydrofuran and
dichloromethane for 2 d, dried at 80 °C under vacuum for overnight. The
2D-PdPor-COF was isolated as a crimson powder (55.4 mg, 88% yield).
Elemental analysis for the calculated formula (C60H36N8Pd)n: C, 73.88%;
H, 3.72%; N, 11.49%. Found: C, 72.08%; H, 3.60%; N, 10.86%.
Synthesis of 3D-PdPor-COF. A Pyrex tube was charged with TAPM
(22.8 mg, 0.06 mmol), p-PdPor-CHO (50 mg, 0.06 mmol), 3.6 mL o-
dichlorobenzene, 0.4 mL n-butanol, and 0.4 mL of 6 M aqueous acetic
acid. After being degassed by freeze-pump-thaw technique for three
times and then sealed under vacuum, the tube was placed in an oven at
120 °C for 7 d. The resulting precipitate was filtered off, exhaustively
washed by Soxhlet extractions with tetrahydrofuran and dichloromethane
for 2 d, dried at 80 °C under vacuum for overnight. The 3D-PdPor-COF
was isolated as a tibetan orange powder (60.3 mg, 83% yield). Elemental
analysis for the calculated formula (C73H44N8Pd)n: C, 76.94%; H, 3.89%;
N, 9.83%. Found: C, 73.66%; H, 4.39%; N, 8.95%.
[5]
[6]
Acknowledgements
C.W. gratefully acknowledge financial support from the National
Natural Science Foundation of China (21772149 and 21572170),
the Funds for Creative Research Groups of Hubei Province
(2017CFA002) and the Fundamental Research Funds for the
Central Universities. J.S. also acknowledge financial support
from the National Natural Science Foundation of China
(21871009, 21621061 and 21527803), the Swedish Research
Council, and the Knut and Alice Wallenberg Foundation for
financial supports.
[7]
[8]
Keywords: dimensionality effect • functional moieties • COFs •
size-selective catalysis • CO2 adsorption
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Entry for the Table of Contents (Please choose one layout)
Layout 2:
RESEARCH ARTICLE
Yi Meng, Yi Luo, Ji-Long Shi, Huimin
Ding, Xianjun Lang, Wei Chen, Anmin
Zheng, Junliang Sun* and Cheng Wang*
Page No. – Page No.
2D and 3D Porphyrinic Covalent
Organic Frameworks: The Influence
of Dimensionality on Functionality
Text for Table of Contents
2D vs 3D COFs: In order to demonstrate the influence of dimensionality on COF functionality, we reported the designed synthesis of
2D-PdPor-COF and 3D-PdPor-COF. Our results showed that, compared with 2D-PdPor-COF, 3D-PdPor-COF can not only display
higher CO2 adsorption capacity, but also exhibit better photocatalytic performance and size-selectivity.
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