Controllable construction of metal-organic polyhedra in confined cavities via in situ site-induced assembly

Article abstract of DOI:10.1039/c7ta01069a

Poor dispersity and low stability are two predominant shortcomings hindering the applications of metal-organic polyhedra (MOPs). The confinement of MOPs in nanoscale cavities of mesoporous matrices is efficient in overcoming both shortcomings, while the i

Full text of DOI:10.1039/c7ta01069a

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ISSN 2050-7488
PAPER
Kun Chang, Zhaorong Chang et al.
Bubble-template-assisted synthesis of hollow fullerene-like
MoS2 nanocages as a lithium ion battery anode material
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DOI: 10.1039/C7TA01069A
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Controllable Construction of Metal-Organic Polyhedra in Confined
Cavities via In Situ Sites-Induced Assembly
Ying-Hu Kang, Ni Yan, Zhen-Yu Gao, Peng Tan, Yao Jiang, Xiao-Qin Liu, and Lin-Bing Sun*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
Poor dispersity and low stability are two predominant MOFs possess interconnected channels, activation improves
shortcomings hindering the applications of metal-organic the accessibility of their active sites greatly.35-37 However, MOP
polyhedra (MOPs). The confinement of MOPs in nanoscale cavities molecules tend to aggregate in solid state after activation,
of mesoporous matrices is efficient in overcoming both which results in the blockage of active sites and compromises
shortcomings, while the improvement of the current double- the catalytic and adsorptive activity of MOPs severely. On the
solvent method is highly expected. Here we develop a facile, other hand, the stability of MOPs is weak since they are
controllable strategy to fabricate three MOPs (coordinated from fabricated by coordination bonds.38-40 The structure of some
dicopper and carboxylates) in confined cavities via in situ sites- MOPs can be degraded even in the presence of trace levels of
induced assembly (SIA), for the first time. The cavities of water.
mesoporous matrix SBA-16 were pre-functionalized with amine
To overcome the shortcomings, the confinement of MOPs in
sites, which induce in situ assembly of precursors that diffused into porous matrices including MOFs and mesoporous silica was
cavities. Hence, both amount and location of MOPs in the reported recently by Li’s group41 and ours.38 In our case, MOP
mesoporous matrix can be easily controlled. Upon confinement,
the dispersity, stability, and catalytic performance (on ring-opening
reactions) of MOPs are greatly improved. Moreover, the
enhancement of stability makes it possible to observe MOPs using
high-resolution transmission electron microscopy (HRTEM) directly.
Metal-organic polyhedra (MOPs, also called molecular
nanocages and nanoballs) are a class of inorganic-organic
discrete coordination complexes constructed from metal ions
and highly directional ligands.1-10 Because of their intriguing
structure, MOPs show high potentials in applications varied
from adsorption and catalysis to biological self-assembly.11-24
Nevertheless, these applications are seriously obstructed by
two shortcomings, that is, poor dispersity and low stability of
MOPs.25-28 On the one hand, MOPs are prone to aggregate in
solid state during activation for the removal of solvent
molecules, although some MOPs can be well dispersed in
solution. Such an activation process is necessary for both metal-
organic frameworks (MOFs) and MOPs prior to use.29-34 Because
State Key Laboratory of Materials-Oriented Chemical Engineering, Jiangsu National
Synergetic Innovation Center for Advanced Materials, College of Chemistry and
Chemical Engineering, Nanjing Tech University, Nanjing 210009, China. E-mail:
lbsun@njtech.edu.cn.
†Electronic Supplementary Information (ESI) available: Full details of sample
preparation, characterizations and additional data. See DOI: 10.1039/x0xx00000x
Scheme 1. Comparison of three different synthetic processes
through adding (a) SBA-16, (b) SBA-16 and the inducer APTES, and (c)
NS to the precursor solution of MOP1.
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molecules were introduced to a three-dimensional cavity-
structured mesoporous matrix (SBA-16). This mesoporous
matrix has large cavities (~6 nm) interconnected by small pore
entrances (~2 nm).42-43 Our MOPs with a dimension of ~3 nm
are just between the size of cavities and pore entrances. As a
result, MOPs are confined in the cavities, which produces
isolated molecules with obviously enhanced dispersity and
stability and overcomes both shortcoming of MOPs. In the
previous study, however, a double-solvent method was
employed, in which porous matrices were dispersed in a
hydrophobic solvent, followed by addition of a tiny amount of
hydrophilic precursor solution and a basic inducer.38 The
volume of precursor solution must be smaller than the pore
volume of porous matrix, so that the hydrophilic precursor
solution is able to enter the pores through capillary force.38, 41,
transmission electron microscopy (HRTEM), although MOPs are
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very sensitive to the high-energy electronDbOeI:a1m0..1039/C7TA01069A
As a proof of concept, we first employed MOP
from Cu(NO3)2 and 5-sulfoisophthalic acid sodium salt (H2L1,
Scheme S1).45 MOP
shows a cuboctahedral geometry when
1 constructed
1
the twelve dicopper units are regarded as vertices and the
linkers as edges. Amine-functionalized mesoporous silica NH2-
SBA-16 (NS) was prepared by a co-condensation approach using
(3-aminopropyl)triethoxysilane (APTES). In a typical SIA process,
the mesoporous matrix NS was added to the precursor solution
containing Cu(NO3)2 and H2L1 (Scheme 1). After 0.5 h of stirring,
the blue solids were separated by centrifugation and wash twice
with methanol. The obtained composites resulted from an
increasing dosage of precursors were denoted as M
2, M N-3, and M N-4, corresponding to 0.7, 1.6, 2.9, and 3.1
MOPs per cavity, respectively, from inductively coupled plasma
(ICP) results. Although the dosage of precursors for M N-4 is 1.5
times higher than that for M N-3, the content of MOPs is similar
1N-1, M1N-
1
1
44
It should be stated that there are several defects for the
confinement of MOPs by the double-solvent method. First, the
synthetic system is sort of complicated due to the use of two
incompatible solvents. Second, all precursors must be dissolved
in a small quantity of solvents (Vsolution < Vpore), and thus the
amount of introduced MOPs is dependent on the solubility of
precursors. Third, the diffusion of both precursor and inducer
molecules in pores matters for the assembly caused by inducer,
which makes the synthetic process hard to control. Taking into
account that the confinement is highly efficient in improving
MOP properties, the development of a facile, controllable
method to introduce MOPs to confined spaces is extremely
desirable.
1
1
in the final composites. This implies that the maximum loading
in the present case is about 3 MOPs per cavity.
Here we report for the first time a facile, controllable strategy
to fabricate MOPs in confined cavities via in situ sites-induced
assembly (SIA, Scheme 1). The cavities of mesoporous matrix
SBA-16 were pre-functionalized with amine sites, which act as
the inducer and trigger in situ assembly of precursors in the
cavities. The present SIA strategy has several advantages over
the double-solvent one. First, the synthetic system is simplified
since only one solvent is involved, and there is no strict
requirements on the properties of solvents. Second, the
solubility of precursors is not a problem any longer, and large
amounts of solvents can be used while the formation of MOPs
only occurs for the precursor molecules diffused into the
cavities in which there are inducer sites. Third, the inducer sites
are already immobilized on the cavities, and only diffusion of
precursor molecules matters, making the synthesis easy to
control. As a result, both amount and location of MOPs in the
mesoporous matrix can be well controlled by means of the SIA
strategy. Because the dimension of MOPs (~3 nm) is smaller
than the size of cavities (~6 nm) but larger than the size of pore
entrances (~2 nm), the formed MOPs are isolated in the cavities.
The high dispersity makes the active sites of MOPs pretty
accessible, and the catalytic activity of isolated MOPs is much
higher than that of aggregated bulk MOPs. Moreover, the
confinement enhances the stability of MOPs. Upon exposure to
humid environment, MOPs in confined cavities maintain the
structure and catalytic activity well, whereas the structure and
catalytic activity of bulk MOPs are degraded evidently. It is
worth noting that the enhancement of stability makes it
possible to observe MOPs directly using high-resolution
Fig. 1 (a) UV-vis and (b) IR spectra. (A) MOP
synthesized by adding NS to the precursor solution of MOP
the sample synthesized by adding SBA-16 and APTES to the
precursor solution of MOP ; (D) the sample synthesized by
adding SBA-16 to the precursor solution of MOP ; (E) NS.
1
; (B) the sample
1
; (C)
1
1
Two control experiments were run to examine the validity of
SIA strategy. Owing to the absence of inducer, no MOP is
formed if unfunctionalized SBA-16 is added to the precursor
solution (Scheme 1a). Further addition of the inducer APTES to
the above system, MOPs can be produced (Scheme 1b).
However, most MOPs locate outside the pores and can be
removed after washing with methanol (MOP
1 is soluble in
methanol). The very slight blue color of the resultant sample
indicates a tiny amount of MOPs are introduced to the cavities.
Interestingly, MOPs are selectively fabricated in the cavities in
the presence of NS, and the final sample is blue even after
thorough washing (Scheme 1c). These results reveal that the
precursors can diffuse into the cavities of NS, and the amine
sites in the cavities are efficient in inducing in situ formation of
MOPs. Also, pre-functionalization with inducer sites favors the
selective formation of MOPs in the cavities, while most MOPs
are formed outside the cavities if the foreign inducer is utilized.
Various techniques were used to characterize the formed MOPs.
In the UV-vis spectra, no absorption peaks are observed for
mesoporous matrix NS, due to the absence of absorption for
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tetrahedral coordinated SiO4 framework (Fig. 1a). MOP
strong absorption peak at 730 nm, which is caused by dicopper MOPs directly by means of TEM. Elemental mapping was also
paddle-wheel structure.45 For the sample prepared by adding employed to examine the distribution of MOPs in mesoporous
SBA-16 to the precursor solution, no absorption for MOPs matrix. For the mesoporous matrix NS, Si and O stemmed from
appears. Further addition of the inducer leads to the generation the silica framework as well as N from amine groups are
of a weak absorption peak at 730 nm, indicating the formation detected (Fig. S6). Besides Si, O, and N from the matrix NS, the
COMMUNICATION
1
has a matrix enhances their stability, making it possiblVeiewtoArtoicblesOenrlvinee
DOI: 10.1039/C7TA01069A
of a small amount of MOPs. Noteworthily, an obvious elements Cu, S, and Na come from MOP1 are observed (Figs. 2
absorption of MOPs becomes visible in the presence of NS, and S3-S5). Furthermore, the elements are distributed in the
which gives further evidence of MOPs formation. Similar trend whole composite homogeneously in spite of different MOP
is also observed from infrared (IR) spectra (Fig. 1b). Due to the contents. In scanning electron microscopy (SEM) images, the
overlapped IR bands of MOPs and the support silica, some matrix NS shows lump-like morphology, while MOP presents
characteristic bands of MOPs are not obvious. However, the flake-like morphology (Fig. S8). In the case of composites, the
bands of MOP1 can be identified in the composite derived from morphology of NS is well preserved and no flake-like material is
NS. Moreover, the intensity of both UV-vis and IR peaks observed. This suggests that MOPs are mainly located inside the
increases gradually with the rise of MOP content in the pores of mesoporous matrix. The wide-angle PXRD pattern of
composites (Figs. S1 and S2). The composites M
4 show comparable peak intensity, which confirms the similar attributed to amorphous silica framework (Fig. S9). It is worthy
1N-3 and M1
N- pristine NS exhibits a broad peak at around 23o, which is
content of MOPs.
of note that all MOPs-containing composites give the identical
patterns to pristine NS, which is apparently different from
aggregated bulk MOPs with obvious diffraction peaks. On the
basis of these results, it is obvious that MOPs are well dispersed
in the mesoporous matrix.
Fig. 3 (a) N2 sorption isotherms and (b) PSDs of MOP1, NS, and
their composite M1N-3.
The change of pore structure was studied by N2 adsorption at
77 K. Because bulk MOPs tend to aggregate, the uptake of N2 is
negligible (Fig. 3). The MOP-containing composites give a type-
IV isotherm and an H2-type hysteresis loop, which is analogous
to the mesoporous matrix NS (Figs. 3 and S10). In contrast to
pristine NS, the hysteresis loop moves to relatively low
pressures after introducing MOPs. The results of pore size
distributions (PSDs) provide further evidence of MOP location.
The matrix NS presents two types of pores centered at 2.0 and
6.4 nm, which originates from pore entrances and cavities
respectively. Interestingly, the incorporation of MOPs results in
Fig. 2 (a) TEM, (b) HRTEM, (c) STEM, and (d) elemental mapping
of the composite M
examples of MOPs.
1N-3. The arrows in b show several
TEM characterization provides information on both
mesoporous matrix and MOPs. TEM images of all composites
exhibit ordered mesoporous structure (Figs. 2 and S3-S5), which
is analogous to the original mesoporous matrix NS (Fig. S6). Also,
the pore regularity of the composites containing MOPs is well
supported by the low-angle powder X-ray diffraction (PXRD)
patterns (Fig. S7). These results demonstrate that the periodic
ordering of mesostructure is well retained after introducing
MOPs. HRTEM technique was also attempted to investigate the
composites. Because MOPs are normally fairly sensitive to the
high-energy electron beam, the report concerning direct
observation of MOPs through TEM is very scarce. Surprisingly,
some spherical nanoparticles, which are believed to originate
from MOPs considering the size and location, can be well
distinguished from the HRTEM image (Fig. 2b). It is apparent
that the confinement of MOPs in the cavities of mesoporous
the decline of cavity size from 6.4 to 5.6 nm (for M1N-3),
whereas the entrance size keeps constant (Table S1). In addition
to M1N-3, the composites with different MOP contents also
show a similar tendency. These results apparently demonstrate
that MOPs are selectively constructed in the cavities of
mesoporous matrix rather than the entrances, which plays an
important role in the generation of isolated MOPs in the
confined space.
The obtained composites were used to catalyze the ring-
opening of styrene oxide (SO) to synthesize 2-methoxy-2-
phenylethanol (MPE), which is a useful intermediate for both
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chemical and pharmaceutical industries.46-47 Traditionally, the of MOPs is evidently enhanced upon confinementViienwnAartnicloesOcnalinlee
DOI: 10.1039/C7TA01069A
ring-opening of styrene oxide is catalyzed by homogeneous cavities.
acids or bases, leading to the problem of waste production and
Besides MOP1, two other MOPs (i.e. MOP2 and MOP3,
the difficulty in separation. The substitution of conventional Scheme S1) with the same geometry but different ligand
homogeneous catalysts with heterogeneous ones thus attracts functionality (i.e. hydroxyl and tert-butyl) were also confined in
increasing attention. MOPs possess coordinatively unsaturated the mesoporous matrix NS by use of SIA. The formation of MOPs
metal sites, which may be active for ring-opening reactions. in NS can be observed visibly from the color change (Figs. S11
Negligible amount of SO is converted over pristine NS (Fig. 4a). and S12). TEM images imply that the ordered mesostructure of
Under the catalysis of MOP
suggesting the presence of active sites. It is interesting to note and S14). UV-vis spectra give further evidence of the successful
that the yield of MPE reaches 80% over the composite M N-3, formation of MOPs (Figs. S15 and S16), which are
1, the yield of MPE is 39% at 120 min, NS is well preserved after the introduction of MOPs (Figs. S13
1
which is apparently higher than that catalyzed by individual homogeneously distributed in the matrix (see elemental
mesoporous matrix and MOPs. Recyclability is of great mappings). The high dispersion of MOPs in NS is also confirmed
importance for the practical applications, and the present by wide-angle PXRD patterns, in which no diffraction peaks
heterogeneous catalysts are thus recovered after reactions and ascribed to MOPs appear (Figs. S17 and S18). The PSD results
reused (Fig. 4b). No loss in activity is observed for the composite show that the cavity size declines while the entrance size keeps
in the four successive cycles. Nonetheless, the yield of MPE over constant (Figs. S19 and S20), which demonstrates the selective
MOP
1 decreases harshly (from 40 % to 3 %) in the second cycle. fabrication of MOPs in cavities of NS. These results prove that
These results clearly show that isolated MOPs are much more the SIA strategy is efficient in introducing different MOPs to
active and stable than aggregated bulk ones.
mesoporous matrix.
Conclusions
In summary, we demonstrate the successful fabrication of
MOPs in the confined nanoscale cavities by using the SIA
strategy. The pre-functionalized amine sites function as the
inducer, trigger in situ assembly of precursors in the cavities,
and avoid the formation of MOPs outside the pores. Isolated
MOPs with unusual dispersity are thus formed, which makes the
active sites of MOPs pretty accessible, and the catalytic activity
of isolated MOPs is much higher than that of aggregated bulk
MOPs. Moreover, upon confinement, the stability of MOPs is
greatly enhanced. After exposure to humid environment, MOPs
in confined cavities maintain the structure and catalytic activity
well, whereas the structure and catalytic activity of bulk MOPs
are degraded seriously. Also, the enhanced stability makes it
possible to observe MOPs using TEM technique directly. The
present SIA strategy may open up an avenue for the
confinement of various MOPs as well as other supramolecular
architectures in nanoscale spaces, leading to the fabrication of
isolated architectures with enhanced stability and dispersity
that are highly expected for various applications but impossible
to achieve for their bulk analogues.
Fig. 4 (a) The ring-opening of styrene oxide catalyzed by MOP1,
NS, and their composite M
N-3. (c) Catalytic capacity and (d) UV-vis spectra of MOP
and M N-3 upon exposure to humid atmosphere.
1N-3. (b) Reusability of MOP1 and
M1
1
1
To further evaluate the stability, the materials were exposed
to humid environment (relative humidity = 50%). The materials
after exposure were used for catalysis and subjected to
structure characterization. Upon exposure to humid
environment (Fig. 4c), the yield of MPE is reduced sharply from
40% to 16% (12 h) and 3% (24 h). However, under the identical
treatment conditions, the composite exhibits a constant activity
in catalysis. UV-vis spectra show that for the MOPs after
exposure, the absorption peak derived from dicopper paddle-
wheel units shifts from 730 to 700 nm, which means the
degradation of MOP structure (Fig. 4d). In the case of the
composite, nevertheless, the absorption at 730 nm keeps
unchanged after exposure for even 24 h. This is in good
agreement with the catalytic results, pointing out the stability
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (21576137), the Distinguished Youth
Foundation of Jiangsu Province (BK20130045), the Fok Ying-
Tong Education Foundation (141069), and the Project of Priority
Academic Program Development of Jiangsu Higher Education
Institutions.
Notes and references
1 T. R. Cook and P. J. Stang, Chem. Rev., 2015, 115, 7001.
4 | J. Name., 2012, 00, 1-3
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Page 5 of 6
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COMMUNICATION
2 R. Chakrabarty, P. S. Mukherjee and P. J. Stang, Chem. Rev., 2011, 28 L. B. Sun, J. R. Li, W. G. Lu, Z. Y. Gu, Z. P. Luo and H. C. Zhou, J. Am.
View Article Online
111, 6810.
Chem. Soc., 2012, 134, 15923.
DOI: 10.1039/C7TA01069A
3 W. J. Ramsay, F. T. Szczypiński, H. Weissman, T. K. Ronson, M. M. J. 29 A. Mallick, B. Garai, D. D. Diaz and R. Banerjee, Angew. Chem. Int.
Smulders, B. Rybtchinski and J. R. Nitschke, Angew. Chem. Int. Ed., Ed., 2013, 52, 13755.
2015, 54, 5636.
30 U. Stoeck, I. Senkovska, V. Bon, S. Krause and S. Kaskel, Chem.
4 S.-T. Zheng, T. Wu, B. Irfanoglu, F. Zuo, P. Feng and X. Bu, Angew. Commun., 2015, 51, 1046.
Chem. Int. Ed., 2011, 50, 8034.
31 Z. Niu, S. Fang, X. Liu, J. G. Ma, S. Q. Ma and P. Cheng, J. Am. Chem.
5 J. M. Teo, C. J. Coghlan, J. D. Evans, E. Tsivion, M. Head-Gordon, C. Soc., 2015, 137, 14873.
J. Sumby and C. J. Doonan, Chem. Commun., 2016, 52, 276.
6 D. Kim, X. F. Liu and M. S. Lah, Inorg. Chem. Front., 2015, 2, 336.
32 J. An, O. K. Farha, J. T. Hupp, E. Pohl, J. I. Yeh and N. L. Rosi, Nat.
Commun., 2012, 3, 604.
7 T.-H. Chen, L. Wang, J. V. Trueblood, V. H. Grassian and S. M. Cohen, 33 S. Pasquale, S. Sattin, E. C. Escudero-Adan, M. Martinez-Belmonte
J. Am. Chem. Soc., 2016, 138, 9646. and J. de Mendoza, Nat. Commun., 2012, 3, 785.
8 H. Furukawa, J. Kim, N. W. Ockwig, M. O'Keeffe and O. M. Yaghi, J. 34 J. R. Li, J. M. Yu, W. G. Lu, L. B. Sun, J. Sculley, P. B. Balbuena and
Am. Chem. Soc., 2008, 130, 11650. H. C. Zhou, Nat. Commun., 2013, 4, 893.
9 H. Furukawa, J. Kim, K. E. Plass and O. M. Yaghi, J. Am. Chem. Soc., 35 Y. Han, J. R. Li, Y. B. Xie and G. S. Guo, Chem. Soc. Rev., 2014, 43,
2006, 128, 8398. 5952.
10 S. Leininger, B. Olenyuk and P. J. Stang, Chem. Rev., 2000, 100, 853. 36 J. J. Perry, J. A. Perman and M. J. Zaworotko, Chem. Soc. Rev., 2009,
11 Y. Kohyama, T. Murase and M. Fujita, J. Am. Chem. Soc., 2014, 136, 38, 1400.
2966.
37 L. E. Darago, M. L. Aubrey, C. J. Yu, M. I. Gonzalez and J. R. Long, J.
Am. Chem. Soc., 2015, 137, 15703.
12 M. Fujita, Chem. Soc. Rev., 1998, 27, 417.
13 M. Yoshizawa, J. K. Klosterman and M. Fujita, Angew. Chem. Int. 38 Y.-H. Kang, X.-D. Liu, N. Yan, Y. Jiang, X.-Q. Liu, L.-B. Sun and J.-R.
Ed., 2009, 48, 3418. Li, J. Am. Chem. Soc., 2016, 138, 6099.
14 K. Takao, K. Suzuki, T. Ichijo, S. Sato, H. Asakura, K. Teramura, K. 39 L. Lu, X.-Y. Li, X.-Q. Liu, Z.-M. Wang and L.-B. Sun, J. Mater. Chem.
Kato, T. Ohba, T. Morita and M. Fujita, Angew. Chem. Int. Ed., 2012, A, 2015, 3, 6998.
51, 5893.
40 D.-D. Zu, L. Lu, X.-Q. Liu, D.-Y. Zhang and L.-B. Sun, J. Phys. Chem.
15 D. Zhao, S. W. Tan, D. Q. Yuan, W. G. Lu, Y. H. Rezenom, H. L. Jiang, C, 2014, 118, 19910.
L. Q. Wang and H. C. Zhou, Adv. Mater., 2011, 23, 90.
41 X. Qiu, W. Zhong, C. H. Bai and Y. W. Li, J. Am. Chem. Soc., 2016,
16 B. Li, Y. Zhang, D. Ma, T. Ma, Z. Shi and S. Ma, J. Am. Chem. Soc., 138, 1138.
2014, 136, 1202.
42 H. Q. Yang, L. Zhang, L. Zhong, Q. H. Yang and C. Li, Angew. Chem.
17 J. Park, L. B. Sun, Y. P. Chen, Z. Perry and H. C. Zhou, Angew. Chem. Int. Ed., 2007, 46, 6861.
Int. Ed., 2014, 53, 5842.
43 D. Y. Zhao, Q. S. Huo, J. L. Feng, B. F. Chmelka and G. D. Stucky, J.
18 Q. G. Zhai, C. Y. Mao, X. Zhao, Q. P. Lin, F. Bu, X. T. Chen, X. H. Bu Am. Chem. Soc., 1998, 120, 6024.
and P. Y. Feng, Angew. Chem. Int. Ed., 2015, 54, 7886.
44 A. Aijaz, A. Karkamkar, Y. J. Choi, N. Tsumori, E. Ronnebro, T.
19 Y. T. Li, D. J. Zhang, F. Y. Gai, X. Q. Zhu, Y. N. Guo, T. L. Ma, Y. L. Liu Autrey, H. Shioyama and Q. Xu, J. Am. Chem. Soc., 2012, 134, 13926.
and Q. S. Huo, Chem. Commun., 2012, 48, 7946.
20 N. Ahmad, H. A. Younus, A. H. Chughtai and F. Verpoort, Chem. 46 G. D. Yadav and S. Singh, Tetrahedron Lett., 2014, 55, 3979.
Soc. Rev., 2015, 44, 9. 47 M. Tokunaga, J. F. Larrow, F. Kakiuchi and E. N. Jacobsen, Science,
45 J. R. Li and H. C. Zhou, Nat. Chem., 2010, 2, 893.
21 N. Ahmad, A. H. Chughtai, H. A. Younus and F. Verpoort, Coord. 1997, 277, 936.
Chem. Rev., 2014, 280, 1.
22 A. Schmidt, A. Casini and F. E. Kuhn, Coord. Chem. Rev., 2014, 275,
19.
23 H. Vardhan, M. Yusubov and F. Verpoort, Coord. Chem. Rev., 2016,
306, 171.
24 J. Roukala, J. Zhu, C. Giri, K. Rissanen, P. Lantto and V.-V. Telkki, J.
Am. Chem. Soc., 2015, 137, 2464.
25 N. Hosono, M. Gochomori, R. Matsuda, H. Sato and S. Kitagawa, J.
Am. Chem. Soc., 2016, 138, 6525.
26 T. F. Liu, Y. P. Chen, A. A. Yakovenko and H. C. Zhou, J. Am. Chem.
Soc., 2012, 134, 17358.
27 Z. Lu, C. B. Knobler, H. Furukawa, B. Wang, G. N. Liu and O. M.
Yaghi, J. Am. Chem. Soc., 2009, 131, 12532.
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Journal of Materials Chemistry A
Page 6 of 6
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DOI: 10.1039/C7TA01069A
Table of Contents
Controllable Construction of Metal-Organic Polyhedra in Confined
Cavities via In Situ Sites-Induced Assembly
Ying-Hu Kang, Ni Yan, Zhen-Yu Gao, Peng Tan, Yao Jiang, Xiao-Qin Liu, and Lin-Bing Sun*
State Key Laboratory of Materials-Oriented Chemical Engineering, Jiangsu National Synergetic
Innovation Center for Advanced Materials, College of Chemistry and Chemical Engineering,
Nanjing Tech University, Nanjing 210009, China.
Controllable fabrication of metal-organic polyhedra in confined cavities with improved properties
was realized through in situ sites-induced assembly.