Gram-Scale Synthesis of Cu(II)@COF via Solid-State Coordination Approach for Catalysis of Alkyne-Dihalomethane-Amine Coupling

Article abstract of DOI:10.1021/acs.inorgchem.0c03783

A novel covalent organic framework material COF-DM, which contains chelating coordination environments, was synthesized at the gram level under mild conditions. In addition, its Cu(II)-loaded complex of Cu(II)@COF-DM was prepared by impregnating COF-DM in

Full text of DOI:10.1021/acs.inorgchem.0c03783

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Gram-Scale Synthesis of Cu(II)@COF via Solid-State Coordination
Approach for Catalysis of Alkyne-Dihalomethane-Amine Coupling
Xuan Kan,† Jian-Cheng Wang,*,† Jing-Lan Kan, Jin-Yan Shang, Hua Qiao, and Yu-Bin Dong*
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ABSTRACT: A novel covalent organic framework material COF-DM,
which contains chelating coordination environments, was synthesized at
the gram level under mild conditions. In addition, its Cu(II)-loaded
complex of Cu(II)@COF-DM was prepared by impregnating COF-
DM in an acetonitrile solution of CuCl2 via a solid-state coordination
approach. The obtained Cu(II)-loaded Cu(II)@COF-DM can be used
as a highly active heterogeneous catalyst to catalyze the alkyne-
dihalomethane-amine coupling reactions.
conditions, which significantly limits their practical applica-
tions.
INTRODUCTION
■
As an important class of structural skeletons and synthetic
intermediates in biologically active compounds, propargyl-
amines have been widely used in medical and synthetic
chemistry.1 In this context, the three-component coupling has
been recognized as a useful approach to synthesize propargyl-
amines. Besides the A3-coupling (aldehyde-alkyne-amine)
reaction,2 the AHA coupling (alkyne-dihaloalkane-amine)
reaction, which is generally catalyzed by discrete metal-
complexes such as Au-,3 Ag-,4 Fe-,5 Cu-,6 and Co-complexes,7
is also an effective way to access propargylamines. Although
In this contribution, we report the gram-scale synthesis of a
new Cu(II)-ion-loaded COF material, in which the COF-DM
contains chelating coordination environments and can bind
and stabilize the Cu(II) ion via Cu-N and Cu-O coordination
interactions in the COF framework. As a heterogeneous
catalyst, the obtained Cu(II)@COF-DM is stable and displays
highly catalytic performance for alkyne-dihalomethane-amine
(AHA) coupling reaction even at the gram-scale level.
EXPERIMENTAL SECTION
■
the reported homogeneous metal-catalysts are the mainstream
Materials and Instrumentations. All the involved chemicals
were from commercial sources and used directly without further
purification. 1,4-Dibenzoylhydrazinyl-2-methylbenzene (DBHMB)
(Scheme 1) was synthesized using a previously reported method.13
In our experiments, there are no new, unexpected, and/or significant
hazards or risks. Infrared (IR) spectra were recorded within 400−
4000 cm−1 by a Bruker ALPHA FT-IR spectrometer. Elemental
in propargylamines synthesis, the issues of environmental
pollution, metal species recovery, and recycling have seriously
hindered their widespread use in industry.
Covalent organic frameworks (COFs), as an important class
of organic crystalline porous materials,8 have drawn consid-
erable attention because of their various potential applications,
especially in catalysis.9 The inherent porosity and good
chemical stability make COFs competent in supporting active
catalytic species for heterogeneous catalysis. Besides organo-
catalysts10 and metal nanoparticles,11 the metal ions can also
be loaded by COFs for Mn+@COFs type of heterogeneous
catalysts.12 In principle, the COFs with metal-ion-binding sites
can be logically designed and synthesized and, furthermore,
used as the COF ligands to trap and stabilize various metal
ions via solid-state coordination reactions. As a result, the
highly ordered arrangement of the metal-ion-binding sites
would allow the metal ions to homogeneously disperse in the
COF matrix. In most cases, however, the reported COF-based
catalysts are prepared at milligram scale under rigorous
1
analyses were conducted on a PerkinElmer model 2400 analyzer. H
NMR data were obtained on an AM-400 spectrometer using TMS as
internal standard. 13C NMR data were collected on a MERCURY plus
400 spectrometer with resonance frequencies of 400 MHz. The BET
(Brunauer−Emmett−Teller) specific surface areas were obtained on a
Micromeritics ASAP 2020 sorption/desorption analyzer by N2
Received: December 25, 2020
Published: February 17, 2021
https://dx.doi.org/10.1021/acs.inorgchem.0c03783
© 2021 American Chemical Society
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a
Scheme 1. Synthesis of COF-DM and Cu(II)@COF-DM
a
Their sample photographs are inserted.
adsorption and desorption experiments at 77 K. The scanning
electron microscopy (SEM) was performed on a Gemini Zeiss Supra
TM scanning electron microscope with an energy-dispersive X-ray
detector (EDX). High resolution transmission electron microscopy
(HR-TEM) analysis was conducted on a JEOL 2100 Electron
Microscope (operating voltage of 200 kV). MS spectra were obtained
by a Bruker maXis ultra-high resolution-TOF MS system. GC analysis
was carried out on a 7890B gas chromatograph (Agilent
Technologies, CA, USA) with a flame ionization detector (FID)
and a split/splitless injector. The GC capillary column (DB-WAX, 30
m length × 0.53 mm; HP-5, 30 m length × 0.32 mm) was purchased
from the Agilent Technologies. X-ray photoelectron spectroscopy
(XPS) was obtained from a THI5300 (PE). Inductively coupled
plasma (ICP) analysis was conducted on an IRIS Interpid (II) XSP
and NU AttoM. Ion chromatograph (IC) analysis was performed on a
Thermo Scientific ICS-5000MSQ at a flowing rate of 0.25 mL/min.
Thermogravimetric analyses (TGA) were conducted on a TA
Instrument Q5 simultaneous TGA under flowing N2 (heating rate,
10 °C/min). Powdered X-ray diffraction (PXRD) patterns were
generated on D8 Advance X-ray powder diffractometer (Cu Kα
radiation, λ = 1.5405 Å).
Synthesis of COF-DM. A mixture of dimethyl sulfoxide/
mesitylene (6/19 mL) solution of DBHMB13 (162 mg, 0.45
mmol), MOP (63 mg, 0.3 mmol), and acetic acid (5 mL, 6 M)
was heated at 60 °C for 3 days. The obtained solids were collected by
centrifugation and separately washed with methanol and acetone, and
dried in vacuum overnight to afford COF-DM (108 mg, 57% yield).
IR (KBr pellet cm−1): 3417(s), 2930(w), 1660(vs), 1576(w),
1486(w), 1439(w), 1414(vw), 1387(s), 1280(s), 1188(s), 1099(w),
825(w), 762(w), 662(w).
1509(vs), 1377(s),1237(w), 1005(w), 853(vw), 823(w), 793(vw),
756(vw), 702(vw), 603(vw). ICP analysis showed that the loading
amount of Cu(II) in Cu(II)@COF-DM was 13.0 wt % based on
three measured results (Supporting Information). The theoretical
calculation content of chlorine is 7.12 wt % based on Cu, and the
experimental measurement by ion chromatography(IC) is 6.93 wt %
(Supporting Information).
Synthesis of Cu(II)@polymer-DM. A mixture of DBHMB (162
mg, 0.45 mmol), MOP (63 mg, 0.3 mmol), and acetic acid (5 mL, 6
M) in dimethyl sulfoxide/mesitylene (6/19 mL) was stirred for 3 days
at room temperature. The obtained solids were isolated by
centrifugation and separately washed with methanol and acetone.
Then generated solids were dried in vacuum overnight to afford
amorphous polymer-DM (118 mg, 62% yield). IR (KBr pellet cm−1):
3416(s), 2931(w), 1660(vs), 1577(w), 1485(w), 1438(w), 1415(vw),
1387(s), 1281(s), 1188(s), 1098(w), 825(w), 763(w), 661(w).
A mixture of polymer-DM (120 mg) and CuCl2 (55.1 mg, 0.41
mmol) was stirred in acetonitrile (20 mL) for 12 h at room
temperature. The product was isolated by filtration and completely
washed with acetonitrile. The obtained solids were dried in vacuum
overnight to provide Cu(II)@polymer-DM (123 mg, 70% yield). IR
(KBr pellet cm−1): 3335(s), 1581(vs), 1507(vs), 1377(s), 1235(w),
1003(w), 851(vw), 822(w), 793(vw), 757(vw), 701(vw), 602(vw).
ICP analysis showed that the loading amount of Cu(II) in Cu(II)@
polymer-DM was 13.2 wt % based on three measured results
(Supporting Information).
Synthesis of Model Compounds A and B. A: A mixture of
benzoyl hydrazine (3 mmol, 0.41 g) in MeOH (30 mL) and 2,4,6-
triformylphloroglucinol (1 mmol, 0. 21 g) in THF (15 mL) was
refluxed at 70 °C for 12 h. Pale yellow solids of A were obtained in
91% yield. IR (KBr pellet cm−1): 3224(s), 3059(s), 2951(w),
1646(vs), 1602(vs), 1532(vs), 1490(s), 1456(s), 1398(w), 1330(s),
1281(s), 1187(s), 1027(w), 1001(w), 959(w), 884(w), 795(w),
776(w), 687(w). 1H NMR (400 MHz, DMSO, 25 °C, TMS, ppm): δ
= 13.93 (s, 3H), 12.27 (s, 3H), 8.94 (s, 3H), 7.96 (d, J = 7.2 Hz, 6H),
7.63 (t, J = 7.3 Hz, 3H), 7.56 (t, J = 7.4 Hz, 6H).
Gram-Level Synthesis of COF-DM. A mixture of dimethyl
sulfoxide/mesitylene (62/186 mL) solution of DBHMB (2.00 g, 5.56
mmol), MOP (0.78 g, 3.7 mmol), and acetic acid (62 mL, 6 M) was
heated at 60 °C for 3 days. The obtained solids were collected by
centrifugation and separately washed with methanol and acetone, and
then dried in vacuum overnight to give COF-DM (1.18 g, 52% yield).
Synthesis of Cu(II)@COF-DM. A mixture of COF-DM (120 mg)
and copper chloride (55.1 mg, 0.41 mmol) was stirred in acetonitrile
(20 mL) for 24 h at room temperature. The product was collected by
filtration and completely washed with acetonitrile. The crystalline
solids were dried in vacuum overnight to afford Cu(II)@COF-DM
(125 mg, 71% yield). IR (KBr pellet cm−1): 3338(s), 1583(vs),
B: A mixture of A (0.16 mmol, 0.1 g) and copper nitrate (0.26
mmol, 0.05 g) in MeOH (30 mL) was stirred for 12 h at room
temperature. B was obtained as yellow-green solids in 95% yield. IR
(KBr pellet cm−1): 3011(s), 2846(w), 1604(s), 1573(vs), 1539(s),
1498(vs), 1446(s), 1413(s), 1360(vs), 1312(s), 1249(w), 1191(w),
1106(w), 1024(w), 998(w), 799(w), 692(s). Single crystals of B were
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Figure 1. (a) SEM image of COF-DM. (b) PXRD patterns of COF-DM. (c) The top and side views of COF-DM. (d) HRTEM image of COF-
DM.
Figure 2. (a) PXRD patterns of COF-DM and Cu(II)@COF-DM. (b) HRTEM image of Cu(II)@COF-DM. (c) XPS spectrum of Cu(II)@
COF-DM. (d) SEM-EDX image of Cu(II)@COF-DM.
gotten through recrystallization of yellow-green solids in methanol. A
suitable crystal was selected and was kept on a clean glass slide on a
Super Nova, Dual, Cu at home/near, Eos diffractometer. The crystal
was kept at 293(2) K during data collection. Using Olex2,14 the
structure was solved with the ShelXT15 structure solution program
using Intrinsic Phasing and refined with the ShelXL16 refinement
package using Least Squares minimization.
General Procedure for AHA Coupling Catalyzed by Cu(II)@
COF-DM. A mixture of alkyne (0.3 mmol), dichloromethane (0.5
mmol, 35 μL), amine (0.5 mmol), DBU (0.6 mmol, 110 μL), and
Cu(II)@COF-DM (5.0 mg) was charged in the reaction tube with 2
mL of CH3CN. After stirring at 80 °C for 12 h, the reaction was
cooled to room temperature. After the catalyst was recovered by
centrifugation, the corresponding products were isolated by column
chromatography on silica gel to provide the corresponding products.
RESULTS AND DISCUSSION
■
Synthesis and Characterization of COF-DM. As shown
in Scheme 1, COF-DM was prepared as yellow crystalline
solids via the aldimine condensation between 1,4-dibenzoylhy-
drazinyl-2-methylbenzene (DBHMB)13 and 2,4,6-trihydroxy-
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Figure 3. Synthesis of model compounds A and B (i: 70 °C, 12 h, MeOH/THF, 91% yield; ii: Cu(NO3)2, MeOH, R.T., 12 h, 95% yield). The
single-crystal structure of B is also shown.
1,3,5-benzenetricarbaldehyde (MOP) at 60 °C for 3 days in
air. Unlike the usual vigorous conditions (high temperature
and high pressure) used for the preparation of CN linked
COFs, the reaction conditions herein are much milder and,
moreover, can achieve gram-level mass production. FT-IR and
solid-state CP-MAS spectroscopies unequivocally confirmed
the formation of COF-DM from DBHMB and MOP
monomers via Schiff-base condensation reaction (Supporting
Information).
As shown in Figure 1a, COF-DM was obtained as the
micron-scale material, and the measured powder X-ray
diffraction (PXRD) pattern indicated that the COF-DM was
highly crystalline (Figure 1b), and it showed a main Bragg
diffraction peak at 2.287° associated with the (010) plane.
Besides, three weak peaks at 3.961°, 4.574°, and 6.053°,
respectively, corresponding to (110), (020), and (120) planes
were also observed. After modeling its structure using
Materials Studio software (ver. 5.0),17 the most reasonable
structure of COF-DM was determined as a two-dimensional
(2D) layered hexagonal net with an eclipsed (AA) stacking
mode (Figure 1c). As shown in Figure 1b, the Pawley
refinement indicated a negligible difference between the
simulated and experimental PXRD patterns. COF-DM was
assigned to the space group P3 with optimized parameters of a
= b = 44.5752 Å, c = 3.8417 Å, α = β = 90°, γ = 120°, and
residuals Rwp = 5.79% and Rp = 3.71% (Supporting
Information). The crystalline nature of COF-DM was further
verified from the clearly observed lattice fringes by HR-TEM
(Figure 1d).
loaded Cu valence was bivalent.18 The SEM-EDX image
showed that C, O, N, and Cu species homogeneously
dispersed in the COF matrix (Figure 2d). ICP analysis showed
that the Cu-loading amount in Cu(II)@COF-DM was 13.0 wt
% (Supporting Information). TGA trace showed that Cu(II)@
COF-DM was intact until the temperature over 220 °C,
implying that it possesses good thermostability (Supporting
Information).
Synthesis and Characterization of Model Com-
pounds A and B. For further demonstrating the Cu(II)
location in COF-DM, we prepared model molecular ligand A
from benzohydrazide and MOP and its Cu(II) complex B in
solution (Figure 3). The X-ray single-crystal analysis showed
that the Cu(II) ion in B is located in a {CuO3N} coordination
sphere, in which the Cu−N and Cu−O bond lengths range
from 1.8 to 2.4 Å (Figure 3, Supporting Information, CCDC
2048265). On the basis of this, we can conclude that the
loaded Cu(II) ions in COF-DM were bound and stabilized by
the N′-((E)-3-oxobut-1-enyl) acetohydrazide chelating group
in the same way. The porosity of COF-DM and Cu(II)@
COF-DM was demonstrated by measuring N2 adsorption−
desorption at 77 K (Supporting Information). The Brunauer−
Emmett−Teller (BET) surface areas of COF-DM and Cu(II)
@COF-DM were estimated to be 701.64 and 445.82 m2 g−1,
respectively. The nonlocal density functional theory (NLDFT)
led to a narrow pore size distribution, and their average pore
widths of COF-DM and Cu(II)@COF-DM are, respectively,
centered at 3.6 and 3.2 nm, which was well consistent with
their simulated structures.
Synthesis and Characterization of Cu(II)@COF-DM.
Scheme 1 shows that Cu(II)@COF-DM was generated as
yellow-brown crystalline solids by simply soaking COF-DM in
a CH3CN solution of CuCl2 for 24 h at room temperature.
The crystallinity and structural integrity of COF-DM was
intact after the Cu(II) loading, which was further verified by
the measured PXRD pattern and HR-TEM analysis (Figure
2a,b). As shown in Figure 2c, the Cu 2p binding energy is
935.42 eV (Cu 2p3/2) in its XPS spectrum, implying that the
Model AHA Coupling Catalyzed by Cu(II)@COF-DM.
The previously reported copper catalyst for the propargyl-
amines formation was Cu(I) salts.6 As we know, the
monovalent copper salts are easily oxidized and difficult to
store, which could lead to a series of resource waste and
environmental pollution issues. Therefore, we expected that
Cu(II)@COF-DM could be used as an effective catalyst to
promote the propargylamines formation in a heterogeneous
way. To this end, the catalytic activity of Cu(II)@COF-DM
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for AHA coupling reaction was examined based on alkynes,
dihaloalkanes, and amines.
As shown in Table 1, the various reaction conditions,
including different temperatures, solvents, and bases, were
temperature increase (Table 1, entries 1 and 2). The best
reaction conditions for the model reaction were determined as
80 °C, 12 h, and in CH3CN (Table 1, entry 2). Other solvent
systems, such as H2O, THF, DMF, and DMSO have also been
employed to perform the reaction, but none of them achieved
the ideal yields (Table 1, entries 3−6). Furthermore, when the
reaction was conducted with an inorganic base such as K2CO3
or Na2CO3, the yield of the AHA coupling under given
conditions was also very high, but it took a longer reaction
time (Table 1, entries 7 and 8). When triethylamine (TEA)
was used, a lower 89% yield for the model AHA coupling
reaction was obtained (Table 1, entry 9). When the reaction
was performed in the presence of CuCl2 in a homogeneous
manner under the optimal conditions, the target propargyl-
amine was obtained with a yield up to 98% (Table 1, entry 10).
On the other hand, when COF-DM was used as the catalyst,
the reaction yield was less than 1% (Table 1, entry 11),
implying that the copper species was the catalytically active site
to promote AHA coupling reaction. While the amorphous
Cu(II)@polymer-DM was used as a catalyst, the product yield
was up to 92% at the first catalytic cycle (Table 1, entry 12),
but it reduced to 16% at the second catalytic cycle (Table 1,
entry 12), suggesting that the Cu-loaded crystalline COF has
higher catalytic activity and much better reusability.
Table 1. Model AHA Coupling Reaction Catalyzed by
a
Cu(II)@COF-DM
b
entry
solvent
base
DBU
T (°C)/t (h)
yield (%)
1
2
3
4
5
6
7
8
9
CH3CN
CH3CN
H2O
THF
DMF
DMSO
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
60/12
80/12
80/24
80/12
80/12
80/12
80/14
80/14
80/14
80/12
80/12
80/12
53
99
73
21
79
32
99
98
89
98
<1
DBU
DBU
DBU
DBU
DBU
K2CO3
Na2CO3
TEA
c
10
11
DBU
DBU
DBU
d
e
f
12
92, 16
a
Reaction conditions: alkyne (0.3 mmol), amine (0.5 mmol), CH2Cl2
The heterogeneous nature of Cu(II)@COF-DM, as a COF-
based solid catalyst, was also examined (Supporting
Information). The leaching test indicated that no further
reaction occurred in the absence of Cu(II)@COF-DM after
triggering of the AHA coupling reaction at 4 h. Of note, Cu(II)
@COF-DM could be readily regenerated by centrifugation and
reused in the next catalytic cycle directly under the same
reaction conditions. As shown in Figure 4a, 90% yield was still
obtained after five catalytic cycles. The structure and
morphology of Cu(II)@COF-DM were almost intact even
(0.5 mmol), base (0.6 mmol), Cu(II)@COF-DM (5 mg, 1.5 mol %
b
Cu equiv), solvent (2.0 mL) in air. Yields are determined by GC.
c
d
CuCl2 as a catalyst (1.5 mol % Cu equiv). COF-DM as a catalyst (5
e
mg). Amorphous Cu(II)@polymer-DM as a catalyst (5 mg, 1.5 mol
% Cu equiv). Amorphous Cu(II)@polymer-DM as a catalyst in the
f
second use.
tested for the model AHA coupling reaction. When 1,8-
diazabicyclo[5.4.0]undec-7-ene (DBU) was employed, the
AHA coupling yield enhanced along with the reaction
Figure 4. (a) Catalytic cycle. (b) PXRD patterns of COF-DM and Cu(II)@COF-DM after five catalytic runs. (c) SEM image and SEM-EDX
spectrum of Cu(II)@COF-DM after five catalytic runs.
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a
Table 2. Scope of the Cu(II)@COF-DM-Catalyzed AHA Coupling Reaction
a
Reaction conditions: Alkyne (0.3 mmol), amine (0.5 mmol), CH2Cl2 (0.5 mmol), DBU (0.6 mmol), Cu(II)@COF-DM (5 mg, 1.5 mol % Cu
b
c
equiv), CH3CN (2.0 mL), 80 °C, 12 h, in air. Determined by GC. TOF = conversion (mmol of substrate/mmol of cat., h).
after five catalytic cycles, which was strongly evidenced by its
PXRD (Figure 4b) and SEM (Figure 4c) measurements. The
XPS spectrum showed basically no valence change after five
catalytic cycles (Supporting Information). In addition, ICP
indicated the loaded amount of Cu species was ca. 12.3 wt %,
suggesting only a 5% Cu loss after five catalytic cycles
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(Supporting Information). So, we can conclude that the COF-
DM herein is an ideal carrier to load Cu(II) species for
heterogeneous catalysis. The catalytic performance of Cu(II)@
COF-DM herein is laudable when it compared with some of
recently reported homogeneous catalysts and heterogeneous
catalysts for AHA coupling reaction (Supporting Information).
The mechanism of Cu(II)@COF-DM-catalyzed AHA cou-
pling was supposed based on the reported gold,3 cooper,6 and
iron19 catalysts (Supporting Information).
Scope of AHA Coupling Catalyzed by Cu(II)@COF-
DM. After that, we explored the scope of the Cu(II)@COF-
DM-promoted AHA coupling with various substituted alkynes,
dihaloalkane, and amines (Table 2, entries 1−12). As expected,
Cu(II)@COF-DM exhibited an excellent catalytic activity for
the various substituted phenylacetylene with diethyl amine and
dihaloalkane (Table 2, entries 1−7, 96−99%) except 3-OH
substituted phenylacetylene (Table 2, entry 8, 68%) and 4-CN
substituted phenylacetylene (Table 2, entry 9, 59%). Regarding
the catalytic behavior of Cu(II)@COF-DM for phenyl-
acetylene and dihaloalkane with various amines, it showed
very different catalytic activity and achieved the AHA coupling
yields ranging from 11% to 92% (Table 2, entries 10−12).
Besides, the Cu(II)@COF-DM-catalyzed AHA coupling
reaction herein could be enlarged to a gram-scale level. For
example, compound a was obtained in 95% yield (1.8 g) under
the given reaction conditions (Supporting Information).
Yu-Bin Dong − College of Chemistry, Chemical Engineering
and Materials Science, Collaborative Innovation Centre of
Functionalized Probes for Chemical Imaging in Universities of
Shandong, Key Laboratory of Molecular and Nano Probes,
Ministry of Education, Shandong Normal University, Jinan
250014, People’s Republic of China; orcid.org/0000-
0002-9698-8863; Email: yubindong@sdnu.edu.cn
Authors
Xuan Kan − College of Chemistry, Chemical Engineering and
Materials Science, Collaborative Innovation Centre of
Functionalized Probes for Chemical Imaging in Universities of
Shandong, Key Laboratory of Molecular and Nano Probes,
Ministry of Education, Shandong Normal University, Jinan
250014, People’s Republic of China
Jing-Lan Kan − College of Chemistry, Chemical Engineering
and Materials Science, Collaborative Innovation Centre of
Functionalized Probes for Chemical Imaging in Universities
of Shandong, Key Laboratory of Molecular and Nano
Probes, Ministry of Education, Shandong Normal University,
Jinan 250014, People’s Republic of China
Jin-Yan Shang − College of Chemistry, Chemical Engineering
and Materials Science, Collaborative Innovation Centre of
Functionalized Probes for Chemical Imaging in Universities
of Shandong, Key Laboratory of Molecular and Nano
Probes, Ministry of Education, Shandong Normal University,
Jinan 250014, People’s Republic of China
Hua Qiao − College of Chemistry, Chemical Engineering and
Materials Science, Collaborative Innovation Centre of
Functionalized Probes for Chemical Imaging in Universities
of Shandong, Key Laboratory of Molecular and Nano
Probes, Ministry of Education, Shandong Normal University,
Jinan 250014, People’s Republic of China
CONCLUSIONS
■
In summary, we reported a gram-scale-synthesized Cu(II)@
COF complex via a solid-state coordination method under
mild conditions. The obtained Cu(II)@COF-DM can be an
ideal heterogeneous catalyst to catalyze the AHA coupling
reaction, even at a gram-scale level. We expect that the solid-
state coordination synthetic approach herein is general and,
moreover, significantly broadens the scope of COF-supported
metal-heterogeneous catalysts.
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.inorgchem.0c03783
Author Contributions
†These authors contributed equally.
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.inorgchem.0c03783.
■
sı
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
Additional characterization of COF-DM, Cu(II)@COF-
DM, A, and B; AHA coupling products characterization
(PDF)
■
We are grateful for financial support from NSFC (Grants
21971153, 21671122 and 21802090), the Major Basic
Research Projects of Shandong Natural Science Foundation
(No. ZR2020ZD32), Shandong Provincial Natural Science
Foundation (No. ZR2018BB006), a Project of the Shandong
Province Higher Educational Science and Technology
Program (J18KA066), and the Taishan Scholars Climbing
Program of Shandong Province.
Accession Codes
CCDC 2048265 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
via www.ccdc.cam.ac.uk/data_request/cif, or by emailing
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REFERENCES
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AUTHOR INFORMATION
Corresponding Authors
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■
Jian-Cheng Wang − College of Chemistry, Chemical
Engineering and Materials Science, Collaborative Innovation
Centre of Functionalized Probes for Chemical Imaging in
Universities of Shandong, Key Laboratory of Molecular and
Nano Probes, Ministry of Education, Shandong Normal
University, Jinan 250014, People’s Republic of China;
Email: wangjiancheng1003@163.com
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Inorganic Chemistry
pubs.acs.org/IC
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