Valorization of Click-Based Microporous Organic Polymer: Generation of Mesoionic Carbene-Rh Species for the Stereoselective Synthesis of Poly(arylacetylene)s

Article abstract of DOI:10.1021/jacs.0c13286

This work reports the functionalization of azide-Alkyne click-based microporous organic polymer (CMOP). The generation of triazolium salts and successive deprotonation induced mesoionic carbene species in hollow CMOP (H-CMOP). Rh(I) species could be coord

Full text of DOI:10.1021/jacs.0c13286

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Valorization of Click-Based Microporous Organic Polymer:
Generation of Mesoionic Carbene−Rh Species for the
Stereoselective Synthesis of Poly(arylacetylene)s
Kyoungil Cho, Hee-Seong Yang, In-Hwan Lee, Sang Moon Lee, Hae Jin Kim, and Seung Uk Son*
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ABSTRACT: This work reports the functionalization of azide−alkyne click-based microporous organic polymer (CMOP). The
generation of triazolium salts and successive deprotonation induced mesoionic carbene species in hollow CMOP (H-CMOP). Rh(I)
species could be coordinated to the mesoionic carbene species to form H-CMOP-Rh, showing excellent heterogeneous catalytic
performance in the stereoselective polymerization of arylacetylenes.
Figure 1 shows a synthetic scheme of H-CMOP bearing
mesoionic carbene−Rh species (H-CMOP-Rh). First, Cu2O
nanocubes were prepared by a literature method.21 Then,
CMOP was formed on the surface of templating Cu2O
nanocubes. The acid etching of Cu2O@CMOP resulted in H-
CMOP. The reaction with methyl iodide generated H-CMOP
with triazoliums (H-CMOP-Me). Finally, abstraction of proton
from triazoliums and successive reaction with [Rh(COD)Cl]2
resulted in H-CMOP-Rh.
Scanning and transmission electron microscopy (SEM and
TEM) showed the hollow morphologies of H-CMOP with a
diameter and a shell thickness of 110 and 20 nm, respectively
(Figures 2a and 2d). The H-CMOP-Me and H-CMOP-Rh
maintained the original hollow morphologies (Figures 2b,c and
2e,f).
The porosity and surface area of H-CMOPs were
characterized by N2 sorption studies (Figure 3a,b and Table
S1). While the surface area of H-CMOP was measured to be
422 m2/g, that of H-CMOP-Me was reduced to 167 m2/g due
to the incorporation of additional chemical component. After
the coordination of Rh, the surface area of H-CMOP-Rh
significantly increased to 310 m2/g, which is attributable to the
enhanced rigidity of network structure (Figure 3c). All
CMOPs in this work were amorphous (Figure S2). It has
been reported35,36 that metal coordination to the relatively
flexible network structure of MOPs enhanced the porosity. In
addition, the further networking by Rh catalysis during PSM
cannot be ruled out.37−40 The pore size distribution analysis
indicated the microporosity of H-CMOP, H-CMOP-Me, and
H-CMOP-Rh with pore volumes of 0.58, 0.28, and 0.55 cm3/g,
respectively (Figure 3b). Interestingly, the significant macro/
he azide−alkyne Huisgen [3 + 2] cycloaddition is a
1
Tversatile reaction for organic synthesis.
Because the
reaction was referred to as an example of click chemistry by
Sharpless in 2001, its application fields have expanded to the
engineering of functional materials.2−4
Recently, microporous organic polymer (MOP) has been
prepared by various coupling reactions of organic building
blocks.5−13 The azide−alkyne click reaction has also been
applied to the synthesis of MOP.14−20 Huang et al. showed
that Cu2O can be used as a catalyst for the azide−alkyne click
reaction.21 Our research group has shown that hollow MOP
could be synthesized through Cu2O-based template syn-
thesis.19,20 The resultant MOPs are rich in 1,2,3-triazoles. A
delicate postsynthetic modification (PSM) approach can be
further applied to generate more advanced chemical species in
the click-based MOP (CMOP).
1,2,3-Triazole compounds can be converted to triazolium
species through a reaction with electrophiles.22,23 The
triazolium rings are used as precursors to generate mesoionic
carbenes through the abstraction of protons.22,23 Recently, the
mesoionic carbenes have been utilized in the synthesis of
metal−carbene complexes.24−27 For example, a reaction of the
mesoionic carbene derived from 3-methyl-1,4-diphenyl-1,2,3-
triazolium iodide with [Rh(COD)Cl]2, (COD: 1,5-cyclo-
octadiene) generates the Model-Rh complex (Figure S1).
In 2011, we reported the synthesis of MOP bearing
imidazolium salts through a predesigned building block
approach.28 Imidazolium moieties could be utilized for the
generation of N-heterocyclic carbene−metal species in
polymeric materials.29−34 However, in spite of the usefulness
of azide−alkyne click reactions, as far as we are aware, the
generation of mesoionic carbene−metal species in CMOP has
not been reported. In this work, we report the generation of
mesoionic abnormal carbenes in hollow CMOP (H-CMOP),
successive incorporation of Rh species, and its heterogeneous
catalytic performance in the stereoselective synthesis of
poly(arylacetylene)s.
Received: December 27, 2020
Published: March 9, 2021
https://dx.doi.org/10.1021/jacs.0c13286
J. Am. Chem. Soc. 2021, 143, 4100−4105
© 2021 American Chemical Society
4100

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Figure 1. Synthesis of H-CMOP-Rh and a SEM image of Cu2O
nanocubes.
Figure 3. (a) N2 sorption isotherm curves at 77K, (b) pore size
distribution diagrams, (c) the porosity enhancement of H-CMOP-Rh
through Rh coordination, and (d) 13C NMR spectra of H-CMOP, H-
CMOP-Me, H-CMOP-Rh, and Model-Rh.
peaks of COD in the H-CMOP-Rh were clearly observed at
29, 72, and 93 ppm, matching with those of Model-Rh (Figure
3d and Figure S4). In the infrared absorption (IR) spectra of
H-CMOP, H-CMOP-Me, and H-CMOP-Rh, aromatic CC
vibration peaks were observed at 1483, 1522, and 1608 cm−1,
in addition to aromatic C−H peaks at 832 and 989−1034
cm−1. The H-CMOP-Rh showed additional aliphatic C−H
vibration peaks of the COD at 2822, 2879, and 2921 cm−1
(Figure S5).
The mesoionic carbene Rh species in the H-CMOP-Rh were
further characterized by X-ray photoelectron spectroscopy
(XPS) (Figures S4 and S6). The major N 1s orbital peak of the
triazole rings of H-CMOP appeared at 399.7 eV with a minor
peak at 401.3 eV. In comparison, the major N 1s orbital peak
of the triazolium rings of H-CMOP-Me was observed at 401.4
eV with an additional peak at 399.9 eV. In the case of H-
CMOP-Rh, the major N 1s orbital peak was shifted to 401.7
eV, matching with that (401.7 eV) of Model-Rh. The 3d
orbital peaks of Rh in H-CMOP-Rh were observed at 312.6
and 307.9 eV, matching with those of the Model-Rh at 312.4
Figure 2. SEM and TEM images of (a, d) H-CMOP, (b, e) H-
CMOP-Me, and (c, f) H-CMOP-Rh.
mesoporosity was also observed over all H-CMOPs, which is
attributable to the inner hollow cube space (Figure 3a and
Figure S3).
The chemical structures of H-CMOPs were characterized by
solid-state 13C nuclear magnetic resonance (NMR) spectros-
copy (Figure 3d). While the 13C peak of benzylic carbon in H-
CMOP appeared at 64 ppm, aromatic 13C peaks were observed
at 110−140 and 147 ppm. The alkyne 13C NMR peaks were
not observed at 70−90 ppm, indicating that the azide−alkyne
reaction was successfully conducted. In comparison, the
methyl 13C peak of H-CMOP-Me was clearly observed at 41
ppm. In addition, the N-phenyl 13C peak of 1,2,3-triazoles
shifted from 135 ppm (H-CMOP) to 144 ppm (H-CMOP-
Me) due to the formation of cationic triazoliums. The 13C
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and 307.7 eV. While the 3d orbital peaks of iodides in H-
CMOP-Me were observed at 631.8 and 620.5 eV, those of the
iodo ligands in H-CMOP-Rh shifted to 630.4 and 618.5 eV. In
comparison, the 3d orbital peaks of iodo ligands in the Model-
Rh were observed at 630.1 and 618.8 eV. Energy-dispersive X-
ray spectroscopy-based elemental mapping confirmed the
homogeneous distribution of Rh species in H-CMOP-Rh
(Figure S6).
The amounts of triazoles, triazoliums, and mesoionic
carbenes in H-CMOP, H-CMOP-Me, and H-CMOP-Rh
were analyzed to be 3.76 mmol/g (15.8 wt % N), 3.16
mmol/g (13.3 wt % N), and 2.2 mmol/g (9.3 wt % N),
respectively. The Cu residues in H-CMOP were measured to
be 0.28 wt % by inductively coupled plasma (ICP) analysis.
The content of Rh in H-CMOP-Rh was measured to be 8.63
wt % (0.849 mmol/g), corresponding to the 38% PSM of
triazoliums. Thermogravimetric analysis showed that the H-
CMOP-Rh is stable up to 228 °C (Figure S7).
Considering the mesoionic carbene−Rh species and
chemical stability of H-CMOP-Rh, we studied its heteroge-
neous catalytic activities in the polymerization of arylacetylenes
(Table 1). Recently, poly(phenylacetylene) (PPA) has
attracted the significant attention of scientists.37−42 While the
PPA has been prepared by various metal catalysts, Rh
complexes have shown high synthetic efficiencies.43−46
However, Rh-based heterogeneous catalytic systems are
relatively rare.47−51
First, we scanned the amount of catalyst. As the amount of
H-CMOP-Rh decreased from 1.2 mol % Rh to 0.60, 0.30, 0.12,
and 0.060 mol % Rh, the isolated yields of PPAs decreased
from 99% to 96, 76, 64, and 24% with the changes of molecular
weights (Mn) from 32100 to 40900, 41300, 42800, and 39300,
respectively (entries 1−5 in Table 1). The stereoselectivities of
cis-transoid PPA were analyzed to be 98−99%.52 We selected
the 0.60 mol % H-CMOP-Rh as an optimal catalyst amount. In
a control test, 0.60 mol % Model-Rh showed a 10% isolated
yield of PPA. The enhanced polymerization of phenylacetylene
in nanospaces53,54 and the extrusion polymerization by
mesoporous catalysts have been reported.55
The H-CMOP-Rh (0.60 mol % Rh) could be recycled.
When the recovered H-CMOP-Rh was used, the PPAs were
obtained with the isolated yields of 92, 96, 94, and 91% and the
Mn values of 42200, 48400, 50500, and 54100 at the 2nd, 3rd,
4th, and 5th runs, respectively (entries 6−9 in Table 1). After
the removal of H-CMOP-Rh through filtration, the Rh was not
detected in the reaction mixture and the reaction did not
proceed, indicating the heterogeneous nature of the catalytic
reactions (Figure S8). SEM, TEM, XPS, IR, and 13C NMR
studies of the H-CMOP-Rh recovered after the fifth reaction
showed that the original hollow morphologies and mesoionic
carbene Rh species were retained (Figure S9).
Next, we studied the polymerization of arylacetylenes
bearing substituents. When we used (4-bromophenyl)-
acetylene, insoluble polymer was obtained (entry 10 in Table
1, Figure S10). When we used a 1:1 mixture of (4-
bromophenyl)acetylene and phenylacetylene, soluble polymer
(Mn of 35200) was obtained with an isolated yield of 70%
(entry 11 in Table 1, Figure S11). In comparison, when we
used the (4-methoxyphenyl)acetylene, polymer was obtained
with a yield of 3% (Mn of 5700) (entry 12 in Table 1). We
suggest that the different activities of H-CMOP-Rh toward (4-
bromophenyl)acetylene and (4-methoxyphenyl)acetylene re-
sult from an initiation step of polymerization. Recently,
Morokuma et al. reported mechanistic studies of the Rh-
catalyzed polymerization of phenylacetylene.56 Among three
mechanistic candidatesRh(I) insertion, Rh(III) insertion,
and Rh−carbene metathesis mechanismsthe Rh(I) insertion
was suggested as the most favorable pathway. In this regard,
the catalytic mechanism of H-CMOP-Rh is suggested in Figure
S12. To initiate the polymerization, the anionic arylethynyl
ligand should be incorporated into Rh through the
deprotonation of arylacetylene. We speculate that the initiation
of polymerization by (4-methoxyphenyl)acetylene would be
relatively slow due to its relatively less acidic feature of the
terminal proton.
Table 1. Synthesis of Poly(Arylacetylene)s by H-CMOP-
a
Rh
b
c
cat.
(mol %)
yield (S )
entry
Ar
(%)
Mn
PDI
1
2
3
4
5
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
1.2
99 (99)
96 (98)
76 (98)
64 (99)
24 (99)
92 (99)
96 (96)
94 (96)
91 (99)
32100
40900
41300
42800
39300
42200
48400
50500
54100
−
35200
5700
6000
2.59
2.47
2.51
2.76
2.84
2.70
2.53
2.34
2.33
0.60
0.30
0.12
0.060
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
0.60
d
6
e
7
f
8
g
9
Ph
4-BrPh
h
h
h
10
11
12
13
14
89 (− )
−
i
When we used the 5:1 and 1:1 mixtures of (4-methoxy-
phenyl)acetylene and phenylacetylene as monomer systems,
the isolated yields of polymer increased to 21% (Mn of 6000)
and 85% (Mn of 21100), respectively (entries 13 and 14 in
Table 1, Figure S11).
4-BrPh:Ph (1:1)
4-MeOPh
4-MeOPh:Ph (5:1)
4-MeOPh:Ph (1:1)
Ph
70 (96)
3.04
2.01
1.92
2.24
2.37
3 (96)
j
21 (99)
k
85 (96)
21100
21000
l
15
37 (86)
While the features of PPA have been extensively
investigated, the copolymers bearing substituted arylacetylenes
have been relatively less explored.57−59 In this regard, the
optical properties of PPA, copolymer of (4-bromophenyl)-
acetylene and phenylacetylene (PBrPAPA), and copolymer of
(4-methoxyphenyl)acetylene and phenylacetylene (PMeOPA-
PA) were studied (Figure S11). While the PPA and the
PMeOPAPA showed two absorption bands at 328 and 388
nm, the absorptions of the PBrPAPA at 320−400 nm were
significantly reduced. Interestingly, the emissions of PBrPAPA
a
Reaction conditions: arylacetylene (2.28 mmol), H-CMOP-Rh (16
b
c
mg for 0.60 mol % Rh), rt, THF, 18 h. Isolated yield. Contents of
cis-transoid polymers.52 The catalyst recovered from entry 2 was
d
e
f
used. The catalyst recovered from entry 6 was used. The catalyst
recovered from entry 7 was used. The catalyst recovered from entry 8
was used. Insoluble polymers were obtained. The 1:1.18 ratio of 4-
bromophenyl and phenyl in copolymer. The 1:0.21 ratio of 4-
methoxyphenyl and phenyl in copolymer. The 1:1.39 ratio of 4-
methoxyphenyl and phenyl in copolymer. Nonhollow CMOP-Rh (34
mg for 0.60 mol % Rh) was used.
g
h
i
j
k
l
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and PMeOPAPA at 494 and 510 nm, respectively, were
significantly enhanced by 8.8 and 6.6 times compared with that
of PPA at 511 nm. The polymer chains of PPA are known to
form a helical structure.37−46,57−59 We speculate that the
existence of substituents in phenyl rings hinders the π−π
stacking-induced emission quenching between polymer chains,
resulting in the enhanced emission.
Finally, when we conducted control studies for the
nontemplate synthesis of CMOP, conventional nonhollow
spherical materials (denoted as CMOP-Rh) were obtained
with diameters of 0.2−0.7 μm, a Rh content of 4.13 wt %, and
a surface area of 147 m2/g (Figure S13). In polymerization
studies, the CMOP-Rh (0.60 mol % Rh) produced PPA (Mn:
21000) with an isolated yield of 37% and a cis-transoid content
of 86% (entry 15 in Table 1), indicating that the hollow
structure and the thin shell of H-CMOP and H-CMOP-Rh are
beneficial in the postsynthetic functionalization and catalytic
performance due to the reduced diffusion pathways of reagents
into materials.60
ACKNOWLEDGMENTS
■
This work was supported by “Carbon to X Project” (No.
2020M3H7A1098283) and Grant 2020R1A2C2004310
through the National Research Foundation (NRF) funded
by the Ministry of Science and ICT, Republic of Korea.
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AUTHOR INFORMATION
■
Corresponding Author
Seung Uk Son − Department of Chemistry, Sungkyunkwan
University, Suwon 16419, Korea; orcid.org/0000-0002-
4779-9302; Email: sson@skku.edu
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Kyoungil Cho − Department of Chemistry, Sungkyunkwan
University, Suwon 16419, Korea; orcid.org/0000-0003-
2506-4951
Hee-Seong Yang − Department of Energy System Research,
Ajou University, Suwon 16499, Korea
In-Hwan Lee − Department of Chemistry, Ajou University,
Suwon 16499, Korea; orcid.org/0000-0002-4848-939X
Sang Moon Lee − Korea Basic Science Institute, Daejeon
34133, Korea
Hae Jin Kim − Korea Basic Science Institute, Daejeon 34133,
Korea; orcid.org/0000-0002-1960-0650
Complete contact information is available at:
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Notes
The authors declare no competing financial interest.
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