One-pot cascade syntheses of microporous and mesoporous pyrazine-linked covalent organic frameworks as Lewis-acid catalysts

Article abstract of DOI:10.1039/c8dt05056b

Covalent organic frameworks (COFs) are crystalline porous solids with broad potential applications. So far, the successful construction of COFs has been limited to a few condensation reactions, and nearly all COFs were obtained by single-step synthesis based on predesigned linkers. Here, we report a general strategy in view of a one-pot cascade reaction to prepare both microporous and mesoporous fully π-conjugated pyrazine-linked COF materials (PZ-COFs). The obtained PZ-COFs show high chemical stability, large specific surface areas and promising H₂, CH₄ and CO₂ uptake capacities. Furthermore, we demonstrate that manganese(ii)-incorporated PZ-COFs can act as excellent Lewis-acid catalysts for the cyanosilylation of aromatic aldehydes. This study not only provides a facile method to synthesize COFs required for multistep reactions but also expands the applications of COFs as promising catalysts.

Full text of DOI:10.1039/c8dt05056b

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Journal Name
ARTICLE
One-Pot Cascade Syntheses of Microporous and Mesoporous
Pyrazine-Linked Covalent Organic Frameworks as Lewis-Acid
Catalysts
Received 00th January 20xx,
Accepted 00th January 20xx
a,†
a,†
a
a
a
a
a,
DOI: 10.1039/x0xx00000x
Yunchao Ma, Xiaozhou Liu, Xinyu Guan, Hui Li, Yusran Yusran, Ming Xue, Qianrong Fang, *
b
a
a,c,
Yushan Yan, Shilun Qiu and Valentin Valtchev
*
www.rsc.org/
Covalent organic frameworks (COFs) are crystalline porous solids with broad potential applications. So far, the successful
construction of COFs was limited to a few condensation reactions, and nearly all COFs were obtained by single-step
synthesis based on predesigned linkers. Here, we report a general strategy in view of a one-pot cascade reaction to
prepare both microporous and mesoporous fully π-conjugated pyrazine-linked COF materials (PZ-COFs). The obtained PZ-
2 4 2
COFs show high chemical stability, large specific surface areas as well as H , CH and CO uptake capacities. Furthermore,
we demonstrate that manganese(II)-incorporated PZ-COFs can act as excellent Lewis-acid catalysts for the cyanosilylation
of aromatic aldehydes. This study not only provides a facile method to synthesize COFs required for multistep reactions
but also expands the applications of COFs as promising catalysts.
exploration of new synthetic strategies, for example,
obtaining linkers at the same time in synthesis of COFs, is an
important and crucial task for the development of this
Introduction
As a new class of crystalline porous polymers, covalent organic
frameworks (COFs)[ have attracted considerable attention
due to their outstanding potential in gas adsorption and
promising class of porous materials.
1]
Herein we report a new synthetic approach based on a
one-pot cascade reaction strategy to produce COF materials. In
view of this synthetic method, two microporous and
mesoporous pyrazine-linked COFs, denoted PZ-COF-1 and PZ-
COF-2, were successfully obtained by one-pot synthesis
involving a two-step dehydration-oxidation reaction. Both
materials show high chemical stability, impressive specific
[
2]
[3]
[4]
separation, proton conduction, optoelectronics, drug
[
5]
[6]
deliver, chemical sensing, and especially heterogenous
catalysis.[ Since the pioneering work of Yaghi in 2005,
7]
[1a]
a
variety of two-dimensional (2D) COFs[ with eclipsed or
8]
staggered structures and three-dimensional (3D) COFs with the
ctn,[ bor,
9]
[10]
dia
[11]
or pts
[12]
topology have been prepared
surface area, and promising gas storage capacities for H
2 4
, CH
over the past decade. However, owing to the complex nature
of reversible synthesis, successful methods for the
constructions of COF materials have been limited to a few
chemical reactions, including three most commonly used
types: boronic acid trimerization, boronate ester formation,
and Schiff base reaction.[
and CO . Furthermore, we demonstrate that PZ-COFs can
2
incorporate manganese(II) ions by coordinating to nitrogen
atoms of adjacent layers in PZ-COFs, and the resulting Mn(II)-
assembled COF materials can act as excellent Lewis-acid
catalysts for the cyanosilylation of aldehyde compounds.
1c,1d]
Furthermore, nearly all COFs
reported were obtained by single-step reaction based on
predesigned linkers. As we all known, to obtain pure
predesigned linkers is general difficulty, and thus the
Results and discussion
Our strategy for preparing PZ-COFs involves a one-pot
dehydration and oxidation cascade reaction. As shown in
Scheme 1a and 1b, 9,10-diazaanthracene (DAA) can be
normally produced by the two-step path of the combination of
a. State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin
University, Changchun 130012, China. E-mail: qrfang@jlu.edu.cn
b.
both dehydration and oxidation reaction, which is a
Department of Chemical and Biomolecular Engineering, Center for Catalytic
[
13]
Science and Technology, University of Delaware, Newark, DE 19716, USA
Normandie Univ, ENSICAEN, UNICAEN, CNRS, Laboratoire Catalyse et
complicated process. Thus, we design the dehydration and
oxidation cascade reaction to obtain DAA by one-pot synthesis
of 1,2-diaminobenzene (DAB) and 1,2-dihydroxybenzene (DHB,
Scheme 1c and Figure S1 in SI). On the basis of the same
c.
Spectrochimie, 6 Marechal Juin, 14050 Caen, France.
E-mail: valentin.valtchev@ensicaen.fr
†
These authors contributed equally to this work.
‡
Electronic Supplementary Information (ESI) available: Procedure for the
1
3
strategy, DHB is replaced by a flat triangular linker,
preparation of the COFs, TEM images, IR spectra, solid-state C NMR, TGA traces,
PXRD patterns and simulations, BET plots, H , CO and CH
adsorption-desorption hexahydroxy triphenylene (HHTP) and the DAB is substituted
2
2
4
isotherms, and fractional atomic coordinates. See DOI: 10.1039/x0xx00000x
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The syntheses of PZ-COFs were carried out by
View Article Online
DOI: 10.1039/C8DT05056B
solvothermal reaction of HHTP, K Cr O and TAB or DABZ in a
2 2 7
mixed solution of N-methyl-2-pyrrolidone (NMP), mesitylene
and acetic acid (AcOH), followed by heating at 120 °C for 3
days. The AcOH is employed as a catalyst to promote the
2 2 7
dehydration reaction and K Cr O is an oxidizer for the
oxidation reaction. The conversion of the reactants was 85%
for PZ-COF-1 and 83% for PZ-COF-2. The products, black solids,
were insoluble in common organic solvents such as
tetrahydrofuran (THF), acetone, methanol (MeOH),
dichloromethane (CH Cl ), chloroform (CHCl ), hexane, N,N-
2 2 3
dimethylformamide (DMF), dimethylsulfoxide (DMSO) and
dioxane.
Scheme 1 Strategy for preparing pyrazine-linked COFs (PZ-COFs).
(
a) Two-step synthesis of DAA involving the dehydration of 1,2-
diaminobenzene (DAB) and 1,2-dihydroxybenzene (DHB) followed
,10-dihydrophenazine (DHP) by the oxidation. (b) Two-step
5
synthesis of DAA involving the oxidation of DHB followed the
dehydration of 1,2-benzoquinone (BQ) and DAB. (c) One-pot
cascade dehydration and oxidation synthesis of DAA from DAB and
DHB. (d) Expanded synthesis of hexahydroxy triphenylene (HHTP)
and 1,2,4,5-tetraminobenzene (TAB) or 3,3 ′ -diaminobenzidine
Fig. 1 PXRD patterns of PZ-COF-1 (a) and PZ-COF-2 (b) with the
observed profile in black, refined in red, the difference
(DABZ) to give 2D crystalline pyrazine-linked COFs, microporous
PZ-COF-1 and mesoporous PZ-COF-2. (e) On the basis of triangular
and linear building units, PZ-COFs show 2D hexagonal frameworks
based on the boron nitride net (bnn).
(observed minus refined) in pink, and calculated based on the
eclipsed structure in blue. Inset: enlarged experimental PXRD
patterns and SEM images.
by linkers with four amine groups, 1,2,4,5-tetraminobenzene
(
TAB) or 3,3′-diaminobenzidine (DABZ), yielding two new large-
Scanning electron microscopy (SEM) and transmission
electron microscopy (TEM) studies revealed that both PZ-COFs
exhibited isometric morphology (Figure 1 inset, Figures S2 and
S3 in SI). The particle size is about 1 µm for both materials;
namely individual particles are observed in PZ-COF-1 while PZ-
COF-2 contains complex aggregates. Fourier transform infrared
pore structures. These new COFs, denoted PZ-COF-1 and PZ-
COF-2 exhibit pore diameter of 18 Å and 25 Å, respectively
(Scheme 1d). In this case, HHTP can be defined as a 3-
connected node, and TAB or DABZ can act as a 2-connected
node, which results in 2D structures with the boron nitride net
bnn, Scheme 1e).[
14]
(
(
FT-IR) spectra of PZ-COFs (Figures S4-S8 in SI) showed the
-1
disappearance of the hydroxyl stretching band (3420 cm for
2
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-
1
HHTP), and the N-H stretching band (around 2952 cm for TAB 90°, and γ = 120°. Simulated PXRD patterns show good match
View Article Online
DOI: 10.1039/C8DT05056B
and 3388 cm-1 for DAB), indicating a completed conversion of with the experimental ones (Figure 1, black and blue curves).
these groups. Meanwhile, the characteristic stretching bands In addition, the full profile pattern matching (Pawley)
of pyrazine linkages (1256 and 1448 cm for PZ-COF-1 as well refinements are performed from the experimental PXRD
as 1265 and 1448 cm for PZ-COF-2) emerged in the IR patterns. PXRD peaks at 4.05, 7.01, 8.10, 10.72 and 25.87° for
spectra.[ The atomic order of PZ-COFs was further studied by PZ-COF-1 can be assigned to the (100), (110), (200), (210) and
-1
-1
8i]
1
3
solid-state
CP/MAS) NMR spectroscopy (Figures S9 and S10 in SI). The 25.89° for PZ-COF-2 correspond to the (100), (110), (200),
two signals at δ = 125 and 134 ppm for PZ-COF-1 and at δ = (210) and (001) Bragg peaks, respectively. The refinement
24 and 133 ppm for PZ-COF-2 can be assigned to different results revealed unit cell parameters nearly equivalent to the
aromatic carbons, respectively. According to the predictions with excellent agreement factors (a = b = 25.761 Å,
thermogravimetric analysis (TGA), the PZ-COFs are stable up to c = 3.555 Å, α = β = 90°, γ = 120°, wR = 1.72%, and R = 0.69%
about 300 °C (Figure S11 in SI). We also tested the chemical for PZ-COF-1; a = b = 32.521 Å, c = 3.532 Å, α = β = 90°, γ =
stability of PZ-COFs by dispersing the samples in aqueous HCl 120°, wR = 1.91%, and R = 0.89% for PZ-COF-2). Besides the
1 M) or NaOH (1 M) solutions and found that there was no eclipsed structure, we also considered an alternative staggered
change in their powder X-ray diffraction (PXRD) patterns model, which was set up from the space groups of P6 /mmc
Figures S12 and S13 in SI). (No. 194) for PZ-COF-1 or P6 /m (No. 176) for PZ-COF-2.
C
cross-polarization magic-angle-spinning (001) Bragg peaks. The peaks at 3.18, 5.53, 6.39, 8.45 and
(
1
p
p
p
p
(
3
(
3
However, these calculated patterns did not match the
experimental PXRD patterns (Figures S14-19 and Tables S1-4 in
SI). On the basis of the above results, we can state that both
PZ-COFs have the expected architectures with the eclipsed
model, which show the microporous hexagonal pores with
diameter of about 18 Å for PZ-COF-1 and mesoporous
channels with diameter of about 25 Å for PZ-COF-2 (Figure 2).
Fig. 2 Structural representations of microporous PZ-COF-1 (a)
and mesoporous PZ-COF-2 (b). C, yellow; N, blue; H, white.
2
Fig. 3 N adsorption-desorption isotherms of microporous PZ-
COF-1 (a) and mesoporous PZ-COF-2 (b) at 77 K. Inset: the pore
size distribution.
The crystalline nature of new PZ-COFs was confirmed by
PXRD analysis (Figure 1). After
a geometrical energy
minimization by using the Materials Studio Software
package[
15]
based on the eclipsed structure the unit cell
parameters were determined. PZ-COF-1 exhibits space group
P6/mmm (No. 191) with unit cell of a = b = 25.184 Å, c = 3.439
Å, α = β = 90°, and γ = 120°. PZ-COF-2 shows space group P6/m
The specific surface area and porosity of PZ-COFs were
determined by measuring N adsorption at 77 K. As can be
2
seen in Figure 3, PZ-COF-1 exhibited the characteristic for
(No. 175) with unit cell of a = b = 32.009 Å, c = 3.440 Å, α = β =
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microporous materials type I isotherm with sharp uptake photoelectron spectroscopy (XPS, Figure S33 inVieSwI)ArtsichleoOwnleinde
below 0.05 P/P
. Type IV isotherm with a two-stmeep uptake that the binding energies of Mn 2p3/2 DiOnI:M10n.1/0P3Z9-/CC8ODFTs05w0e56rBe
below 0.2 P/P , which is typical of ordered mesoporous about 642 eV, indicating that the Mn species were in +2 state.
0
0
materials, was recorded for PZ-COF-2. The absence of Mn/PZ-COFs and a model complex Mn/Phen (Phen = 1,10-
hysteresis during desorption for PZ-COF-2 is a common feature phenanthroline) had a similar shift of 1 eV in comparison with
of materials containing hexagonally aligned 1D mesopores.[
16]
2
that of free Mn(OAc) , which suggested that Mn ions were
The application of the Brunauer-Emmett-Teller (BET) model in most probably located in between the adjacent layers of PZ-
the low pressure region (0.005 < P/P < 0.105) showed a BET COFs and efficiently coordinated with two nitrogen atoms
0
2
-1
2
-1
[7a]
surface areas of 845 m g for PZ-COF-1 and 1130 m g for from different layers.
PZ-COF-2 (Figures S20 and S21 in SI). The pore-size
distributions of PZ-COFs were calculated by nonlocal density Table
1
Catalytic activities of Mn/PZ-COFs in the
a
functional theory (NLDFT) and showed a narrow pore width cyanosilylation of aldehyde compounds
16 Å for PZ-COF-1 and 24 Å for PZ-COF-2, Figure 3 inset),
(
which was in good agreement with the pore sizes predicted
from their crystal structures (18 Å for PZ-COF-1 and 25 Å for
PZ-COF-2). In addition the adsorption of H
both PZ-COFs was studied in order to evaluate their potential
application in gas storage (Figures S22-24 in SI). PZ-COF-1
2
, CO
2
and CH
4
for
Entry
Ar
phenyl
Catalyst
Time
(h)
6
5
6
5
6
5
8
Yield
(%)
b
1
2
3
4
5
6
7
8
9
Mn/PZ-COF-1
Mn/PZ-COF-2
Mn/PZ-COF-1
Mn/PZ-COF-2
Mn/PZ-COF-1
Mn/PZ-COF-2
98
99
97
97
96
97
97
98
96
98
3
−1
3
−1
showed uptake of 121 cm g of H
2
, 68 cm g of CO
2
and 14
phenyl
3
−1
cm g of CH
4
. The mesoporous PZ-COF-2 could store up to
biphenyl
biphenyl
1-naphthyl
1-naphthyl
methoxyphenyl Mn/PZ-COF-1
methoxyphenyl Mn/PZ-COF-2
3
−1
3
−1
3
−1
1
56 cm g of H
2
, 91 cm g of CO
2
and 21 cm g of CH
4
.
8
3
3
nitrophenyl
nitrophenyl
Mn/PZ-COF-1
Mn/PZ-COF-2
1
0
a
Reaction conditions: Me
mmol), dry CH Cl (6.0 mL), Mn/PZ-COF-1 or Mn/PZ-COF-2 (0.1
mmol), room temperature, under Ar. Determined by H NMR
3
SiCN (1.0 mmol), aldehyde (1.0
2
2
b
1
Scheme 2 Schematic representation for the syntheses of based on the starring materials.
Mn/PZ-COFs.
The catalytic activities of Mn/PZ-COFs were subsequently
Encouraged by high porosity and the appropriate distance examined in one of the representative Mn(II)-catalyzed
~3.4 Å) of eclipsed nitrogen atoms in adjacent layers, which reactions, i.e., the cyanosilylation reaction, which is an
(
makes PZ-COFs an ideal scaffold for incorporating metal important step to key derivatives in the syntheses of fine
ions,[
7a]
we successfully assembled the manganese(II)- chemicals and pharmaceuticals. The catalytic reactions were
[17]
coordinated COF materials (denoted as Mn/PZ-COFs), and performed with 1.0 mmol of each reactant in dry CH Cl (6.0
2
2
explored their catalytic potential for the cyanosilylation of mL) with PZ-COF-1 or PZ-COF-2 (10 mol%) at room
aldehyde compounds. Typically, through simple post- temperature for 5~6 h. The conversion and the product
treatment of PZ-COFs with manganese acetate, Mn(OAc)
distribution were monitored by H NMR spectroscopy based
a
2
,
1
Mn/PZ-COFs were facilely prepared (Scheme 2 and see SI for on the starting materials. As shown in Table 1, Me SiCN
3
details). A comparison of PXRD patterns of PZ-COFs and reacted with benzaldehyde to form the product α-
Mn/PZ-COFs revealed that crystal structures of PZ-COFs were (trimethylsilyloxy)phenylacetonitrile (Ar = phenyl) in excellent
well preserved after the treatment with Mn(OAc)
and S26 in SI). SEM images suggested that layer structures of Furthermore, by replacing benzaldehyde reactant with 4-
PZ-COFs also remained unchanged after the reaction with biphenylcarboxaldehyde,
1-naphthaldehyde, 4-
Mn(OAc) (Figures S27 and S28 in SI). The well-dispersed methoxybenzaldehyde or 4-nitrobenzaldehyde, and keeping all
2
(Figures S25 yields (98% for Mn/PZ-COF-1 and 99% for Mn/PZ-COF-2).
2
manganese species could be clearly observed in the energy other conditions the same, high yields (96-99%) can be
dispersive X-ray (EDX) mapping analysis (Figures S29 and S30 in obtained under different reaction time (3-8 hrs, Table 1).
SI). Nitrogen adsorption isotherms at 77 K of Mn/PZ-COFs Figures 4, S34 and S35 depict the concentration of products as
indicated a lower N
2
adsorption which is due to the presence a function of time. We verified that the reaction was indeed
of Mn(OAc) in the pores (Figures S31 and S32 in SI). catalyzed by Mn/PZ-COFs instead of free Mn(OAc)2 by a
2
Manganese content of 6.3 wt% for Mn/PZ-COF-1 and 6.6 wt% control experiment, in which the catalyst was removed from
for Mn/PZ-COF-2 was determined by ICP analysis. X-ray the reaction mixture after 1 h, and the isolated solution was
4
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retained under the same reaction conditions. No further
conversion was observed in this case (Figure S36 in SI). After
the catalytic reactions, the results of PXRD confirmed the
structural integrity of Mn/PZ-COFs, thus revealing the high
stability of new COF materials in the cyanosilylation reaction
Acknowledgements
This work was supported by National Natural Science
Foundation of China (21571079, 21621001, 21390394,
View Article Online
DOI: 10.1039/C8DT05056B
2
1571076, and 21571078), “111” project (B07016 and
B17020), Guangdong Science and Technology Department
Project (2012D0501990028) , and the program for JLU Science
and Technology Innovative Research Team. Q.F and V.V.
acknowledge the support from Thousand Talents program
(Figures S37 and S38 in SI). The COF crystals can be easily
isolated from the reaction mixture by a simple filtration and
reused at least four times with almost no loss of activity and
similar TOF (Figures S39 and S40 in SI).
(China). V.V., Q.F. and S.Q. acknowledge the collaboration in
the framework of China-French joint laboratory Zeolites.
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of benzaldehyde (blue), 4-biphenylcarboxaldehyde (red), and
1
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COF-2 (b). Inset: the structures of products. C, green; N, blue;
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2
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