A novel porous anionic metal-organic framework with pillared double-layer structure for selective adsorption of dyes

Article abstract of DOI:10.1016/j.jssc.2015.10.022

A novel porous anionic metal-organic framework, (Me₂NH₂)₂[Zn₂L_1.5bpy]·2DMF (BUT-201; H₄L=4,8-disulfonaphthalene-2,6-dicarboxylic acid; bpy=4,4-bipyridine; DMF=N,N-dimethylformamide), with pillared double-layer structure has been synthesized through the reaction of a sulfonated carboxylic acid ligand and Zn(NO₃)₂·6H₂O with 4,4-bipyridine as a co-ligand. It is found that BUT-201 can rapidly adsorb cationic dyes with a smaller size such as Methylene Blue (MB) and Acriflavine Hydrochloride (AH) by substitution of guest (CH₃)₂NH₂⁺, but has no adsorption towards the cationic dyes with a lager size such as Methylene Violet (MV), the anionic dyes like C. I. Acid Yellow 1 (AY1) and neutral dyes like C. I. Solvent Yellow 7 (SY7), respectively. The results show that the adsorption behavior of BUT-201 relates not only to the charge but also to the size/shape of dyes. Furthermore, the adsorbed dyes can be gradually released in the methanol solution of LiNO₃.

Full text of DOI:10.1016/j.jssc.2015.10.022

Journal of Solid State Chemistry 233 (2016) 143–149
Contents lists available at ScienceDirect
Journal of Solid State Chemistry
journal homepage: www.elsevier.com/locate/jssc
A novel porous anionic metal–organic framework with pillared
double-layer structure for selective adsorption of dyes
n
Shu-Nan Sheng, Yi Han, Bin Wang, Cui Zhao, Fan Yang, Min-Jian Zhao, Ya-Bo Xie ,
n
Jian-Rong Li
Department of Chemistry and Chemical Engineering, College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100124,
PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
A novel porous anionic metal–organic framework, (Me2NH2)2[Zn2L1.5bpy] ꢀ 2DMF (BUT-201; H4L¼4,8-
disulfonaphthalene-2,6-dicarboxylic acid; bpy¼4,4-bipyridine; DMF¼N,N-dimethylformamide), with
pillared double-layer structure has been synthesized through the reaction of a sulfonated carboxylic acid
ligand and Zn(NO3)2 ꢀ 6H2O with 4,4-bipyridine as a co-ligand. It is found that BUT-201 can rapidly ad-
sorb cationic dyes with a smaller size such as Methylene Blue (MB) and Acriflavine Hydrochloride (AH)
by substitution of guest (CH3)2NH2þ, but has no adsorption towards the cationic dyes with a lager size
such as Methylene Violet (MV), the anionic dyes like C. I. Acid Yellow 1 (AY1) and neutral dyes like C. I.
Solvent Yellow 7 (SY7), respectively. The results show that the adsorption behavior of BUT-201 relates
not only to the charge but also to the size/shape of dyes. Furthermore, the adsorbed dyes can be gradually
released in the methanol solution of LiNO3.
Received 1 August 2015
Received in revised form
12 October 2015
Accepted 13 October 2015
Keywords:
Anionic metal–organic framework
Pillared double-layer structure
Selective adsorption of dyes
& 2015 Elsevier Inc. All rights reserved.
1. Introduction
various dyes in industrial effluents which must be removed before
discharged into natural environment. Compared with conven-
Recently, as a class of organic–inorganic hybrid porous mate-
rial, metal–organic frameworks (MOFs) [1–3] composed of organic
ligands and metal ions (clusters) have received a considerable
attention owing to their emerging applications in many areas, such
as gas storage/separation [4–9], ion exchange [10,11], catalysis
[12–14], and so on [15–19]. The structures and properties of MOFs
usually depend on the organic ligands and metal ions (or metal
clusters). Metal clusters [20,21], also called secondary building
units (SBUs), are usually formed in situ. Generally, under given
synthetic conditions [22–28], it is easy to predict the structures of
the resulting SBUs after a long time efforts of this respect in MOFs
field. On the other hand, organic ligands have usually been syn-
thesized prior to MOFs' construction, thus the structures and
properties of MOFs can be easily tailored for some pre-designed
applications to some extent [29].
tional techniques [39,40], the methods based on adsorption are
promising because of their low energy consumption and ease to
operate. A representative example was reported by Bu's group
[30]. They synthesized a series of cationic indium MOFs and ap-
plied them into the adsorption and separation of organic dyes
based on anionic guest substitution. Despite some examples were
reported on the exploration of organic dye removal using MOFs
based on guest molecule substitution [30–38], the study in this
area is still at the early stage.
Many efforts have been focused on modifying the pore chem-
istry by incorporating functional moieties in order to optimize the
adsorption performance of MOFs. Sulfonate groups (–SO3ꢁ) were
often selected to endow the framework of porous materials with
free Lewis base sites to make strong interactions between guest
molecules and the framework skeleton. For MOFs' construction,
when sulfonate and carboxylic groups coexist in a ligand, the
carboxylic groups are expected to preferentially coordinate with
metal ions (clusters) from first-row transition-metal because of
their relatively stronger coordination ability [41]. In this context,
the generated framework might leave the sulfonate groups free
and possibly make the resulted MOF with negative charges.
Herein, 4,8-disulfonaphthalene-2,6-dicarboxylic acid (H4L), syn-
thesized through functionalizing 2,6-dicarboxylic acid with sulfo-
nate groups was advisedly selected as organic ligand reacting to Zn
(NO3)2 ꢀ 6H2O under solvothermal conditions. A novel anionic
Charged MOFs are very appealing due to their inherent features
such as easy guest substitution. Recent studies show that charged
MOFs as a class of excellent porous materials, exhibit a potential
application for dye removal by guest molecule substitution [30–
38]. Dyes are widely used in some industries including medicine,
paper, leather, plastics and textiles, leading to the existence of
n
Corresponding authors. Fax: þ86 10 6739 2332.
E-mail address: xieyabo@bjut.edu.cn (Y.-B. Xie).
http://dx.doi.org/10.1016/j.jssc.2015.10.022
0022-4596/& 2015 Elsevier Inc. All rights reserved.

144
S.-N. Sheng et al. / Journal of Solid State Chemistry 233 (2016) 143–149
three-dimensional (3D) pillared double-layer MOF with the for-
mula of (Me2NH2)2[Zn2L1.5bpy] ꢀ 2DMF (BUT-201, BUT¼Beijing
University of Technology) was synthesized in the presence of 4,4-
bipyridine (bpy) as a co-ligand. It was found that BUT-201 can
rapidly adsorb cationic dyes with a smaller size such as Methylene
Blue (MB) and Acriflavine Hydrochloride (AH), but hardly adsorb
such dyes as neutral Solvent Yellow 2 (SY2) and negative Methyl
Orange (MO). Furthermore, the larger cationic dye, Methylene
Violet (MV), was rarely adsorbed, and no uptake was found upon
neutral (C. I. Solvent Yellow 7, SY7) and anionic dyes (C. I. Acid
Yellow 1, AY1) with even smaller sizes compared with SY2 and MO
[38], respectively.
Table 1
Crystal data and structure refinement for BUT-201.
Empirical formula
Formula weight
Crystal system
Space group
a (Å)
b (Å)
c (Å)
α (°)
β (°)
C38H44N6O17S3Zn2
1083.7
Triclinic
P-1
12.6390 (3)
13.9706 (4)
16.2850 (4)
68.414 (3)°
83.532 (2)°
73.525 (2)°
2567.86 (12)
2
γ (°)
Volume (Å3)
Z
Calculated density (mg mꢁ3
)
1.402
Independent reflections (I42s(I))
F (000)
θ range for data collection
Limiting indices
9534
1116
4.3–73.6°
ꢁ15 rhr15
ꢁ17 rkr15
ꢁ20rlr20
0.722
R1¼0.0583,wR2¼0.1623
R1¼0.0563,wR2¼0.1598
1.38 and ꢁ1.11
2. Experimental
2.1. Materials and general methods
All the reagents and solvents (AR grade) for the synthesis were
purchased from commercial sources and used without further
purification. The ligand H4L was synthesized according to the
modified previous reports [41,42]. IR spectra were monitored with
a Shimadzu IR435 spectrometer as KBr pellet (4000–400 cmꢁ1).
Thermal analysis data were collected on a SHIMADZU DTG-60
thermal analyzer from 40 to 800 °C with a heating rate of
5 °C minꢁ1 under N2 atmosphere. Powder X-ray diffraction (PXRD)
patterns were recorded on a PANalytical X'Pert PRO Diffractometer
Goodness-of-fit on F2
R1a, wR2b [I42s(I)]
R1a, wR2b (all data)
Largest diff. peak and hole (e Åꢁ3
)
a
R1¼ Σ(||F0|ꢁ|FC||)/Σ|F0| and
wR2¼[Σw(|F0|2ꢁ|FC|2)2/Σw(F02)]1/2
b
Table 2
Selected bond lengths (Å) and angles (°) for BUT-201.
by using Cu-K
α
radiation (λ¼1.541874 Å) at room temperature.
Zn1–O11
Zn1–O9
1.932 (2)
1.974 (2)
1.954 (2)
2.013 (3)
2.140 (3)
102. 0 (1)
111.1 (1)
97.1 (1)
112.8 (1)
87.5 (1)
99.6 (1)
89.4 (1)
168.4 (1)
Zn1–O1a
Zn1–N1
Zn2–O2a
Zn2–O5c
1.944 (2)
2.005 (3)
1.959 (2)
2.085 (3)
111.9 (1)
129.9 (1)
103.4 (1)
146.3 (1)
100.7 (1)
90.1 (1)
Simulation of the PXRD pattern was performed by the single-
crystal data and diffraction-crystal module of the Mercury pro-
gram. UV–vis spectra data were obtained with a SHIMADZU UV-
2600 Spectrophotometer.
Zn2–O10
Zn2–N2b
Zn2–O12
O11–Zn1–O1a
O1a–Zn1–O9
O1a–Zn1–N1
O10–Zn2–O2a
O2a–Zn2–N2b
O2a–Zn2–O5c
O10–Zn2–O12
N2b–Zn2–O12
O11–Zn1–O9
O11–Zn1–N1
O9–Zn1–N1
O10–Zn2–N2b
O10–Zn2–O5c
N2b–Zn2–O5c
O2a–Zn2–O12
O5c–Zn2–O12
2.2. Synthesis of H4L ligand
20 mL of fuming sulfuric acid (SO3, 20 wt%) was slowly added
to a 100 mL three-neck flask containing 4 g (18.5 mmol) naph-
thalene-2,6-dicarboxylic acid under stirring. Then the reaction
mixture was stirred at 120 °C for 12 h. After cooling to room
temperature, the mixture was transferred into concentrated HCl
and the white power of acid H4L was precipitated. The power was
washed serveral times with concentrated HCl. Then pure product
was collected by centrifuge and dried at 80 °C. Yield 6.0 g (ꢂ86%)
based on naphthalene-2,6-dicarboxylic acid. IR (KBr pellet, cmꢁ1):
1287 (m), 1196 (s), 1113 (w), 1047 (m) (O¼S¼O of –SO3H group)
[42], 623 (m).
86.5 (1)
92.0 (1)
Symmetry transformations used to generate equivalent atoms:
a
xþ1, y, z;
b
x, yþ1, z;
c
ꢁxþ1, ꢁyþ1, ꢁzþ2.
2.3. Preparation of (Me2NH2)2[Zn2L1.5bpy] ꢀ 2DMF (BUT-201)
A mixture of Zn(NO3)2 ꢀ 6H2O (10 mg, 0.035 mmol), H4L (13 mg,
0.035 mmol), bpy (3 mg, 0.019 mmol) and 1.6 mL DMF with
6 drops HBF4 was sealed into a 5 mL vial and then heated at 100 °C
for 48 h. After the reaction system was cooled down to room
temperature, the products were washed with DMF twice to obtain
the pure colorless block crystals. The as-synthesized BUT-201 was
hardly soluble in common organic solvents such as DMA, DMF,
CH2Cl2, CHCl3, MeOH, EtOH, and acetone. IR (KBr, cmꢁ1): 3475 (m),
3097 (w), 2812 (w), 2359 (w), 1714 (m), 1613 (s), 1395 (s), 1345 (s),
1194 (s), 1035 (s), 809 (m), 750 (w), 607 (s), 515 (m).
2.4. X-ray crystallography
Fig. 1. TG curve of as-synthesized BUT-201.
The diffraction data for BUT-201 were collected on an Agilent
Technologies SuperNova Single Crystal Diffractometer that was
equipped with graphite-monochromatized Mo-K
α
radiation
(λ
¼0.71073 Å) at ꢁ173 °C. Empirical absorption correction was

S.-N. Sheng et al. / Journal of Solid State Chemistry 233 (2016) 143–149
145
positions with a riding model and refined isotropically. There are
large solvent accessible pore volumes in the crystals of BUT-201,
which are occupied by highly disordered solvent molecules. No
satisfactory disorder model for these guest molecules could be
achieved, and therefore the SQUEEZE program implemented in
PLATON was used to remove the electron densities of these dis-
ordered species. Thus, all of the electron densities from free guest
molecules have been “squeezed” out [45]. The details of structural
refinement can be found in Table 1, while the selected bond
lengths and angles are summarized in Table 2.
2.5. Dyes absorption and release
Dyes selective absorption: as-synthesized BUT-201 crystals were
successively washed with DMF and MeOH three times. Then the
samples were transferred into MeOH solutions containing MB, AH,
MV, MO, SY2, AY1, and SY7 with certain concentrations at the
detectable range by UV–vis spectra in vials, respectively. After that,
the concentrations of dyes were measured every several minutes
with UV–vis to assess the adsorption property of BUT-201. In ad-
dition, the pure dye solution is replaced with the mixture of two
different dyes, including MB&MO and MB&SY2, which were em-
ployed to further verify the selective uptake property of BUT-201.
Dyes release: the BUT-201 samples loaded with MB or AH
(MB@BUT-201 or AH@BUT-201) were transferred into pure MeOH
and MeOH solutions of LiNO3 in vials, respectively. Then the re-
leasing process was monitored by UV–vis.
Fig. 2. The PXRD patterns for simulated and as-synthesized BUT-201.
applied using spherical harmonics and implemented in SCALE3
ABSPACK scaling algorithm. The structures were solved by direct
methods and refined by full-matrix least-squares on F2 with ani-
sotropic displacement using the SHELXTL software package [43].
All non-H atoms were refined anisotropically during the final cy-
cles. Hydrogen atoms of ligands were calculated at idealized
Fig. 3. The structural presentation of BUT-201 (hydrogen atoms, dimethylaminecations, and solvent molecules are omitted for clearly): (a) Coordinaton environments of
Zn2þ, H4L and bpy ligands. Symmetry codes:A, (x, 1þy, z); B, (1ꢁx, 1ꢁy, 2ꢁz); C, (1þx, y, z); D, (1ꢁx, 2ꢁy, 1ꢁz); (b) View of the 2D layer assembled by Zn2þ, L4ꢁ and bpy
ligands; (c) 3D pillared double-layer structure of BUT-201, showing the rhombic channel along b axis; (d) The space-filling structure of BUT-201. Color scheme: Zn, cyan; N,
blue; S, yellow; O, red; C, gray. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

146
S.-N. Sheng et al. / Journal of Solid State Chemistry 233 (2016) 143–149
Fig. 4. Changes of UV–vis spectra in MeOH solutions of MB (a), AH (b), MO (c), SY2 (d), and MV (e) AY1 (f) SY7 (g) containing BUT-201 with the time past; the inset
photographs for the changes of crystals color before and after adsorption in MeOH solutions towards the corresponding dyes.

S.-N. Sheng et al. / Journal of Solid State Chemistry 233 (2016) 143–149
147
Fig. 5. UV–vis spectra changes of dye mixture in the presence of BUT-201. (a) MB&MO; (b) MB&SY2. The inset photographs are before and after adsorption.
Fig. 6. UV–vis spectra monitored the process of dye release in a solution of MeOH with LiNO3. (a) MB@BUT-201; (c) AH@BUT-201; (b) The release-rate comparison of MB
from MB@BUT-201 in pure MeOH and in a MeOH solution of LiNO3; (d) The release-rate comparison of AH from AH@BUT-201 in pure MeOH and in MeOH solution of LiNO3.
3. Results and discussion
DMF molecules, and then there is an additional weight loss of 10%
which is in good agreement with the removal of dimethylamine
molecules (calc. 8%). The dimethylamine molecules mentioned
3.1. Synthesis and general characterizations of BUT-201
þ
above should be from (CH3)2NH2 with a proton transfer process
Transparent block crystals of BUT-201 were prepared from H4L,
bpy, and Zn(NO3)2 ꢀ 6H2O in DMF-HBF4 mixed solution under sol-
vothermal conditions. The TGA was employed to check the ther-
mal stability of as-synthesized BUT-201. The curve of thermal
gravimetric analysis in Fig. 1 shows that two processes of rapid
weight loss are observed before 250 °C. The weight loss of 14% is
corresponding to the calculated value (13%) for the removal of
between the counter cations and the anionic framework [41,44].
The host framework decomposes after an obvious platform and
the thermal stability of BUT-201 is up to ꢂ380 °C. The phase
purity of as-synthesized BUT-201 was tested by PXRD. Fig. 2 shows
that the experimental PXRD pattern is almost coincident with the
simulated one from the single crystal data, suggesting the phase
purity of as-synthesized BUT-201. The difference in reflection

148
S.-N. Sheng et al. / Journal of Solid State Chemistry 233 (2016) 143–149
intensities between the simulated and experimental patterns may
be attributed to the variation in preferred orientation of the
powder samples during the collection of the experimental PXRD
data.
towards the anionic and neutral dye molecules in solutions (Fig. 5).
For comparison, the adsorption of another cationic dye with a
larger size and different shape, namely MV, was examined [Fig. 4
(e)]. But no incorporation was observed, and the size/shape ex-
clusion effect may be the dominant factor. All tested results sug-
gest that the adsorption behavior not only follows a charge but
also a size/shape exclusion effect. In addition, we also tested dyes
with even smaller sizes (compared with MB and AH [38]): anionic
AY1 [Fig. 4(f)] and neutral SY7 [Fig. 4(g)], and no obvious ad-
sorption was found by UV–vis spectra, even though the selected
dyes seem to be able to accommodate pore considering the size. It
further suggests that cationic guest molecule substitution may be
the dirven-force and plays a primary role.
The reversibility of the dyes adsorption is extremely vital for
application in practice, so dye release processes were also in-
vestigated in pure MeOH and a saturated MeOH solution of LiNO3,
respectively (Fig. 6). It was found that, the loaded dye molecules
are barely released in pure MeOH, but can be readily released in
saturated MeOH solution of LiNO3, which is demonstrated that dye
release in this work is also a guest cationic substitution-driven
process. Furthermore, the processes of dye release recorded by
UV–vis spectra were quickly achieved an equilibrium towards
MB@BUT-201 and AH@BUT-201 over a period of time, and after
that the release rate of dye molecules became slower, with the
concentrations of released dyes in solutions increased (Fig. 6).
3.2. Structure of BUT-201
The formula of BUT-201 is (Me2NH2)2[Zn2L1.5bpy] ꢀ 2DMF ob-
tained by single-crystal X-ray diffraction studies, thermal gravi-
metric analysis, and charge-balance theories. Single-crystal X-ray
diffraction shows that BUT-201 crystallizes in the triclinic space
group P-1. In the structure, the crystallographically asymmetric
unit contains two Zn2þ ions, one and a half L4ꢁ, one bpy, two
þ
(CH3)2NH2þ cations, and two DMF molecules [Fig. 3(a)]. The
(CH3)2NH2 cations in pores should be originated from the de-
composition of DMF during the reaction [38]. The Zn1 ion is sur-
rounded by three O atoms of carboxylate groups from three dif-
ferent L4ꢁ and one N atom from bpy, forming a distorted tetra-
hedral geometry. The Zn1–O bond distances range from 1.932 to
1.973(5) Å, and the Zn1–N bond distance is 2.005(4) Å. The Zn2 ion
adopts a distorted trigonalbipyramid geometry finished by three O
atoms of carboxylate groups and one O atom of sulfonate group
from four independent L4ꢁ, as well as one N atom from bpy. The
Zn2–O bond lengths are between 1.954 and 2.084(5) Å, and the
Zn2–N bond distance is 2.013(2) Å. Each carboxylate group bridges
two Zn2þ ions in a syn–syn-m2-η1 η1 linking mode to form a di-
:
nuclar unit, which is connected by two L4ꢁ and two bpy to gen-
erate a two-dimensional (2D) layer [Fig. 3(b)]. Meanwhile, Zn1
ions in one single layer are coordinated with O atoms of sulfonate
groups of L4ꢁ from adjacent layer resulting in a double-layered
structure, which is further extended through L4ꢁ to form a three-
dimensional (3D) pillared double-layer structure, featuring
rhombic channels with a pore dimension of 12 ꢃ 12 Å (the dis-
tance between the atoms) [Fig. 3(c)], in which disordered
4. Conclusions
In summary, a novel anionic MOF with pillared double-layer
structure was successfully synthesized, structurally characterized,
and used in selective adsorption of dyes. BUT-201 can rapidly and
selectively adsorb the cationic dyes with a smaller size (MB and
AH) by cationic guest molecule substitution, being controlled by
charge and size/shape exclusion effect. Moreover, dye release is
realized in a saturated MeOH solution of LiNO3. Dye adsorption
and release studies reveal that BUT-201 possesses potential ap-
plications in selectively removing cationic dyes with a smaller size
from effluents, which is very meaningful for environmental
cleaning.
þ
(CH3)2NH2 cations accommodate. Topologically, the dinuclar Zn
unit serves as a six-connected node and the L4ꢁ as a three-con-
nected linker, affording a (3,6)-connected binodal 3D structure
with 3,6T24 topological type. After removing all of the guest mo-
lecules from the channels, the calculated total accessible volume is
47.7% by the PLATON.
3.3. Dyes absorption and release of BUT-201
Supplementary data
In this work, BUT-201 was studied for adsorption of organic
dyes owing to its porous anion framework nature. Four dyes were
selected to assess the adsorption property of BUT-201, which
possess the similar size but different charges: positively charged
MB and AH, electrically neutral SY2 and negatively charged MO.
The as-synthesized BUT-201 was immersed in MeOH solutions
containing the above dyes at room temperature respectively. It
was observed that the solutions containing MB and AH were ob-
viously faded after several minutes, meanwhile the colorless
crystals of BUT-201 turned blue of MB and yellow of AH, respec-
tively (Fig. 4). However, the colors of solutions with negatively
charged MO and electrically neutral SY2 remained unchanged
(Fig. 4). These phenomena coincide with the measurement results
by UV–vis spectra (Fig. 4). The results could be attributed to ionic
interaction between anionic framework and cationic guest mole-
cules, as well as cationic guest substitution occurring between
Crystallographic data for the structure reported in this paper
has been deposited on the Cambridge Crystallographic Data Center
(CCDC No. 1416214). The material can be obtained free of charge
via https://www.ccdc.cam.ac.uk/deposit.
Acknowledgments
This work was financially supported by the NSFC (No.
21271015, 21322601, and U1407119), the Program for New Century
Excellent Talents in University (No. NCET-13-0647) and Beijing
Municipal Natural Science Foundation (No. 2132013).
References
þ
(CH3)2NH2 and different cationic dye molecules.
Mixed dyes, namely MB&MO and MB&SY2, were chosen in
order to further verify the selective uptake property of BUT-201.
Experimentally, the solutions gradually turned intrinsic color of
pure MO or SY2. Meanwhile the original crystals became blue of
MB. The UV–vis spectra also demonstrated that BUT-201 can ra-
pidly and selectively adsorb cationic dyes, but has no adsorption
[1] J.R. Long, O.M. Yaghi, The pervasive chemistry of metal–organic frameworks,
Chem. Soc. Rev. 38 (2009) 1213–1214.
[2] H.C. Zhou, J.R. Long, O.M. Yaghi, Introduction to metal–organic frameworks,
Chem. Rev. 112 (2012) 673–674.
[3] H.C. Zhou, S. Kitagawa, Metal–organic frameworks (MOFs), Chem. Soc. Rev. 43
(2014) 5415–5418.
[4] J.R. Li, R.J. Kuppler, H.C. Zhou, Selective gas adsorption and separation in

S.-N. Sheng et al. / Journal of Solid State Chemistry 233 (2016) 143–149
149
metal–organic frameworks, Chem. Soc. Rev. 38 (2009) 1477–1504.
[28] J. Gao, K. Ye, M. He, W.-W. Xiong, W. Cao, Z.Y. Lee, Y. Wang, T. Wu, F. Huo,
[5] J.R. Li, J. Sculley, H.C. Zhou, Metal–organic frameworks for separations, Chem.
Rev. 112 (2012) 869–932.
[6] M.P. Suh, H.J. Park, T.K. Prasad, D.W. Lim, Hydrogen storage in metal–organic
frameworks, Chem. Rev. 112 (2012) 782–835.
[7] Y.B. He, W. Zhou, G.D. Qian, B.L. Chen, Methane storage in metal–organic
frameworks, Chem. Soc. Rev. 43 (2014) 5657–5678.
[8] W.Y. Gao, Y. Chen, Y.H. Niu, K. Williams, L. Cash, P.J. Perez, L. Wojtas, J.F. Cai, Y.
S. Chen, S.Q. Ma, Crystal engineering of an nbo topology metal–organic fra-
mework for chemical fixation of CO2 under ambient conditions, Angew. Chem.
Int. Ed. 53 (2014) 2615–2619.
X. Liu, Q. Zhang, Tuningmetal–carboxylate coordinationin crystalline metal–
organic framework sthrough surfactant media, J. Solid State Chem. 206 (2013)
27–31.
[29] W.G. Lu, Z.W. Wei, Z.Y. Gu, T.F. Liu, J. Park, J. Park, J. Tian, M.W. Zhang, Q. Zhang,
T. Gentle III, M. Bosch, H.C. Zhou, Tuning the structure and function of metal–
organic frameworks via linker design, Chem. Soc. Rev. 43 (2014) 5561–5593.
[30] X. Zhao, X.H. Bu, T. Wu, S.T. Zheng, L. Wang, P.Y. Feng, Selective anion exchange
with nanogated isoreticular positive metal–organic frameworks, Nat. Com-
mun. 4 (2013) 2344–2345.
[31] J.S. Qin, S.R. Zhang, D.Y. Du, P. Shen, S.J. Bao, Y.Q. Lan, Z.M. Su, A microporous
anionic metal–organic framework for sensing luminescence of lanthanide(III)
ions and selective absorption of dyes by ionic exchange, Chem. Eur. J. 20
(2014) 1–7.
[9] Y.M. Li, Z.F. Ju, B.L. Wu, D.Q. Yuan, A water and thermally stable metal–organic
framework Featuring selective CO2 adsorption, Cryst. Growth Des. 13 (2013)
4125–4130.
[10] Y. Han, J.R. Li, Y.B. Xie, G.S. Guo, Substitution reactions in metal–organic fra-
meworks and metal–organic polyhedra, Chem. Soc. Rev. 43 (2014) 5952–5981.
[11] C.K. Brozek, M. Dincă, Cation exchange at the secondary building units of
metal–organic frameworks, Chem. Soc. Rev. 43 (2014) 5456–5467.
[12] T. Zhang, W.B. Lin, Metal–organic frameworks for artificial photosynthesis and
photocatalysis, Chem. Soc. Rev. 43 (2014) 5982–5993.
[13] C.C. Wang, J.R. Li, X.L. Lv, Y.Q. Zhang, G.S. Guo, Photocatalytic organic pollu-
tants degradation in metal–organic frameworks, Energy Environ. Sci. 7 (2014)
2831–2867.
[14] R.X. Yao, R. Hailili, X. Cui, L. Wang, X.M. Zhang, A perfectly aligned 63 helical
tubular cuprous bromide single crystal for selective photo-catalysis, lumi-
nescence and sensing of nitro-explosives, Dalton Trans. 44 (2015) 3410–3416.
[15] L.E. Kreno, K. Leong, O.K. Farha, M. Allendorf, R.P. Van Duyne, J.T. Hupp, Metal–
organic framework materials as chemical sensors, Chem. Rev. 112 (2012)
1105–1125.
[16] Z.C. Hu, B.J. Deibert, J. Li, Luminescent metal–organic frameworks for chemical
sensing and explosive detection, Chem. Soc. Rev. 43 (2014) 5815–5840.
[17] B.L. Chen, S.C. Xiang, G.D. Qian, MetalꢁOrganic frameworks with functional
pores for recognition of small molecules, Acc. Chem. Res. 43 (2010) 1115–1124.
[18] H.Y. Ren, C.Y. Han, M. Qu, X.M. Zhang, Luminescent group 12 metal tetra-
carboxylate networks as probe for metal ions, RSC Adv. 4 (2014) 49090–49097.
[19] S.L. Qiu, M. Xue, G.S. Zhu, Metal–organic framework membranes: from
synthesis to separation application, Chem. Soc. Rev. 43 (2014) 6116–6140.
[20] B. Wang, Y.B. Xie, H. Yang, M. Li, J.R. Li, A fluorescent 3-D metal-organic fra-
mework with unusual tetranuclear zinc secondary building units, J. Coord.
Chem. 67 (2014) 3484–3491.
[32] D.M. Chen, W. Shi, P. Cheng, A cage-based cationic body-centered tetragonal
metal–organic framework: single-crystal to single-crystal transformation and
selective uptake of organic dyes, Chem. Commun. 51 (2015) 370–372.
[33] Z.F. Zhu, Y.L. Bai, L.L. Zhang, D.F. Sun, J.H. Fang, S.R. Zhu, Two nanocage anionic
metal–organic frameworks with rht topology and {[M(H2O)6]6}12 þ charge
aggregation for rapid and selective adsorption of cationic dyes, Chem. Com-
mun. 50 (2014) 14674–14677.
[34] X.L. Lv, M.M. Tong, H.L. Huang, B. Wang, L. Gan, Q.Y. Yang, C.L. Zhong, J.R. Li, A
high surface area Zr(IV)-based metal–organic framework showing stepwise
gasad sorption and selective dye uptake, J. Solid State Chem. 223 (2014)
104–108.
[35] J.A. Johnson, X. Zhang, T.C. Reeson, Y.S. Chen, J. Zhang, Facile control of the
charge density and photocatalytic activity of an anionic indium porphyrin
framework via in situ metalation, J. Am. Chem. Soc. 136 (2014) 15881–15884.
[36] E.H. Victor Lo, A.I. Minett, A.T. Harris, T.L. Church, Dichotomous adsorption
behaviour of dyes on an amino-functionalised metal–organic framework,
amino-MIL-101(Al), J. Mater. Chem. A 2 (2014) 193–203.
[37] L.L. Lv, J. Yang, H.M. Zhang, Y.Y. Liu, J.F. Ma, Metal–Ion exchange, small-mo-
lecule sensing, selective dye adsorption, and reversible iodine uptake of three
coordination polymers constructed by a new resorcin[4]arene-Based tetra-
carboxylate, Inorg. Chem. 54 (2015) 1744–1755.
[38] Y. Han, S.N. Sheng, F. Yang, Y.B. Xie, M.J. Zhao, J.R. Li, Size-exclusive and co-
ordination-induced selective dye adsorption in a nanotubular metal–organic
framework, J. Mater. Chem. A 3 (2015) 12804–12809.
[39] H.H. Li, X.H. Zeng, H.Y. Wu, X. Jie, S.T. Zheng, Z.R. Chen, Incorporating guest
molecules into honeycomb structures constructed from uranium(VI)-poly-
carboxylates: structural diversities and photocatalytic activities for the de-
gradation of organic dye, Cryst. Growth Des. 15 (2015) 10–13.
[21] Y.B. Xie, H.Y. Zheng, F. Yang, B. Wang, J.P. Zhao, H. Yang, J.R. Li, An anti-
ferromagnetic metal-organic framework with high symmetry octanuclear
Mn8(
2606–2614.
μ
4-O)3(COO)12 secondary building units, J. Coord. Chem. 67 (2014)
[40] R. Zhang, S.L. Ji, N.X. Wang, L. Wang, G.J. Zhang, J.R. Li, Coordination-driven
in situ self-assembly strategy for the preparation of metal–organic framework
hybrid membranes, Angew Chem. Int. Ed. 53 (2014) 9775–9779.
[41] I. Papadaki, C.D. Malliakas, T. Bakas, P.N. Trikalitis, Molecular supertetrahedron
[22] W.-W. Xiong, J. Miao, K. Ye, Y. Wang, B. Liu, Q. Zhang, Threading chalcogenide
layers with polymer chains, Angew. Chem. Int. Ed. 54 (2015) 546–550.
[23] W.-W. Xiong, E.U. Athresh, Y.T. Ng, J. Ding, T. Wu, Q. Zhang, Growing crystalline
chalcogenidoarsenates in surfactants: from zero-dimensional cluster to three-
dimensional framework, J. Am. Chem. Soc. 135 (2013) 1256–1259.
[24] W. Xiong, G. Zhang, Q. Zhang, New strategies to prepare crystalline chalco-
genides, Inorg. Chem. Front. 1 (2014) 292–301.
[25] W.-W. Xiong, P.-Z. Li, T.-H. Zhou, A.I.Y. Tok, R. Xu, Y. Zhao, Q. Zhang, Kinetically
controlling phase transformations of crystalline mercury selenidostannates
through surfactant media, Inorg. Chem. 52 (2013) 4148–4150.
[26] H.-S. Lu, L. Bai, W.-W. Xiong, P. Li, J. Ding, G. Zhang, T. Wu, Y. Zhao, J.-M. Lee,
Y. Yang, B. Geng, Q. Zhang, Surfactant media to grow new crystalline cobalt
1,3,5-benzenetricarboxylate metalꢁorganic frameworks, Inorg. Chem. 53
(2014) 8529–8537.
nuclear Fe33þFe2þ
9968–9970.
(μ3
–
Ο)(
decorated with exposed suμlf3o–nSaOte4)g3(r–oCuOps2)b3ucillutsftreorms, Imnoixregd. -Cvhaelemn.c4e8te(t2r0a0-9)
[42] N. Zhang, Q.Y. Liu, Y.L. Wang, L.L. Chen, Z.B. Wen, A two-dimensional co-
ordination polymer with Eu(III) luminescence sensitized by an aromatic 4,8-
disulfonyl-2,6-naphthalenedicarboxylic acid ligand, Inorg. Chem. Commun. 20
(2012) 299–302.
[43] G.M. Sheldrick, SHELXTL 2008/4, Structure Determination Software Suite,
Bruker AXS, Madison, Wisconsin, USA.
[44] L.H. Xie, J.B. Lin, X.M. Liu, W. Xue, W.X. Zhang, S.X. Liu, J.P. Zhang, X.M. Chen,
Organic ammonium ion-occluded flexible coordination polymers Thermal
activation, structure transformation and proton transfer, Sci. China Chem. 53
(2010) 2144–2151.
[45] A.L. Spek, Single-crystal structure validation with the program PLATON, J. Appl.
Crystallogr. 36 (2003) 7–13.
[27] J. Gao, K. Ye, L. Yang, W.-W. Xiong, L. Ye, Y. Wang, Q. Zhang, Growing crystalline
zinc-1,3,5-benzenetricarboxylate metalꢁorganic frameworks in different
surfactants, Inorg. Chem. 53 (2014) 691–693.