The Catalytic Properties of a Copper-Based Nanoscale Coordination Polymer Fabricated by a Solvent-Etching Top-Down Route

Article abstract of DOI:10.1002/ejic.201700597

Manipulating particle size is a powerful means of creating unprecedented applications in both inorganic and organic materials. Coordination polymers, which are emerging as a type of organic–inorganic hybrid materials, have attracted thriving interest in a variety of applications, but nanoscale coordination polymers have scarcely been touched. In this work, the pure-phase {Cu₆[1,4-bis(imidazol-1-yl)butane]₃I₆}_∞ coordination polymer with different sizes and morphologies was synthesized for the first time through a facile top-down route assisted by solvent etching. The size and morphology could be adjusted simply by varying the participating etching solvents. Our mechanistic investigations suggest that the bulk coordination polymer as a precursor in the etching solvents may experience a process of dispersion, dissolution, and recrystallization to generate the nanoscale counterpart. High catalytic activity of the nanoscale coordination polymer was observed in the N-arylation of imidazole aryl halides, and this was attributed to a high surface area and a low coordination number of unsaturated coordination sites. This simple and rapid preparation, requiring neither specialized equipment nor harsh conditions, suggests a wealth of potential for reducing the size of coordination polymers to comply with various practical applications.

Full text of DOI:10.1002/ejic.201700597

A Journal of
Accepted Article
Title: The Catalytic Properties of Copper-based Nanoscale
Coordination Polymer Fabricated by Solvent-Etching Top-Down
Route
Authors: Qiang Ju, Xiaowei Cao, Wei Huang, and Zhenlan Fang
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To be cited as: Eur. J. Inorg. Chem. 10.1002/ejic.201700597
Link to VoR: http://dx.doi.org/10.1002/ejic.201700597

10.1002/ejic.201700597
European Journal of Inorganic Chemistry
Communication
The Catalytic Properties of Copper-based Nanoscale
Coordination Polymer Fabricated by Solvent-Etching Top-Down
Route
Xiaowei Cao, Zhenlan Fang, Wei Huang and Qiang Ju*
Abstract: Manipulating particle size is a powerful mean of creating
unprecedented applications both in inorganic and organic materials.
Coordination polymer, emerging as one sort of organic-inorganic
hybrid materials, has attracted thriving interests in a variety of
applications, but nanoscale coordination polymer has scarcely been
touched. In this work, pure-phase coordination polymer [Cu6(1,4-
bis(imidazol-1-yl)butane)3I6]∞ with different sizes as well as
morphologies was synthesized through facile top-down route assisted
with solvent-etching for the first time. The size and morphology could
be adjusted just via varying the participated etching solvents. Our
mechanistic investigation suggest that the bulk coordination polymer
as precursor in the etching solvents may experience a process of
dispersion, dissolvation, recrystalization to generate the nanoscale
counterpart. Higher catalytic activity of nanoscale coordination
polymer was observed in N-arylation of imidazole aryl halide, and was
attributed to higher surface area and lower coordination number of
unsaturated coordination sites (CUSs). This simple and rapid
preparation, requiring neither specialized equipment nor harsh
conditions, suggests a wealth of potential for reducing down the size
of coordination polymer to comply with various practical applications.
synthesized with the assistance of surfactant or/and interface,
while the synthesis strategy would inevitably demand CPs
endowing with fast nucleation rate to make it possible to control
the formation of nanoparticles.[5] For the CPs with low nucleation
rate, it is conducive/necessary to conduct the reaction under high-
temperature, high-pressure, time-resuming, and more reactants
than obtained products, in order to yield pure CPs with high
crystallinity. However, all of these conditions would play
detrimental roles in controlling morphology, size, and phase purity
of NCPs. Thus, it is urgent to propose one route for generating
pure, and monodispersed NCPs with adjustable size.
Bottom-up method, which can manipulate the assembly of
atoms and/or clusters, may be the most common strategy to
fabricate nanoparticles with tunable size, monodispersion, and
high-crystallinity.[6] Top-down route is performed via using bulk
materials as precursor to generate nanoscale counterpart through
physical and/or chemical effect shrinking bulk material into
nanoscale counterpart, which has also been extensively
investigated in the synthesis of nanoparticles.[7] In the last
decades, shrinking bulk materials into nanometer dimension
without the re-assembly of atoms has been found considerable
utilization for the preparation of two-dimension nanomaterial
(such as graphene nanosheet)[8] and ionic liquid solid/frozen
nanoparticles.[9] However, this way often face the challenges in
term of uniformity of obtained nanoparticles. As other type of top-
down route, the way of in situ dissolve-recrystallize-formation of
nanoparticles in appropriate solvents, is anticipated to efficiently
manipulate the size of obtained nanoparticles and promise the
phase purity of obtained nanoparticles. But to the best of our
knowledge, this way has not drawn attention on the controllable
synthesis of nanomaterials, not to mention the synthesis of NCPs.
In this work, we have utilized a facile solvent-etching top-down
route to synthesize pure, uniform and monodispersed NCPs. The
size and morphology of obtained NCPs could be modulated by
varying applied etching solvents. The generated NCPs could be
used as efficient catalysis for the N-arylation of imidazole aryl
halide.
Introduction
The last decade has witnessed rapid developments and
innovations in both coordination polymer/metal organic
frameworks (CPs/MOFs) and nanotechnology.[1] CPs/MOFs are
materials consisting of metal ions or clusters coordinated to
organic molecules, and have been explored in diverse technical
applications, such as heterogeneous catalysis, optical materials,
and gas storage.[2] Nanoparticles, owing to their small size as well
as large surface-to-volume ratio, have also been extensively
employed in catalysis, biodetection, lighting, and drug delivery.[3]
Thus, nanoscale coordination polymer (NCPs), which combine
the merits of CPs and nanoparticles, have become one of the
hottest topics as their charming properties could address the
issues confronted in fundamental researches and technical
applications. For example, NCPs have been applied as contrast
agents to perform multimodal bioimaging, as vehicle for drug
delivery and release, as catalyst in chiral catalysis, and as
platform for lighting.[4] Most of the reported NCPs were
Results and Discussion
Structure Description. Bulk CPs [Cu6(L1)3I6]∞ (BCPs), which
contains two active Cu1+ and four inactive Cu1+ ions, were
prepared via the self-assembly of ligand L1 [1,4-bis(imidazol-1-
yl)butane] with CuI under hydrothermal conditions for 24 hours,
taken as an example to illustrate the synthesis of nanoscale
counterpart (Figure 1).[10] Single-crystal X-ray diffraction analysis
revealed that BCPs crystallizes in the monoclinic C2/c space group
and has a corrugated layer configuration (Figure S1). The detailed
crystal data as well as the bond length and angles were shown in
X.W. Cao, Z.L. Fang, W. Huang, Q. Ju
Key Laboratory of Flexible Electronics (KLOFE) & Institute of Advanced
Materials (IAM), Jiangsu National Synergetic Innovation Center for
Advanced Materials (SICAM), Nanjing Tech University (NanjingTech), 30
South Puzhu Road, Nanjing 211816, P.R. China.
E-mail: iamqju@njtech.edu.cn
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10.1002/ejic.201700597
European Journal of Inorganic Chemistry
Communication
consisting of metal-organic macrocycles. It should be mentioned that
the layers are further interpenetrated to form 1D large channels with
the effective dimensions being 11.26 × 8.62 Å2 (Figure S2-3).
Synthesis of NCPs. Two categories of methods, bottom-up
and top-down, were adopted to synthesize NCPs, respectively.
Firstly, we attempted to synthesize NCPs via common-used
bottom-up method arranging atoms and molecules in
nanostructures, where CuI and L1 were used as starting materials
under hydrothermal condition. The reaction time was reduced to
4 hours, with the addition of polyvinylpyrrolidone (PVP) serving as
surfactant to manipulate the nucleation and growth of NCPs. From
the powder X-ray diffraction (XRD) results (Figure 2), the obtained
material demonstrated diffraction peaks of BCPs, but it was
always accompanied with remaining CuI, which cannot be
completely run out even under the condition that the ligand was
ten times more than that of stoichiometric ratio. Besides, the size
of obtained particles was larger than 100 μm, failing to reduce the
size down to nanoscale. Therefore, bottom-up method is not
suitable for synthesizing this NCPs, indicating that an effective
synthesis strategy for fabricating crystalline NCPs is urgent
desired.
Figure 1. Perspective view of coordination environments of Cu and L1 (All
hydrogen atoms were omitted for clarity).
Table S1-2. As shown in Figure 1, BCPs possesses functional
tetranuclear Cu4I4 and dinuclear Cu2I2 clusters simultaneously. Cu4I4
unit displays a centrosymmetric cubane-like arrangement with Cu(I)
and iodide occupying alternate corners of the cube, in which Cu(I)
centers are in a distorted tetrahedral geometry and are coordinated
by three iodides and one nitrogen atom from bimb (Cu1 and Cu2 in
Figure 1). The Cu-Cu separations are 2.72-2.88 Å, which are
comparable with those in the reported cubane-like Cu4I4 analogues.
Cu2I2 unit shows a rhomboidal arrangement, in which Cu(I) centers
are in a distorted triangular geometry and are coordinated by two
iodides and one nitrogen atom from bimb (Cu3 in Figure 1). The Cu-
Cu separation in Cu2I2 unit is 2.47 Å, which is much shorter than those
in the Cu4I4 unit. With respect to Cu1 and Cu2 (four-coordinated), Cu3
(three-coordinated) can serve as coordination unsaturated site (CUS).
The prominent copper-iodine aggregates acting as inorganic building
blocks have attracted considerable attentions due to their fascinating
and efficient catalysis originating from CUS, such as the formation of
C-N bond[11] and the azide–alkyne cycloaddition (CuAAC).[12] Thus,
the obtained BCPs at smaller size may be endowed with good
catalysis. Bimb shows anti-anti-anti and anti-gauche-anti
conformations with the twisting angle of two imidazolyl rings in bimb
being 86.5o and 87.1o, respectively (Figure S1). The two type of bimb
alternatively link Cu4I4 and Cu2I2 units into a corrugated layer
For the top-down route, BCPs utilized as precursor were
processed under solvothermal condition. The bulk crystals were
put into etching solvents in a glass vessel, then heated for 2 hours,
and the obtained resultant microemulsion was finally poured into
solvent with floating ice under ultrasound before centrifugation. In
stark contrast to the bottom-up method, no trace of CuI was found
out in the XRD and the pattern was in accordance with the file
simulated from single crystals data, confirming the purity of
obtained NCPs (Figure 2). Moreover, different sizes and diverse
morphologies could also be generated when different etching
solvents participated (Figure 3). The obtained NCPs were
Figure 3. SEM images of NCPs obtained by top-down route via the
application of different etching solvents: a) ethanol, b) n-butyl acetate, and
c) n-butyl chloride, showing that the appropriate selection of etching
solvents play an important role in the synthesis of NCPs.
Figure 2. XRD patterns of cubic NCPs and spherical NCPs obtained by
top-down route, NCPs synthesized by bottom-up method, BCPs, CuI and
the simulated data of BCPs obtained from single-crystals analysis
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10.1002/ejic.201700597
European Journal of Inorganic Chemistry
Communication
Table 1: Screening of Reaction Conditions in N-arylation of
imidazole and 4-iodobenzene.
Entry Catalysta
Base
Solvent Yield(%)b
1c
BCPs
BCPs
BCPs
BCPs
BCPs
CuI
K2CO3
DMF
DMF
DMF
41
50
2
KOH
NEt3
3
Trace
28
4d
5
Cs2CO3 H2O
Cs2CO3 THF
Cs2CO3 DMF
Cs2CO3 DMF
28
6
68
7e
CuI and
bimb
78
8
9
BCPs
Cs2CO3 DMF
Cs2CO3 DMF
95
Cubic
NCPs
100
Figure 4. SEM images of top-down synthesis NCPs at different stages
for a) ethanol, and c) n-butyl acetate, respectively. The proposed
fabrication mechanism for b) cubic NCPs and d) spherical NCPs,
respectively.
10
Spherical
NCPs
Cs2CO3 DMF
100
a Reaction conditions: iodobenzene (0.5 mmol), imidazole (0.75
mmol), base (0.1 mmol), Cu source (0.05 mmol), solvent (2.0
mL), 100 oC, 24 h, under N2; b GC yields; cAverage of two runs;
d 0.5 mmol tetrabutyl ammonium bromide (TBAB) was added
as additive; e bimb as a ligand with the molar ratio of CuI:bimb
is 2:1.
monodispersed cubic particles with the size to be ~145 nm, when
ethanol was selected as solvent (cubic NCPs, Figure 3a). Smaller
(~91 nm) and spherical particles were observed in SEM image
when n-butyl acetate was implemented as solvent (spherical
NCPs, Figure 3b). The size distribution both of cubic and spherical
nanocrystals were demonstrated in Figure S4. Interestingly, much
larger particles with quasi-rod shape (4~10 μm in length and ~2
μm in width) were yielded when n-butyl chloride was employed
(Figure 3c). These results indicate that the applied solvents
played an important role in adjusting size and morphology of
NCPs obtained by top-down route. Besides, both spherical NCPs
and cubic NCPs could be dispersed in aqueous solution, which
were confirmed by Tyndall effect in their corresponding colloidal
suspensions (Figure S5), promising their potential application in
biodetection.
attached on the rod-like BCPs in the intermediate and spherical
particles were presented in the final obtained nanoparticles
(Figure 4c). Both of the morphologies of these intermediates are
in accordance with the final obtained nanoparticles. Based on
these results, the plausible formation mechanism of NCPs is
proposed. Firstly, the bulk crystal could be partially dissolved to
generate supersaturated micro-emulsion in appropriate solvents
under appropriate temperature and pressure, accompanied with
in-situ generated small nanoparticles. Secondly, more uniform
NCPs were yielded when this dissolve-recrystallization reached
equilibrium. The in situ generation and formation of NCPs should
be the key point for yielding pure and uniform NCPs without
impurity. While for the modulation of morphology and size of
yielded nanoparticles, it should be determined by the polarity of
applied etching solvents.
Synthesis Mechanism. To illustrate the growth mechanism of
NCPs via top-down route, the morphologies of particles obtained
at different stages were acquired. The starting bulk crystals were
quasi-rod with a size in the mm range and demonstrated length
to width ratio to be 8~12 (Figure 4), showing larger length-to-width
ratio than that of quasi-rod obtained by n-butyl chloride (Figure
3c). This variation indicated that n-butyl chloride preferred to
crumble BCPs in the length dimension. When the synthesis
procedure of spherical NCPs by ethanol lasted for 1 hour
(intermediate), cubic particles with different sizes could be clearly
observed on the surface of rod-like BCPs (Figure 4a). When the
synthesis time extended to two hours, there were only cubic NCPs
in the yielded products. Similarly, when n-butyl acetate was used
as solvent, there were spherical particles with different sizes
Catalysis. Aforementioned analysis on the structure has
pointed out that the rhomboid geometry centrosymmetric
[(Cu3)2(I3)2] clusters may enable BCPs with catalysis activity.
Taken the small size of NCPs into account, its catalytic activity
and stereoselectivity would be greatly improved, as high surface
area can implement high possibility for substrates to access
catalytically active sites. To this end, the catalysis behavior of
BCPs and NCPs on the N-arylation of imidazole aryl halide has
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10.1002/ejic.201700597
European Journal of Inorganic Chemistry
Communication
Table 2. Scope of N-arylation of imidazole and halide-benzene reactions catalyzed by cubic NCPs
Entry
1
Ar-X
Nucleophile
Producta
Yield(%)b
100(96)
2
3
100(88)
100(92)
4
43
45
4c
5
75
78
5d
6
7
83
55
8
9
100(97)
100(97)
10
100(88)
11
12
100(95)
40
13
77
a Reaction conditions: aryl halide (0.5 mmol), imidazole (0.75 mmol), Cs2CO3 (0.1 mmol), cubic NCPs (0.05 mmol), DMF (2.0
mL), 100 C, 24 h, under N2; b GC yields; c the spherical NCPs was used as catalyst; d the spherical NCPs was used as catalyst .
cIsolated yields are given in parentheses.
been performed. BCPs were chosen as catalyst to firstly optimize
the reaction condition. As shown in Table 1, this cheap, air-stable
BCPs catalyst was active in promoting Ullmann N-arylation by
achieving a high conversion of iodobenzene up to 95%, where
Cs2CO3 was used as a base in N, N-dimethylforamide (DMF).
Importantly, compared with BCPs, the yields of products for cubic
and spherical NCPs have been improved and reach as high as
100%. This should be induced by the relative high surface to
volume ratio, bringing out more accessible coordination
unsaturated sites (CUSs) as well as lower coordination number of
surface CUSs, normally terminated by vacancies.[13]
consistent with the well-established trend in Cu-catalyzed
Ullmann reactions.[14] The yield of arylation of imidazole with 2-,
3- or 4- iodotoluene reduced in turn, which could be ascribed to
the steric effect of the methyl group (entries 4-6). It should be
pointed out that the spherical NCPs show similar catalysis
efficiency when they were used in entries 4-5 in contrast to Cubic
NCPs. Interestingly, except imidazole, other azoles such as
pyrrole (entry 8), pyrazole (entry 9) and triazoles (entry10) could
also couple with 4-iodotoluene to produce the target product in
moderate condition to an excellent yield (~100%). Due to the
steric hindrance, imidazole (83%, entry 6) was proved to be more
reactive than indole (55%, entry 7), much less reactive than
pyrazole, pyrrole and triazole (~100%, entries 8-10). Arylation of
imidazole and aryl bromide containing the electron-withdrawing
groups (-NO2) can be carried out with desirable products in a high
yield (~100%, entry 11). Noticeably, arylation of imidazole can
even take place with aryl bromide bearing electron-donating
group (-COMe) (~40%, entry 12) in an acceptable yield, and with
the heteroaromatic 2-bromopyridine afforded the desirable
Under the above-optimized conditions of N-arylation with
imidazole, the catalysis effect of varying aryl halides was also
investigated on cubic NCPs (Table 2). The aryl iodides bearing
electron-withdrawing groups, such as -NO2, -F and -Br, provided
the desirable products in a quantitative yield (~100%, entry 1, 2
and 3, respectively). However, moderate yields were observed for
aryl iodides with electron-donating groups, such as -Me (43%,
75%, 83%, entry 4, 5, 6, respectively). These results are
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10.1002/ejic.201700597
European Journal of Inorganic Chemistry
Communication
products in a satisfactory yield (77%, entry 13). In order to check
the reusability and stability of the NCPs catalysts, the reaction of
azide-alkyne cycloaddition was chosen as model (Table S3). The
yield of cubic and spherical NCPs show the yield to be 100%,
which is higher than that of BCPs (90%). As shown in Figure S6,
the reaction of NCPs could finish the experiment in 20 hour with
the yield to be 100%, further demonstrating the better catalysis of
NCPs. Especially, after four runs, the yield of product was still high
up to 88%. The XRD pattern of cubic NCPs after catalysis reaction
maintains as well as the starting one, demonstrating the
reusability and stability of NCPs.
Z. Y. Du, X. Q. Wang, S. H. Yua, H. L. Jiang, Chem. Commun. 2014, 50,
1092; d) S. Hermes, T. Witte, T. Hikov, D. Zacher, S. Bahnmuller, G.
Langstein, K. Huber, R. A. Fischer, J. Am. Chem. Soc. 2007, 129, 5324;
e) Z.-W. Wei, C.-X. Chen, S.-P. Zheng, H.-P. Wang, Y.-N. Fan, Y.-Y. Ai,
M. Pan, C.-Y. Su, Inorg. Chem. 2016, 55, 7311; f) T. Yang, H. Cui, C.
Zhang, L. Zhang, C.-Y. Su, Inorg. Chem. 2013, 52, 9053.
[3] P. Zrazhevskiy, M. Sena, X. H. Gao, Chem. Soc. Rev. 2010, 39, 4326.
[4] a) T. Baati, L. Njim, F. Neffati, A. Kerkeni, M. Bouttemi, R. Gref, M. F.
Najjar, A. Zakhama, P. Couvreur, C. Serre, P. Horcajada, Chem. Sci.
2013, 4, 1597; b) T. Rodenas, I. Luz, G. Prieto, B. Seoane, H. Miro, A.
Corma, F. Kapteijn, F. X. L. I. Xamena, J. Gascon, Nature Mater. 2015,
14, 48; c) Y. Lu, B. Yan, Chem. Commun. 2014, 50, 13323; d) B. J. Yao,
W. L. Jiang, Y. Dong, Z. X. Liu, Y. B. Dong, Chem. Eur. J. 2016, 22,
10565; e) Y. Jiang, X. Zhang, X. Dai, W. Zhang, Q. Sheng, H. Zhuo, Y.
Xiao, H. Wang, Nano Res. 2017, 10; f) B. Rungtaweevoranit, Y. Zhao, K.
M. Choi, O. M. Yaghi, Nano Res. 2016, 9, 45.
Conclusions
In summary, we have firstly proposed a solvent-etching top-down
route for the fabrication of NCPs. The cubic and spherical NCPs
could be generated by selecting appropriate etching solvents and
using BCPs as precursor under mild experiment conditions.
Different with the bottom-up route, no impurity were observed in
the obtained sample of solvent-etching top-down route. The
intrinsic advantage of CPs in catalysis has be further
strengthened when they combined with smaller size, and the
cubic NCPs have been demonstrated as efficient catalyst for
Ullmann N-arylation. This work may open the door for the facile
synthesis and catalysis application of NCPs.
[5] a) J. Della Rocca, D. M. Liu, W. B. Lin, Acc. Chem. Res. 2011, 44, 957; b)
P.-Z. Li, Y. Maeda, Q. Xu, Chem. Commun. 2011, 47, 8436.
[6] C. B. Murray, D. J. Norris, M. G. Bawendi, J. Am. Chem. Soc. 1993, 115,
8706.
[7] W. J. Roth, P. Nachtigall, R. E. Morris, P. S. Wheatley, V. R. Seymour, S.
E. Ashbrook, P. Chlubna, L. Grajciar, M. Polozij, A. Zukal, O. Shvets, J.
Cejka, Nature Chem. 2013, 5, 628.
[8] Y. X. Wang, M. T. Zhao, J. F. Ping, B. Chen, X. H. Cao, Y. Huang, C. L.
Tan, Q. L. Ma, S. X. Wu, Y. F. Yu, Q. P. Lu, J. Z. Chen, W. Zhao, Y. B.
Ying, H. Zhang, Adv. Mater. 2016, 28, 4149.
[9] A. Tesfai, B. El-Zahab, D. K. Bwambok, G. A. Baker, S. O. Fakayode, M.
Lowry, I. M. Warner, Nano Lett. 2008, 8, 897.
Acknowledgements
[10] D. Sun, S. Yuan, H. Wang, H. F. Lu, S. Y. Feng, D. F. Sun, Chem.
Commun. 2013, 49, 6152.
This work was financially supported by National Basic Research
Program of China (973 Program, No. 2015CB932200), National
Natural Science Foundation of China (61136003, 51173081,
21501089 and 61505077), Natural Science Foundation of
Jiangsu Province, China (BM2012010, BK20150936 and
BK20150939).
[11] a) G. Evano, N. Blanchard, M. Toumi, Chem. Rev. 2008, 108, 3054; b) F.
Monnier, M. Taillefer, Angew. Chem. Int. Ed. 2008, 47, 3096; c) I. P.
Beletskaya, A. V. Cheprakov, Coord. Chem. Rev. 2004, 248, 2337.
[12] a) M. Meldal, C. W. Tornoe, Chem. Rev. 2008, 108, 2952; b) A. Dondoni,
Chem-Asian J 2007, 2, 700; c) J. F. Lutz, Angew. Chem. Int. Ed. 2007,
46, 1018; d) T. S. A. Hor, F. W. Li, Chem-Eur J 2009, 15, 10585; e) J. E.
Moses, A. D. Moorhouse, Chem. Soc. Rev. 2007, 36, 1249.
[13] a) Z. Fang, B. Bueken, D. E. De Vos, R. A. Fischer, Angew. Chem. Int.
Ed. 2015, 54, 7234; b) Z. L. Fang, J. P. Durholt, M. Kauer, W. H. Zhang,
C. Lochenie, B. Jee, B. Albada, N. Metzler-Nolte, A. Poppl, B. Weber, M.
Muhler, Y. M. Wang, R. Schmid, R. A. Fischer, J. Am. Chem. Soc. 2014,
136, 9627.
Keywords: Coordination Polymer, Nanomaterials, Catalysis,
Top-Down
[1] a) C. He, D. Liu, W. Lin, Chem. Rev. 2015, 115, 11079; b) M. Sindoro, N.
Yanai, A.-Y. Jee, S. Granick, Acc. Chem. Res. 2014, 47, 459; c) P.
Mahato, A. Monguzzi, N. Yanai, T. Yamada, N. Kimizuka, Nature Mater.
2015, 14, 924; d) Q. H. Yang, Y. Z. Chen, Z. Y. U. Wang, Q. Xu, H. L.
Jiang, Chem. Commun. 2015, 51, 10419.
[14] J. Hassan, M. Sevignon, C. Gozzi, E. Schulz, M. Lemaire, Chem. Rev.
2002, 102, 1359.
[2] a) Q.-L. Zhu, Q. Xu, Chem. Soc. Rev. 2014, 43, 5468; b) Y. Cui, B. Chen,
G. Qian, Coord. Chem. Rev. 2014, 273, 76; c) J. W. Zhang, H. T. Zhang,
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10.1002/ejic.201700597
European Journal of Inorganic Chemistry
Communication
Entry for the Table of Contents (Please choose one layout)
Layout 1:
FULL PAPER
The Catalytic Properties of
Copper-based Nanoscale
Coordination
Polymer
Fabricated by Solvent-
Etching Top-Down Route
Nanoscale coordination polymers, which are emerging as a new generation of
functional materials, have been firstly synthesized through facile top-down route
assisted with solvent-etching and further been applied as catalysis in N-arylation
of imidazole aryl halide
Xiaowei Cao, Zhenlan Fang, Wei Huang
and Qiang Ju*
*nanocale coordination polymer
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