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A stable anionic metal-organic framework with open coordinated sites: selective

separation toward cationic dyes and sensing properties
Wei Gaoab, Feng Liub, Chang-Wei Pana, Xiu-Mei Zhang*bc, Jie-Ping Liub and Qing-Yu Gao*a

CrystEngComm Accepted Manuscript

Published on 07 January 2019. Downloaded on 1/21/2019 3:03:07 AM.

Received (in XXX, XXX) Xth XXXXXXXXX 200X, Accepted Xth XXXXXXXXX 200X
DOI:

A novel metal-organic framework, [H2bpy]0.5[Cd3(OH)(L)2(bpy)(H2O)2]·(bpy)0.5·2H2O (1) H3L = 3-(3,5-dicarboxylphenyl)-4-

carboxylpyridine, bpy = 4,4’-bipyridine), with blue luminescence, was successfully synthesized under solvothermal conditions. Structure
analysis indicates that this compound is comprised of triangle [Cd3(µ3-OH)] clusters linked by the L ligands, forming a novel 3D
framework with a (3,3,8)-connected (42·6)(42·6)(44·55·64·78·87) topology and contains accessible Lewis-base sites (N), uncoordinated
carboxylate groups and coordinated H2O molecules, which are easy to recognize various small molecules. Meanwhile, this compound
exhibits microporous structure with the [H2bpy]2+ cations being located in the channels, which can be easily replaced by some cationic
dyes. Particularly, Cd-MOF-1 displays high water and pH stability. Based on aforementioned considerations, when Cd-MOF-1 was
immersed in the different metal ions aqueous solutions and different nitro explosives EtOH solutions, it performs as a highly selective
and sensitive sensing for Fe3+ ions and TNP (2,4,6-Trinitrophenol), Moreover, the probable sensing mechanism was also investigated in
detail. More interestingly, dye adsorption studies revealed that Cd-MOF-1 can adsorb cationic dyes in aqueous solution while the anionic
and neutral dyes can not be absorbed and the cationic dye adsorption amounts decrease with the increase of dye size. Therefore, Cd-
MOF-1 can potentially act as a column-chromatographic filter for the separation of dye molecules.
designing a fast and reliable method to detect TNP is of great
significance.6e, 9 Up to now, a great variety of analytical
Introduction techniques have been developed to detect these pollutants (Fe3+
ions and nitroaromatic compounds) such as mass spectrometry,10
With the rapid development of industry, environmental pollution infrared and electrochemical methods,11 fluorescence and
becomes more and more prominent. Therefore, designing and chemiluminescence.12 Compared with these traditional detection
synthesizing new materials to detect pollutants have attracted methods, the luminescent MOFs are more attractive due to their
tremendous attention in recent years.1 Metal-organic frameworks high sensitivity, high selectivity and short response time. In
(MOFs), as porous materials that consist of metal ions/clusters particular, the electron-rich frameworks, such as anionic MOFs
connected by organic ligands, have been intensively investigated or MOFs with electron-donating site (N), are good candidates for
owing to their fascinating typologies, unique properties and the detection of TNP because the electron transfer occurs from
potential applications such as catalysis,2 magnetism,3 gas storage frameworks to the electron-deficient TNP, which results in
and separation,4 ion-exchange5 and chemical sensing.6 Among luminescent changes.13
MOFs with various applications, the luminescent MOFs as The dyes have high toxicity and have been widely used in the
chemical sensors represent high selectivity and sensitivity for field of textiles, paper, printing, plastics, clothing and so on.14
detection of environment pollutants (metal ions, explosives, etc.) Therefore, the development of new materials for efficient
and have been widely studied.7 Fe3+ ions are an indispensable removal of dyes has received considerable attentions. So far, two
trace element in the organism and human body. However, main approaches have been explored: one is photocatalytic
excessive Fe3+ ions may affect signal transmission of cells and degradation15 and the other is adsorption.16 The latter is regarded
cause liver cell damage and fibrosis. Nitroaromatic compounds, as one of the most effective, feasible and promising ways. MOFs
such as nitrobenzene (NB), 1,3-dinitrobenzene (1,3-DNB) and have many advantages as adsorbents because their pore size,
2,4,6-trinitrophenol (TNP), are a class of important explosives. shape and chemical environment are regulated by the appropriate
They as chemical raw materials have been widely used in selection of metal ions and organic ligands. Specially, the ionic
laboratories and industrial production.8 Especially, TNP is a MOFs can selectively adsorb cationic or anionic dyes by ion
common model explosion analyte and it plays important roles in exchange interactions and in most instances, dye adsorption
leather, pharmaceutical and dye industries. However, this kind of depends on the size-exclusion effect.17 For example, Zhang et al.
compounds is toxic, explosive and harmful to the human body have reported a microporous anionic MOF,
and environment. Once TNP enters the human body through the [Zn(ABTC)0.5(NO3)][(CH3)2NH2]·DMA·3H2O, which can serve
food chain, it will do fatal harm to the human health. Therefore, as a column-chromatographic filter for the separation of dyes.17a

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Lan et al. have reported three mesoporous MOFs with size- sealed in a 25 mL vessel and heated at 180 °C for 2 days, giving
tailored cages which can be used for column-chromatographic the yellow block crystals of Cd-MOF-1. Yield: 69%, based on
separation for large dye molecules.17b H3L. Elem anal. calcd (%) for C48H38Cd3N6O17: C, 43.90; H, 2.92;
All above descriptions suggest the MOFs, especially ionic MOFs N, 6.40. Found: C, 43.95; H, 2.89; N, 6.46%. IR bands (KBr, cm-
or MOFs with electron-donating sites, have more unique 1): 3395s, 1629s, 1550s, 1434s, 1396s, 1294w, 1237w, 1072m,

advantages for the selective sensing small molecules and the 1011m, 939m, 939m, 842s, 776s, 689m.
selective adsorption of dyes. Consequently, from the viewpoint of
Crystal structure analysis
environmental protection, it is necessary to design and synthesis
Crystallographic data of Cd-MOF-1 were collected on a
of ionic MOFs for the detection and adsorption/ separation of
Bruker Apex II CCD diffractometer using graphite-
environment pollutants (Fe3+ ions, TNP and dyes). To meet the
monochromated Mo-Kα (λ = 0.71073 Å) radiation at 293 K.
requirements of the above applications, here we synthesized a
Empirical absorption corrections were applied using the
novel microporous anionic MOF,
SADABS program.18 The structures were solved by direct
[H2bpy]0.5[Cd3(OH)(L)2(bpy)(H2O)2]·(bpy)0.5·2H2O (1), using

CrystEngComm Accepted Manuscript

methods and refined by full-matrix least-squares on F2 with the
Cd(NO3)2 and 4,4’-bipyridine (bpy) and 3-(3,5-
SHELXL-2014 program.19 All non-hydrogen atoms refined with
dicarboxylphenyl)-4-carboxylpyridine (H3L) (Scheme 1). Cd-
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anisotropic thermal parameters. All the hydrogen atoms attached

MOF-1 displays a 3D network based on triangle [Cd3(µ3-OH)]
to carbon atoms were placed in calculated positions and refined
clusters and it can be used as a luminescent sensor for recyclable
using the riding model. The hydrogen atoms attached to H2O
selective detectability for Fe3+ ions and TNP molecules.
molecules or N atoms of bpy were located from the difference
Meanwhile, Cd-MOF (1) can selectively absorb cationic dye
Fourier maps and refined isotropically. The relevant
molecules because of its anionic framework. More importantly,
crystallographic data are listed in Table S1. The selected bond
Cd-MOF-1 can act as a column-chromatographic filter for
lengths and angles are shown in Table S2 (ESI†). CCDC number
efficient separation of mixed dyes in the aqueous system. The
is 1872878.
results illustrate that Cd-MOF-1 is a versatile material for
detection of Fe3+ ions and TNP molecules with high sensitivity
and selectivity, and high selective adsorption of dyes. Results and discussion
Crystal structure descriptions
Single-crystal X-ray analysis reveals that Cd-MOF-1
crystallizes in the monoclinic crystal system with the space group
of P21/c, displaying a 3D framework based on trinuclear [Cd3(μ3-
OH)] clusters. Its asymmetric unit is comprised of three Cd(II)
ions, two L ligands, one µ3-OH group, one coordinated bpy
ligand, two coordinated H2O molecules, a half lattice bpy
molecule, a half lattice protonated [H2bpy]2+ ion, and two lattice
H2O molecules. There are three kinds of independent CdII ions
Scheme 1. 3-(3,5-dicarboxylphenyl)-4-carboxylpyridine (H3L).
(Cd1, Cd2 and Cd3) in the framework. They all are six-
coordinated with distorted octahedral geometries, but with
Experimental section
somewhat difference: both Cd2 and Cd3 are furnished by one
Materials and physical measurements nitrogen atom from one bpy ligand, three carboxylate oxygen
atoms from three different L ligands, one µ3-OH oxygen atom
All chemicals including the organic ligand H3L (3-(3,5-
and one coordinated H2O molecule, while Cd1 is coordinated by
dicarboxylphenyl)-4-carboxylpyridine) were obtained from
five carboxylate oxygen atoms from three different L ligands and
commercial sources and were used as received. Elemental
one µ3-OH oxygen atom. The Cd-O bond distances are from
analysis (C, H, and N) was carried on an Elementar Vario El III
2.194(4) to 2.441(5) Å, and the Cd-N bond distances are 2.344(5)
elemental analyzer. Infrared spectra were recorded in the range of
and 2.351(5) Å (Table S2), which are comparable to those
500-4000 cm-1 using KBr pellets on a NEXUS 670 FT-IR
reported in the CdII compounds.20 It should be noted that Cd1 is
spectrometer. The TG curves were performed using a Mettler
weakly coordinated by one carboxylate oxygen atom (O3A), with
Toledo TGA/SDTA851 instrument at a heating rate of 5 °C min-1
a rather long Cd3-O distance of 2.84 Å. If this weak coordinated
under an air atmosphere over the temperature range of 25-800 °C.
bond is included, the geometry of Cd1 may be described as a
Powder X-ray diffraction (PXRD) was measured at room
distorted single-cap triangular prism. Three CdII ions are bridged
temperature on a Bruker D8-Advance diffractometer equipped
by one μ3-OH group into a triangle [Cd3(µ3-OH)] cluster (Fig. 1a),
with Cu Kα. Luminescence excitation/emission spectra were
which is reinforced by three carboxylate bridges and two
recorded on a Jasco FP-8300. The UV-Vis absorption spectra
independent O-H···O bridges: one involves the coordinated H2O
were measured in the 200-800 nm range with a Pgeneral TU-
molecule (O15) and the coordinated carboxylate oxygen (O1)
1901 spectrophotometer.
with O15···O1 = 2.757(7) Å and O15-H···O1 = 173.3(3)°; the
Synthesis of Cd-MOF-1. other one also involves the coordinated H2O molecule (O13) and
A mixture of bpy (0.0078 g, 0.05 mmol) and H3L(0.017 g, 0.05 the coordinated carboxylate oxygen (O8) with O13···O8 =
mmol), H2O (8 mL) CH3CN (6 mL) was stirred for 30 min and 2.683(8) Å and O13-H···O2 =162.9(4)°. Two different
then Cd(NO3)2·6H2O was added to the solution. The mixture was coordination modes of the L ligands are recognized in Cd-MOF-1:

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one mode serves as a μ5 bridge, in which one carboxylate group sample (Fig. S5). And the N2 adsorption of Cd-MOF-1 is
adopts μ2-η1:η1-bridging mode, another adopts chelating bridging negligible, suggesting that the framework may distort or collapse
mode and the third carboxylate group is in the monodentate mode; into the amorphous after the removal of the guest molecules.
the other acts as a μ6 bridge, in which two carboxylate group
Luminescence properties
adopt μ2-η1:η1-bridging mode and the third carboxylate group
The solid state luminescent measurement of the free H3L
adopts chelating bridging mode. Adjacent clusters are further
ligand and Cd-MOF-1 were carried out at room temperature (Fig.
linked by six L ligands and two bpy ligands into a 3D framework
S6, S7). The free H3L ligand shows a strong broad emission peak
(Fig, 1b), containing exposed nitrogen atoms sites of the L
at 443 nm (λex = 357 nm), which may be ascribed to the ligand-
ligands (Fig. S1). PLATON calculations revealed that the
centered (LC) π* → π electronic transitions. The broad emission
solvent-accessible volume is about 43.4% of the cell volumes.
peak of Cd-MOF-1 is at 454 nm (λex = 322 nm), which also are
The open space in the framework is occupied by 1/2 bpy
attributable to intraligand transitions because the CdII ions are
molecule, 1/2 protonated [H2bpy]2+ ion and two H2O molecules.
very difficult to oxidize or to reduce.
Thus, the anionic framework of Cd-MOF-1 is compensated for

CrystEngComm Accepted Manuscript

Selective sensing of cations
by the protonated [H2bpy]2+ ions. Noteworthily, the lattice bpy
Owing to intense luminescence and the good stability of Cd-
and [H2bpy]2+ spacers are assembled through N5-H···N6
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MOF-1, it can be employed as a luminescence sensor for

interactions [N5···N6 = 2.842(3) Å and N5-H···N6 =172.8(4)°]
detection of metal ions. The finely ground samples (3 mg) of Cd-
to give a 1D chain (Fig. S2). Topologically, Each L ligand as 3-
MOF-1 were immersed in the aqueous solutions containing
connected nodes, with trinuclear clusters as 8-connected nodes,
M(NO3)n (1.0 mM; Mn+ = Hg2+, Na+, K+, Mg2+, Ag+, Al3+, Co2+,
and then the 3D network can be simplified to a 3,3,8-connected
Mn2+, Zn2+, Cu2+, Ni2+, Cr3+, Fe2+ and Fe3+, respectively). As
net with a Schläfli symbol of (42·6)(42·6)(44·55·64·78·87)(Fig. 1c).
shown in Fig. 2a, the luminescent intensity of Cd-MOF-1 (λmax =
454 nm) is largely dependent on metal ions, particularly Fe3+ ions,
which exhibits the almost drastic and rapid quenching effects.
Cr3+ and Fe2+ ions show the moderate quenching effects while
other metal ions show no obvious change on luminescent
intensity. Such different luminescent effects suggest that Cd-
MOF-1 can act as a chemical sensor for detection of Fe3+ ions.
Further, to explore the sensing selectivity of Cd-MOF-1 towards
Fe3+ ions in the presence of other metal ions, anti-interference
experiments were performed. The samples (3 mg) of Cd-MOF-1
were immersed in aqueous solutions containing mixed metal ions
(Hg2+, Na+, K+, Mg2+, Ag+, Al3+, Co2+, Mn2+, Zn2+, Cu2+, Ni2+,
Cr3+, Fe2+, 1.0 mM). As shown in Fig. 2b, the luminescent
intensity at 454 nm shows a little change. However, the
luminescent intensity was almost completely quenched by
introducing an equal amount of Fe3+ ions into above solutions.
The results indicated that Fe3+ ions can still be sensed in the
Fig. 1 (a) Coordination environments of Cd2+ ions and and the presence of other metal ions. That is to say, Cd-MOF-1 can sense
ligands (Symmetry codes are A -x+1, y+1/2, -z+3/2; B -x+2, - Fe3+ ions with high selectivity. In addition, to study the
y+1, -z+2; C -x+1, -y+1, -z+1; D x-1, -y+3/2, z-1/2 and E -x+2, sensitivity of Cd-MOF-1 as a Fe3+ sensor, the quantitative
y+1/2, -z+3/2); (b) 3D network of Cd-MOF (1) and the lattice luminescent titration experiments were performed by changing
[H2bpy]2+ and bpy molecules; (c) The view of the 3D (3,3,8)- the concentration of Fe3+ solutions from 1 mM to 10-3 mM. As
connected topology of Cd-MOF-1. shown in Fig. 2c, the intensities at 454 nm are gradually
decreased with the concentration of Fe3+ ions increasing. Finally,
Thermal analysis and powder XRD patterns
the quenching efficiency could almost reach 98.4% (Fig. S8)
To evaluate the stability of Cd-MOF-1, TGA measurement was
when the concentration of Fe3+ ions increased to 1 mM.
performed and is shown in Fig. S3. The TGA curve of Cd-MOF-
Furthermore, the quantified value of the quenching efficiency
1 shows weight loss of 11.4% (calc. 11.5%) in the range of 28-
can be obtained by the Stern-Volmer equation: I0/I = 1 + Ksv[C],
178 °C, which corresponds to the loss of lattice and coordinated
where [C] is the concentration of the analyte, I0 and I are the
water molecules and lattice bpy molecules, and then no obvious
luminescent intensity without and with addition of the analyte,
weight loss is observed until the collapse of the framework at 311
respectively and KSV is the Stern-Volmer constant. As shown in
°C, indicating its good thermal stability. The experimental PXRD
Fig. 2d, the Stern-Volmer curve of Cd-MOF-1 shows a nearly
patterns of Cd-MOF-1 are in agreement with that for calculated
linear relationship in low the concentration of Fe3+ ions and the
from the single-crystal data. And Cd-MOF-1 still can maintain its
Ksv value is calculated to be 5.27 × 104 M-1. However, Stern-
crystalline structure in water, boiling water and water with pH =
Volmer curves deviate from the linearity in high concentrations
2 and 12 for several hours as demonstrated by PXRD (Fig. S4).
(Fig. S9), which can be explained by self-absorption or energy-
However, the PXRD pattern for the evacuated sample of Cd-
transfer processes.
MOF-1 obtained by heating Cd-MOF-1 at 160 °C under a
vacuum for 24 h is different from that of the as-synthesized

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water, which excludes the possibility of (II). Thirdly, we studied

the UV-vis absorption spectrum of the analytes in the aqueous
phase. As shown in Fig. S11, only the Fe3+ aqueous solution
shows a strong absorption band between 270 to 320 nm, which
overlaps the excitation peak of Cd-MOF-1, whereas the solutions
of other metal ions have very weak or no obvious absorption
band. In other words, the luminescent quenching of Cd-MOF-1
may be due to the competition absorption of excitation energy
between Fe3+ aqueous solution and framework. Additionally, the
interaction between the framework and Fe3+ ions may be lead to
the luminescent quenching. However, this kind of the interaction
is very weak because the samples quenched by Fe3+ (Fe3+@Cd-
MOF-1) can be easily washed with deionized water to remove

CrystEngComm Accepted Manuscript

Fe3+ ions.
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Detection of small organic molecules.

Fig. 2 (a) (a) Luminescence intensities at 454 nm of Cd-MOF-1 To explore the potential applications of Cd-MOF-1 in sensing
dispersed in the aqueous solutions of different metal ions; (b) small solvent molecules, the finely ground samples (3 mg) of Cd-
Luminescence intensities at 545 nm for Cd-MOF-1, H2O (left MOF-1 were immersed in methanol (MeOH), ethanol (EtOH),
column), with the addition of other metal ions (middle column), DMF, DMA, acetonitrile (CH3CN), trichloromethane (CHCl3),
and the addition of Fe3+ ions (right column); (c) The emission acetone, H2O, benzene (BZ), toluene and nitrobenzene (NB) to
spectra of Cd-MOF-1 in water solution with incremental addition form stable suspensions. As shown in Fig. 4a, the luminescent
of Fe3+ ion aqueous solution; (d) The Stern-Volmer plot of I0/I intensity is largely dependent on small molecules. In particular,
versus Fe3+ concentration. NB shows an evident quenching effect, which inspires us to
The detection limits of Cd-MOF-1 is estimated to be 1.34 μM by further investigate the possibility of sensing other nitro
ratio of 3σ/S in which δ is the standard deviation of the blank explosives (NACs). Therefore, the finely ground samples (3 mg)
solutions measurement and S is the slope of the calibration curve. of Cd-MOF-1 were immersed in EtOH solutions of nitrobenzene
In order to reduce the cost of material, the recyclable (NB), 1,3-dinitrobenzene (1,3-DNB) and 2,4,6-trinitrophenol
performance as a Fe3+ luminescent probe have attracted great (TNP). As shown in Fig. 4b, all three NACs can weaken the
attention. Fortunately, the luminescent intensities of Cd-MOF-1 luminescent intensities of Cd-MOF-1 to some degree. Thus, the
are easily recovered by centrifuging the suspensions after sensing sensing properties of Cd-MOF-1 for above three NACs are
Fe3+ ions and washing several times with deionized water (Fig. 3). further investigated.
More importantly, Cd-MOF-1 sample can be regenerated and
reused after five cycles.

Fig. 4 (a) The luminescence intensity at 454 nm of Cd-MOF-1 in

various pure solvents; (b) The luminescence intensity at 454 nm
of Cd-MOF-1 dispersed in the different NACs (200 ppm) in
EtOH solutions.
As shown in Fig. 5a-c, the luminescent intensities gradually
decrease with increasing NB, 1,3-DNB and TNP concentration,
Fig. 3 Five cycle tests of Cd-MOF-1 towards sensing Fe3+ in
respectively. When the concentration of NB, 1,3-DNB and TNP
water system.
increased to 1400/1000/200 ppm, the quenching efficiency could
Up to now, the luminescent quenching induced by metal ions
reach 90.6/94.2/97.7 % (Fig. S12-S14). And the TNP shows the
may be owing to following four approaches: (I) the collapse of
highest quenching efficiency (97.7%) among the NACs (NB:
the host framework; (II) the ions exchange between central metal
61.4%, 1,3-DNB: 65.9%) in the same concentration of 200 ppm
ions of compounds and the targeted metal ions; (III) the
(Fig. 4b), indicating Cd-MOF-1 can selectively detect TNP from
interaction between metal ions and organic ligands; (IV) the
NB and 1,3-DNB. Moreover, the PXRD patterns (Fig. S15) of
overlap between the excitation wavelength energy between the
the immersed samples (NB, 1,3-DNB and TNP) are well
framework and analyte. Herein, the possible qeuenching
consistent with the simulated one, confirming the stability of the
mechanism of Cd-MOF-1 toward Fe3+ ions has been further
framework in the process of detecting NACs. Furthermore, the
investigated. Firstly, we excludes the possibility of (I) because
quantified value of the quenching efficiency can be obtained
the PXRD pattern of Fe3+@Cd-MOF-1 is very well agreement
using the Stern-Volmer equation: I0/I = 1 + Ksv[C]. Further
with the the simulated one (Fig. S10). Secondly, the samples of
analysis revealed that there exist the nearly linear relationships
Cd-MOF-1 are easily regenerated by washing several times with

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between the luminescent intensities and the TNP concentrations MOF-1 towards TNP, the anti-interference experiments were also
in the range of 0-20 μM. And the Ksv value is calculated to be performed. As shown in Fig. S16, the luminescent intensity
2.34 × 104 M-1 (Fig. 3d inset). However, the plots subsequently rapidly drops when introducing TNP into the single NB or 1,3-
become bent upward with the increasing concentration (Fig. 3d), DNB solution, indicating that Cd-MOF-1 can selectively detect
which may be attributed to both static and dynamic quenching towards TNP.
simultaneously. According to 3δ/S, the detection limit is obtained
to be 0.21 μM. To further explore the sensing selectivity of Cd-

CrystEngComm Accepted Manuscript

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Fig. 5 Emission spectra of Cd-MOF-1 dispersed in EtOH solutions in different concentrations of NB (a), 1,3-DNB (b) and TNP (c). (d)
The Stern-Volmer plot of I0/I vs TNP concentration for Cd-MOF-1 (The insets indicate the quenching linearity relationship at low
concentrations of TNP).

Most importantly, Cd-MOF-1 can be easily regenerated by the excitation band of Cd-MOF-1 and the absorption band of the
washing several times with EtOH and the quenching efficiency of TNP, NB and 1,3-DNB. Therefore, the competition between the
five cycles maintains high efficiency (Fig. 6). All these results excitation wavelength energy of Cd-MOF-1 and the absorption of
confirm that Cd-MOF-1 can act as a fast and recyclable sensor NACs may cause a luminescent quenching or decrease of the
for sensing of TNP. luminescence. Additionally, the weak hydrogen bonding
interactions between the open N atoms of the L ligands in Cd-
MOF-1 and the -OH groups of the TNP may be responsible for
the luminescent quenching. Finally, as mentioned above, the
luminescence of Cd-MOF-1 originates from the intraligand of the
L ligand. Thus, the electron-rich L ligand can give a higher low
unoccupied molecular orbital (LUMO) energy than the LUMOs
of the electron deficient nitro compounds, which can force the
electrons transfer from the conduction-band (CB) of the Cd-
MOF-1 to the LUMOs of nitro compounds, leading to the
luminescent quenching. On the basis of above discussion, the
quenching effect of Cd-MOF-1 towards TNP may be attributed to
Fig. 6 Five cycle tests of Cd-MOF-1 towards sensing TNP in the competitive adsorption of energy and the electronic transfer
EtOH solutions. between the framework and TNP, and the electronic static
To understand the luminescent quenching mechanism, UV-Vis interactions between the free Lewis-base sites of the L ligands in
spectra of EtOH solutions of the three nitro compounds were Cd-MOF-1 and the -OH groups of the TNP.
recorded. As shown in Fig. S17, there is a good overlap between

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Adsorption and separation of dyes solution was recorded through UV-Vis spectra. As shown in Fig.
The anionic framework of Cd-MOF-1 and excellent stability in 7a-c, the adsorption peaks of all three cationic dyes are gradually
aqueous system encourage us to explore its dyes selective decreased as time passed, indicating the concentration of cationic
adsorption in water. Here, we choose six kinds of organic dyes dyes in aqueous solution gradually decreases. In addition, it is
with different charges and size (Fig. S18), including cationic dyes evidently seen from Fig. 7 that MB can be adsorbed rapidly and
(methylene blue (MB), basic green 1(BG1) and Rhodamine B completely nearly within 120 min, while it will take about 280
(Rh B)), neutral dye basic red 1 (BR1) and anionic dyes (methyl min for BG 1 to adsorb completely nearly, and RhB can not be
orange (MO) and congo red (CR)) to evaluate the adsorption adsorbed completely even after 7 h. The adsorption capacity of
ability of Cd-MOF-1 toward organic dyes. Typically, the finely Cd-MOF-1 for MB, BG 1 and RhB is 187, 102 and 12 mg g-1,
ground samples (20 mg) of Cd-MOF-1 were immersed in the respectively. Noteworthily, the MB adsorption capacity is higher
aqueous solutions containing different kinds of dyes (4 mL, 1 than some reported materials.7a, 21 The salient different adsorption
mM). It was found that all the cationic dyes can be absorbed and behaviors for cationic dyes may be attributable to the shape and
the light yellow samples gradually became blue for MB, green size of the dyes. These three kinds of cationic dyes show different

CrystEngComm Accepted Manuscript

for BG 1 and red for Rh B while the neutral and anionic dyes can sizes: MB < BG 1 < RhB, and MB is linear but BG 1 and Rh B
not be absorbed (Fig. 7a-c inset), indicating that Cd-MOF-1 can are planar. Therefore, the shape and size of MB may be a more
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selectively absorb cationic dyes. Moreover, the crystalline suitable size for the 1D channels of Cd-MOF-1 compared with
integrity of Cd-MOF-1 can be maintained after the adsorption the other two dyes, so Cd-MOF-1 can rapidly and completely
dyes which was confirmed by the PXRD (Fig. S19). Meanwhile, absorb MB dyes.
the capability of Cd-MOF-1 to absorb cationic dyes in aqueous

Fig. 7 UV-vis spectra of MB (a), BG 1 (b) and Rh B (c) in aqueous solutions at different time during the adsorption for Cd-MOF-1, The
insets are the corresponding photographs before (left) and after (right) the adsorption.
Encouraged by the above results, we attempt to explore Cd-
To confirm whether the selective absorption is due to ion- MOF-1 as a potential absorbent to remove cationic dyes (MB)
exchange, dye releasing experiment was performed in deionized from effluents. Therefore, the finely ground samples (20 mg) of
water and the saturated solution of NaCl which is monitored by Cd-MOF-1 were immersed in aqueous solutions containing two
UV-Vis spectra (Fig. 8, S20-S21). The result shows that the MB dyes with different charges (MB/MO, MB/BR 1) at room
and BG1 dyes can be gradually released in the saturated solution temperature. The adsorption behaviors of Cd-MOF-1 toward the
of NaCl, while in deionized water this two kinds of dyes are mixed dyes (MB/MO, MB/BR 1) were monitored by UV-Vis
hardly released. The release of MB reaches a plateau within 180 spectra. As shown in Fig. 9, the characteristic peaks of MB
min while the release of BG 1 takes 420 minutes to reach the decrease gradually with time passed while the peaks of MO and
plateau. Hence, we can speculate that selective absorption for BR 1 unchanged. Meanwhile, the samples color deepened
MB and BG1 is due to interaction between cationic dyes and quickly and the color of the mixed dye solution gradually
anionic framework. For RhB dyes, it is very hardly released changed into single component color: from cyan to light orange
whether in aqueous solution or in the saturated solution of NaCl for MB/MO, as well as from olive to orange-red for MB /BR 1.
because the larger size of RhB dyes are not easily exchanged by These results indicated that the cationic dyes MB were rapidly
Na+ ions. The release percentage for MB, BG1 and RhB is 21.8%, absorbed into the framework of Cd-MOF-1, while anionic and
5.9%, 3.6%, respectively, which are not very high. neutral dye molecules were left in the solution. This may be
ascribed to the charge of MB is positive which is opposite to the
framework of Cd-MOF-1. The opposite charge enhances the
columbic interaction between the anionic framework and dyes
and the ion-exchange between [H2bpy]2+ and cationic dyes
promote the adsorption simultaneously. For the neutral dye BR 1,
the interactions are weaker and almost no adsorption is observed.
As has been stated above, Cd-MOF-1 has the potential
application of removal cationic dyes from effluents.
Fig. 8 (a) UV-vis spectra of the MB released from MB@Cd-
MOF-1 in a saturated NaCl aqueous solution. (b) The release-rate
comparison of MB from MB@Cd-MOF-1 in a saturated NaCl
aqueous solution and deionized water.

6 | Journal Name, [year], [vol], 00–00 This journal is © The Royal Society of Chemistry [year]
 Page 7 of 9 CrystEngComm View Article Online
DOI: 10.1039/C8CE02060D

sensor to detect Fe3+ ions and TNP and excellent cationic dye
adsorbent.
Acknowledgements
We are thankful for the key projects of Anhui province
university outstanding youth talent support program
(gxyqZD2017050). The Fundamental Research Funds for
the Central Universities (No. 2015XKZD09).
Fig. 9 UV-vis spectra of the mixture dyes for MB/MO (a) and Notes and references
MB /BR 1 (b). The insets are the corresponding photographs aCollege of Chemical Engineering China University of Mining and
before (left) and (right) the adsorption. Technology, Xuzhou, Jiangsu 221116, China, E-mail:
gaoqy@[Link]
To further confirm the separation abilities of Cd-MOF-1 to a bCollege of Chemistry and Materials Science, Huaibei Normal

dye mixture, a chromatographic column was prepared by using University, Anhui 235000, China, E-mail: zhangxiumeilb@[Link]

CrystEngComm Accepted Manuscript

cState Key Laboratory of Coordination Chemistry, Nanjing University,
the powder samples of Cd-MOF-1 (70 mg) as the filter. As
displayed in Fig. 10, when 40 mL the aqueous solutions of mixed Nanjing, China,
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MB/MO (1:1, 1 mmol) were passed through the column at the

Electronic Supplementary Information (ESI) available: [The data can
room temperature, the orange dye MO is eluted out immediately be obtained free of charge via
and the color of the column gradually became blackish green, <[Link] or from the
indicating that the blue dye MB was absorbed inside Cd-MOF-1. Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge
No blue dye MB is observed after washing with deionized water. CB2 1EZ, UK; fax:(+44) 1223-336-033; or e-mail:
deposit@[Link],Table S1-S2 and Fig. S1-S21]. See DOI:
However, when the saturated NaCl solutions were traversed the 10.1039/b000000x/. CCDC Number: 1872878. For ESI and
column, the MB dye is eluted out again. All results manifested crystallographic data in CIF or other electronic format See DOI:
that Cd-MOF-1 could be used to separate dyes with opposite 10.1039/x0xx00000x
charges. 1. (a) H.-Y. Zhao, J. Jin, W.-J. Tian, R. Li, Z. Yu, W. Song, Q. Cong,
B. Zhao, Y. Ozakic, J. Mater. Chem. A., 2015, 3, 4330-4337; (b) C.-H.
Zhu, G.-W. Meng, P. Zheng, Q. Huang, Z.-B. Li, X.-Y. Hu, X.-J.
Wang, Z.-L. Huang, F.-D. Li, N.-Q. Wu, Adv. Mater., 2016,
4871-4876; (c) Q. Sui, P. Li, N.-N. Yang, T. Gong, R. Bu, E.-Q.
Gao, ACS Appl. Mater. Interfaces, 2018, 10, 11056-11062.
2. (a) J. Liu, L. Chen. H. Cui, J. Zhang, L. Zhang, C.-Y. Su,
Chem. Soc. Rev., 2014, 43, 6011-6061; (b) X.-P. Wu, L.
Gagliardi, D.-G. Truhlar, J. Am. Chem. Soc., 2018, 140, 7904-
7912; (c) H. Xu, J. Gao, D. Jiang, Nat. Chem., 2015, 7, 905-
912; (d) P. Puthiaraj, K. Pitchumani, Chem. Eur. J., 2014, 20,
8761-8770.
3. (a) M. J. Giansiracusa, E. Moreno-Pineda, R. Hussain, R. Marx,
M. M. Prada, P. Neugebauer, S. Al-Badran, D. Collison, F. Tuna,
Fig. 10 Column-chromatographic separation of MB/MO mixture J. V. Slageren, S. Carretta, T. Guidi, E. J. L. McInnes, R. E. P.
in which (I) as-prepared column, (II) 60 min after the addition of Winpenny, N. F. Chilton, J. Am. Chem. Soc., 2018, 140, 2504-
MB/MO mixture, (III) washing with deionized water and (IV) 2513; (b) Y.-X. Wang, Y.-N.-N. Ma, Y.-S. Chai, W. Shi, Y. Sun,
washing with NaCl@water solution. P. Cheng, J. Am. Chem. Soc., 2018, 140, 7795-7798; (c) K.
Zhang, V. Montigaud, O. Cador, G.-P. Li, B. L. Guennic, J. K.
Conclusions Tang, Y.-Y. Wang, Inorg. Chem., 2018, 57, 8550-8557; (d) P. Hu,
In summary, a Cd-based MOF (Cd-MOF-1) with a rare X.-N. Wang, C.-G. Jiang, F. Yu, B. Li, G.-L. Zhuang, T.-L.
(3,3,8)-connected topology was solvothermally synthesized, Zhang, Inorg. Chem., 2018, 57, 8639-8645.
which shows remarkable water stability and chemical stability in 4. (a) S. Qiu, M. Xue, G. Zhu, Chem. Soc. Rev., 2014, 43,
various organic solvents. The structure of this compound features 6116-6140; (b) D.-Q. Yuan, D. Zhao, D.-F. Sun, H.-C. Zhou,
a triangle [Cd3(µ3-OH)] cluster linked by the pyridyl- Angew. Chem. Int. Ed., 2010, 49, 5357-5361. (c) E. Barea, C.
tricarboxylate ligand (L) and bpy ligand to generate a 3D Montoro, J. A. R. Navarro, Chem. Soc. Rev., 2014, 43, 5419-
framework. Cd-MOF-1 displays highly selective and sensitive 5430; (d) Y.-B. He, W. Zhou, G.-D. Qian, Chen, B.-L. Chem.
detection of TNP in EtOH solution. More importantly, this sensor Soc. Rev., 2014, 43, 5657-5678; (e) Y. Yan, M. Juríček, F. X.
can be easily regenerated, suggesting good recyclability for the N. A. Coudert, Vermeulen, S. Grunder, A. Dailly, W. Lewis,
detection of Fe3+ ions and TNP. Moreover, Cd-MOF-1 displays A. J. Blake, J. F. Stoddart, M. Schröder, J. Am. Chem. Soc.,
selective absorption toward cationic dyes and can potentially act 2016, 138, 3371-3381; (f) Y.-W. Li, H. Yan, T.-L. Hu, H.-Y.
as a column-chromatographic filter to adsorb MB from MB/MO Ma, D.-C. Li, S.-N. Wang, Q.-X. Yao, J.- M. Dou, J. Xu, X.-H. Bu,
and MB/BR 1 in their mixed water solution. Thus, this work Chem. Commun., 2017, 53, 2394-2397.
provides a new functional material used as excellent luminescent 5. (a) Y. Noori, K. Akhbari, RSC Adv., 2017, 7, 1782-1808; (b)
M.-L. Feng, D.-N. Kong, Z.-L. Xie, X.-Y. Huang, Angew.
Chem., 2008, 74, 8623-8626; (c) P. Wang, J.-P. Ma, Y.-B.

This journal is © The Royal Society of Chemistry [year] Journal Name, [year], [vol], 00–00 | 7
 CrystEngComm Page 8 of 9
View Article Online
DOI: 10.1039/C8CE02060D

Dong, R.-Q. Huang, J. Am. Chem. Soc., 2007, 129, 10620- 15. (a) J. Li, Y. Yu, L.-Z. Zhang, Nanoscale, 2014, 6, 8473-8488; (b)
10621; (d) S.-H. Yang, S. K. Callear, A. J. Ramirez-Cuesta, S.-F. Yang, C.-G. Niu, D.-W. Huang, H. Zhang, C. Liang, G.-M.
W. I. F. David, J. L. Sun, A. J. Blake, N. R. Champness, M. Zeng, Environ. Sci.: Nano., 2017, 4, 585-595; (c) L.-X. Hu, G.-H.
Schröder, Faraday Discuss., 2011, 151, 19-36. Deng, W.-C. Lu, S.-W. Pang, X. Hu, Appl. Surf. Sci., 2017, 410,
6. (a) Y.-M. Zhang, S. Yuan, G. Day, X. Wang, X.-Y. Yang, H.- 401-413; (d) W.-J. Ji, R.-Q. Hao, W.-W. Pei, L. Feng, Q.-G. Zhai,
C. Zhou, Coord. Chem. Rev., 2018, 354, 28-45; (b) M. D. Dalton Trans., 2018, 47, 700-707.
Allendorf, C. A. Bauer, R. K. Bhakta, R. J. T. Houk, Chem. Soc. 16. (a) M. Rafatullah, O. Sulaiman, R. Hashim, A. Ahmad, J.
Rev., 2009, 38, 1330-1352; (c) S. Khatua, S. Goswami, S. Biswas, Hazard. Mater., 2010, 177, 70-80; (b) K. P. Singh, D. Mohan, S.
K. Tomar, H. S. Jena, S. Konar, Chem. Mater., 2015, 27, 5349- Sinha, G. S. Tondon, D. Gosh, Ind. Eng. Chem. Res., 2003, 42,
5360; (d) J.-C. Jin, J. Wu, G.-P. Yang, Y.-L. Wu, Y.-Y. Wang, Chem. 1965-1976; (c) J.-H. Qiu, Y. Feng, X.-F. Zhang, M.-M. Jia, J.-
Commun., 2016, 52, 8475-8478; (e) W. Liu, X. Huang, C. Xu, C.-Y. F. Yao, J. Colloid. Interf. Sci., 2017, 499, 151-158; (d) S. Yao,
Chen, L.-Z. Yang, W. Dou, W.-M. Chen, H. Yang, W.-S. Liu, T. Xu, N. Zhao, L.-R. Zhang, Q.-S. Huo, Y.-L. Liu, Dalton Trans.,
Chem. Eur. J., 2016, 22, 18769-18776; (f) B. Parmar, Y. Rachuri, 2017, 46, 3332-3337; (e) J.-J. Li, C.-C. Wang, H.-F. Fu, J.-R. Cui,

CrystEngComm Accepted Manuscript

K. K. Bisht, E. Suresh, Inorg. Chem., 2017, 56, 10939-10949. P. Xu, J. Guo, J.-R. Li, Dalton Trans., 2017, 46, 10197-10201; (f)
7. (a) C.-H. Chen, X.-S. Wang, L. Li, Y.-B. Huang, R. Cao, W. Yan, L.-J. Han, H.-L. Jia, K. Shen, T. Wang, H.-G. Zheng,
Published on 07 January 2019. Downloaded on 1/21/2019 3:03:07 AM.

Dalton Trans., 2018, 47, 3452-3458; (b) W.-J. Gong, R. Yao, H.- Inorg. Chem., 2016, 55, 8816-8821.
X. Li, Z.-G. Ren, J.-G. Zhang, J.-P. Lang, Dalton Trans., 2017, 17. (a) S.-R. Zhang, J. Li, D.-Y. Du, J.-S. Qin, S.-L. Li, W.-W. He,
46, 16861-16871; (c) B. Joarder, A. V. Desai, P. Samanta, S. Z.-M. Su, Y.-Q. Lan, J. Mater. Chem. A., 2015, 3, 23426-23434;
Mukherjee, S. K. Ghosh. Chem. Eur. J., 2015, 21, 965-969. (b) Y.-Q. Lan, H.-L. Jiang, S.-L. Li, Q. Xu, Adv. Mater., 2011, 23,
8. (a) L.-R. Yang, C. Lian, X.-F. Li, Y.-Y. Han, L.-L. Yang, T. 5015-5020; (c) X. Zhao, X. Bu, T. Wu, S.-T. Zheng, L. Wang, P.
Cai, C.-Y. Shao, ACS Appl. Mater. Interfaces, 2017, 9, 17208- Feng, Nat. Commun., 2013, 4, 2344 (1-9); (d) Y.-C. He, J. Yang,
17232; (b) S. S. Nagarkar, A. V. Desai, S. K. Ghosh, Chem. W.-Q. Kan, H.-M. Zhang, Y.-Y. Liu, J.-F. Ma, J. Mater. Chem. A.,
Commun., 2014, 50, 8915-8918; (c) B. Gole, A. K. Bar, P. S. 2015, 3, 1675-1681; (e) Z. Cui, X.-Y. Zhang, S. Liu, L. Zhou,
Mukherjee, Chem. Eur. J., 2014, 20, 2276-2291. W.-L. lian Li, J.-P. Zhang, Inorg. Chem., 2018, 57, 11463-
9. (a) G. Lin, H. Ding, D. Yuan, B. Wang, C. Wang, J. Am. 11473.
Chem. Soc., 2016, 138, 3302-3305; (b) J.-P. Zhang, X.-M. 18. G.-M. Sheldrick, SADABS, Program for Empirical
Chen, J. Am. Chem. Soc., 2008, 130, 6010-6017; (c) A. Absorption Correction, University of Göttingen, Göttingen,
Karmakar, A. Kumar, A. K. Chaudhari, P. Samanta, A. V. Germany, 1996.
Desai, R. Krishna, S. K. Ghosh, Chem. Eur. J., 2016, 22, 19. G.-M. Sheldrick, SHELXS-2014, Program for the solution
4931-4937; (d) J. Akhavan, The Chemistry of Explosives, and refinemen to fcrystal structures, University of Gottingen,
Royal Society of Chemistry, Cambridge 2004. Göttingen, Germany, 2014.
10. (a) C. Mullen, A. Irwin, B. V. Pond, D. L. Huestis, M. J. 20. (a) A. K. Gupta, K. Tomar, P. K. Bharadwaj, CrystEngComm,
Coggiola, H. Oser, Anal. Chem., 2006, 78, 3807-3814; (b) B. V. 2017, 19, 2253-2263; (b) B. Ugale, S. S. Dhankhar, C. M.
Pond, C. Mullen, I. Suarez, J. Kessler, K. Briggs, S. E. Young, Nagaraja, Inorg. Chem. Front., 2017, 4, 348-359; (c) R.-Y. Wang,
M. J. Coggiola, D. R. Crosley, H. Oser, Appl. Phys. B, 2007, 86, L.-L. Liu, L.-L. Lv, X. Wang, R. Chen, B.-L. Wu, Cryst.
735-742. Growth Des., 2017, 17, 3616-3624.
11. (a) F. Yan, Y.-Y. He, L.-H. Ding, B. Su, Anal. Chem., 21. (a) F.-Y. Yi, J.-P. Li, D. Wu, Z.-M. Sun, Chem. Eur. J.,
2015, 87, 4436-4441; (b) H.-X. Zhang, A.-M. Cao, J.-S. Hu, L.- 2015, 21, 11475-11482; (b) C.-Y. Sun, X.-L. Wang, C. Qin,
J. Wan, S.-T. Lee, Anal. Chem., 2006, 78, 1967-1971. J.-L. Jin, Z.-M. Su, P. Huang, K.-Z. Shao, Chem. Eur. J., 2013,
12. (a) M.-H. Lu, P.-W. Zhou, Y.-H. Ma, Z. Tang, Y.-Q. Yang, 19, 3639-3645; (c) Y. Zhu, Y.-M. Wang, S.-Y. Zhao, P. Liu,
K.-L. Han, J. Phys. Chem. A., 2018, 122, 1400-1405; (b) G. P. C. Wei, Y.-L. Wu, C.-K. Xia, J.-M. Xie, Y. Zhu, Y.-M. Wang,
Anderson, S. C. Moreira, P. T. Charles, I. L. Medintz, E. R. S.-Y. Zhao, P. Liu, C. Wei, Y.-L. Wu, C.-K. Xia, J.-M. Xie,
Goldman, M. Zeinali, C. R. Taitt, Anal. Chem., 2006, 78, Inorg. Chem., 2014, 53, 7692-7699.
2279-2285; (c) T. Naddo, Y. Che, W. Zhang, K. Balakrishnan,
X.-M. Yang, M. Yen, J.-C. Zhao, J. S. Moore, L. Zang, J. Am.
Chem. Soc., 2007, 129, 6978-6979.
13. (a) M.-E. Germain, M.-J. Knapp, Chem. Soc. Rev., 2009,
38, 2543-2555; (b) E.-L. Zhou, P. Huang, C. Qin, K.-Z. Shao, Z.-
M. Su, J. Mater. Chem. A., 2015, 3, 7224-7228; (c) P. Das, S. K.
Mandal, J. Mater. Chem. A., 2018, 6, 16246-16256; (d) Z.-J. Li,
X.-Y. Li, Y.-T. Yan, L. Hou, W.-Y. Zhang, Y.-Y. Wang,
Cryst. Growth Des., 2018, 18, 2031-2039; (e) X.-Y. Guo, F.
Zhao, J.-J. Liu, Z.-L. Liu, Y.-Q. Wang, J. Mater. Chem. A.,
2017, 5, 20035-20043.
14. (a) G. Crini, Bioresour. Technol., 2006, 97, 1061-1085; (b) A.
Mittal, A. Malviya, D. Kaur, J. Mittal, L. Kurup, J. Hazard. Mater.,
2007, 148, 229-240.

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A stable anionic metal-organic framework with open coordinated DOI: 10.1039/C8CE02060D

sites: selective separation toward cationic dyes and sensing properties

Wei Gaoab, Feng Liub, Chang-Wei Pana, Xiu-Mei Zhang*bc, Jie-Ping Liub and Qing-Yu Gao*a

CrystEngComm Accepted Manuscript

A multifunctional anionic metal-organic frameworks were successfully synthesized using
a new pyridyl-tricarboxylate ligand. It could be applied as a luminescent sensor for Fe3+
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ions and TNP detection and it showed selective adsorption of cationic dyes.