A luminescent 2D zinc(II) metal–organic framework for selective sensing of Fe(III) ions and adsorption of organic dyes

Article abstract of DOI:10.1016/j.poly.2018.09.039

A 2D porous multifunctional Zn(II) metal–organic framework (MOF) [ZnL(H₂O)₃]·3H₂O·DMF (BIPT-1·3H₂O·DMF) has been successfully synthesized by using bis-(3-carboxy-phenyl)furan-2,5-dicarboxamide (H₂L) a

Full text of DOI:10.1016/j.poly.2018.09.039

Accepted Manuscript
A luminescent 2D Zinc(II) metal-organic framework for selective sensing of
Fe(III) ions and adsorption of organic dyes
Tao-Guang Qu, Xue-Min Hao, Hao Wang, Xiu-Guo Cui, Fei Chen, Yi-Bo Wu,
Dan Yang, Min Zhang, Wen-Li Guo
PII:
S0277-5387(18)30591-6
https://doi.org/10.1016/j.poly.2018.09.039
POLY 13438
DOI:
Reference:
To appear in:
Polyhedron
Received Date:
Revised Date:
Accepted Date:
19 July 2018
9 September 2018
15 September 2018
Please cite this article as: T-G. Qu, X-M. Hao, H. Wang, X-G. Cui, F. Chen, Y-B. Wu, D. Yang, M. Zhang, W-L.
Guo, A luminescent 2D Zinc(II) metal-organic framework for selective sensing of Fe(III) ions and adsorption of
organic dyes, Polyhedron (2018), doi: https://doi.org/10.1016/j.poly.2018.09.039
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A luminescent 2D Zinc(II) metal-organic framework for selective sensing of
Fe(III) ions and adsorption of organic dyes
b,1
a,b,1
a,c
a
a
a
a
Tao-Guang Qu , Xue-Min Hao , Hao Wang *, Xiu-Guo Cui , Fei Chen , Yi-Bo Wu , Dan Yang , Min
a
a*
Zhang , Wen-Li Guo
a
Beijing Key Lab of Special Elastomer Composite Materials, College of Materials Science and Engineering,
Beijing Institute of Petrochemical Technology, Beijing, 102617, P. R. China
b
College of Materials Science and Engineering, Beijing University of Chemical Technology, Beijing 100029,
P. R. China
c
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin
University, Changchun 130012, P.R. China
_
________________________________________________________________________
*
1
Corresponding author. E-mail: wangh@bipt.edu.cn. gwenli@bipt.edu.cn. Fax: +86-10-81292011.
These authors contributed equally.

ABSTRACT
A 2D porous multifunctional Zn(II) metal-organic framework (MOF) [ZnL(H O) ]·3H O·DMF (BIPT-
2
3
2
1
·3H O·DMF) has been successfully synthesized by using bis-(3-carboxy-phenyl)furan-2,5-dicarboxamide
2
(
H L) as organic linkers under solvothermal conditions and characterized by single crystal X-ray diffraction
2
analysis, IR spectroscopy, thermogravimetric analyses (TGA) and powder X-ray diffraction spectra (PXRD).
The participation of long chain flexible organic ligands (H L) not only offered BIPT-1·3H O·DMF larger
2
2
pore size and stronger fluorescence emission as expect, but also introduced more functional groups and active
sites into the MOF structure which is conducive to its further applications. The luminescence analysis
indicated that BIPT-1·3H O·DMF exhibited a high selectivity and sensitivity fluorescence quenching toward
2
to Fe3+ ions in water medium, which can be observed by naked eyes under UV light. This remarkable
quenching effect can be explained by the competitive absorption of excited energy mechanism and the
impediment of energy transfer mechanism. Meanwhile, BIPT-1·3H O·DMF exhibited a rare capability of
2
neutral MOF, i.e., to selectively adsorb cationic dyes, especially for methylene blue.
Keywords: Metal-organic framework; Fluorescence; Sensing Fe(III) cation; Dye adsorption

1
. Introduction
Metal–organic frameworks (MOFs) can be defined as a new class of crystalline materials comprised of
organic ligands and metal ions or clusters. MOFs have experienced a rapid development in the past two
decades due to their intriguing topological diversity and various valuable potential applications, including
drug delivery, gas separation, chemical sensing and heterogeneous catalysis [1-5]. It is worth noting that
fluorescence sensing based on luminescent MOFs (LMOFs) gradually receives considerable attentions
among the numerous applications mentioned above. For LMOFs constructed from transition metals, the
luminescence commonly arises from conjugated organic ligands [6]. In this case, the selection of organic
linkers with π electron system and amide groups not only endows the LMOFs with strong luminescent
performance, but also provides multiple reactive sites for π-π stacking, electrostatic interaction, Lewis
acid/base interaction and hydrogen bonds between LMOFs and analytes [7]. Either variation in emission
wavelength or intensity of the LMOFs can occur depending on the nature of the analytes being recognized
and different host-guest interaction. This significant change in the emission spectrum should attribute to the
electron transfer or energy transfer between molecules/ions and MOFs [8].
To date, many analytical techniques have been applied for chemical substance identification, such as ion
mobility spectrometry, Raman spectroscopy and gas chromatography-mass spectrometry, etc [9]. Compared
with these methods, fluorescence sensing is more attractive due to their reusability, operability, stability and
inexpensiveness [10]. During recent years, many LMOF sensors have been reported by Bu and other groups
for the detection of ions, small organic molecules and even biomacromolecules [11]. However, designing
and constructing LMOFs with selective, fast and sensitive fluorescence response is still an ongoing pursuit.
In addition, as a class of new porous materials, MOFs exhibit a particular application in water purification
area, i.e., selective adsorption of organic dyes. Drinking water shortage is a worldwide problem exacerbated
by geometric growth of population and industrialization. Many industries (e.g., printing, dyestuff, paper,
textile, leather and plastic) generated a large amount of colored waste water containing organic dyes [12].
Removal of dyes is essential for water quality and ecosystem due to extremely adverse influence by colorants
+
[
13]. For instance, methylene blue (MB ) is a commonly used toxic cationic dye in textile industry, which
leads to serious health risks upon long-term exposure, such as dyspnea, excessive perspiration and etc [14].

For the treatment of organic dyes, the adsorption route based on porosity and large surface area of MOFs and
other porous materials, such as porous carbon, own great advantages over other methods and thus is adopted
by lots of research groups already made significant progress [15-16].
Follow above considerations, we conceive and synthesize a new symmetric semirigid ligand bis-(3-
carboxy-phenyl)furan-2,5-dicarboxamide (H L) with two carboxylic substituents as coordination sites and
2
two amide groups as active sites based on the following reasons: (1) H L can adopt multiple conformations
2
according to the nature of various center ions, because the introduction of the amide bond increases the
flexibility of the linkers, which may construct some intriguing topological structures with unique properties
[
17]; (2) the length of bent H L in the skeleton approximate to 2 nm, may facilitate the formation of MOFs
2
with larger pores and specific surface area for inclusion of various analytes [18]; (3) the π-electron of the
aromatic in H L allows MOFs to exhibit strong ligand-based luminescence; (4) the amide bond can be used
2
as the Lewis base reaction sites which endow MOFs as attractive candidates for adsorption and chemical
sensing [19]. Herein, a novel Zn(II) MOF, namely [ZnL(H O) ]·3H O·DMF (H L=bis-(3-carboxy-
2
3
2
2
phenyl)furan-2,5-dicarboxamide) (BIPT-1·3H O·DMF, where BIPT = Beijing Institute of Petrochemical
2
Technology) is successfully synthesized by using a solvothermal method. The measurement results of
3
+
luminescence indicate that BIPT-1·3H O·DMF can be treated as a luminescent probe for Fe in aqueous
2
-6
solution through a strong fluorescence quenching with high selectivity and sensitivity (5×10 mol/L). In
addition, BIPT-1·3H O·DMF is a rare example of neutral MOFs adsorbing cationic dyes, of which the
2
possible mechanism is also discussed. The results imply that BIPT-1·3H O·DMF is promising in chemical
2
sensing and colored waste solution treatment.
2
2
. Experimental Section
.1 Materials and physical measurements
All reagents and solvents were purchased from commercial sources and used without further purification.
Element analysis was carried out with a Perkin-Elmer 240C elemental analyzer. Powder X-ray diffraction
(PXRD) data were collected on a Bruker D8 ADVANCE X-ray diffractometer with Cu-Kα radiation
(λ=1.5418 Å) over the 2θ range of 5–50° at room temperature with a scanning rate of 4° per min and a step
size of 0.02°. The simulated powder patterns were calculated using Mercury 3.0. The purity and homogeneity
of the bulk products were determined by comparison of the simulated and experimental X-ray powder

diffraction patterns. Fourier transform infrared (FTIR) spectra of samples as KBr pellets were measured using
-1
a Nicolet Impact 750 FTIR spectrometer in the range of 400–4000 cm . Thermogravimetric analysis was
-1
performed under air atmosphere from room temperature to 800°C at a heating rate of 10°C min , using a
SDT Q600 thermogravimetric analyzer. Photoluminescence analyses were performed on an Edinburgh FS-5
luminescence spectrometer equipped with a xenon lamp and a quartz carrier at ambient temperature.
Absorption spectra were conducted on HITACHI U-4100 UV–vis Spectrophotometer. The quantum yields
3
+
of BIPT-1·3H O·DMF and Fe @ BIPT-1·3H O·DMF were determined according to an absolute method
2
2
using an integrating sphere from Edinburgh Instruments FLS 980. XPS analyses were performed on a
PHI5000VersaProbe X-ray photoelectron spectroscopy.
2
.2 Synthesis of bis-(3-carboxy-phenyl)furan-2,5-dicarboxamide (H L)
2
A solution of 2,5-furandicarboxylic acid (1.56 g, 10 mmol) in thionyl chloride (50 mL, 256 mmol) was
stirred for 72 h under reflux and N . After the mixture was cooled to ambient temperature, the solvent was
2
slowly distilled off under reduced pressure to afford 1 (1.65 g, 86%) as white needle crystals. Then 1 was
dissolved in anhydrous DMAc (20 mL) to form solution 1 with brownish yellow color.
Solution 1 was added dropwise to a mixture of 3-aminobenzoic acid (3.80 g, 21 mmol) and 4-
(dimethylamino)pyridine (0.25 g, 2.1 mmol) in anhydrous DMAc (50 mL) with stirring at ambient
temperature for 30 min. The reaction mixture was stirred for extra 36 hours followed by addition of 0.1 M
HCl (60 mL), a precipitate formed was filtered off and washed with DI water (15 mL×2), anhydrous ethanol
(
15 mL×2) and 0.1 M HCl (30 mL×2) to afford H L (2.43 g, 72%), as shown in Scheme 1. Elemental analysis
2
for H L (C H O N ), calcd (%): C, 60.30; H, 3.52；N, 7.04; found(%): C, 60.1; H, 3.39; N, 7.01. IR (KBr,
2
20 14
7
2
−
1
cm ): 3301 (s), 3081 (m), 1691 (s), 1656 (s), 1538 (m), 1438 (w), 1322 (m), 1261 (m), 819 (w), 757 (w),
6
80 (w).
2
Scheme 1 Synthetic procedure of H L

In order to obtain crystals of H L for further structural analysis, the as-prepared H L (30 mg) was dispersed
2
2
in DMSO (10 mL). The mixture was transferred into a 25 mL Teflon-lined stainless steel autoclave and
heated at 120°C for 72 h. Then after cooling to room temperature, the colorless crystals (H L·DMSO) were
2
obtained from DMSO solution.
2
.3 Synthesis of [ZnL(H O) ]·3H O·DMF (BIPT-1·3H O·DMF)
2 3 2 2
A mixture of ZnCl (0.20 mmol) and H L (0.10 mmol) was added to 5 mL DMF-H O (1:1 in v/v) solution.
2
2
2
The mixture was sonicated for 10 minutes followed by sealed in a 25 mL Teflon-lined stainless steel
autoclave and then heated at 120°C for 48 h. After then after cooling to room temperature, the colorless block
crystals were obtained with a yield of 36% based on Zn. Elemental analysis for BIPT-1·3H O·DMF
2
(
C H ZnO N ), calcd (%): C, 43.09; H, 4.85; N, 6.56; Found (%):C, 42.96; H, 4.92; N, 6.46. IR (KBr,
23 31 14 3
−
1
cm ): 3417 (s), 3295 (m), 1668 (s), 1614 (s), 1540 (m), 1395 (w), 1321 (m), 1261 (m), 831 (w), 771 (w),
6
47 (w).
2
.4 Luminescent sensing experiments
Same amounts of finely ground BIPT-1·3H O·DMF (3.0 mg) were added into 3.0 mL aqueous solution
2
-2
of different metal ions at the same concentration (1×10 mol/L). The mixtures were treated by ultrasonication
for 5 min before luminescent measurements.
2
.5 Selective adsorption of organic dyes
The as-synthesized BIPT-1·3H O·DMF crystals (10 mg) were soaked into 5 mL EtOH solutions
2
containing six different organic dyes with the same concentration of 20 mg/L. At a given time interval, the
changes of concentration of dye solutions were determined with UV-vis spectrophotometer to assess the
selective adsorption of BIPT-1·3H O·DMF. In addition, the organic dyes loaded MOFs were transferred into
2
fresh EtOH or LiCl saturated EtOH solution to evaluate the removal effect of adsorbed dyes.
2
.6 Single-crystal structure determination
Single-crystal X-ray diffraction data were collected with a Bruker SMART APEX II CCD diffractometer
equipped with graphite-monochromated Mo-Kα radiation (λ=0.71073 Å) by using an ω-scan technique at
96 K. The empirical absorption correction was applied by using SADABS [20]. All non-hydrogen atoms
2

were refined anisotropically. The structures were solved by direct methods and refined by full matrix least
2
squares method on F using SHELXS-2014 and SHELXL-2014 programs [21]. The crystallographic data
and results of structure refinement are given in Table S1. The selected bond angles and distances are shown
in Table S2. CCDC (No.1561706) and CCDC (No.1561707) contain the complete crystal data for
H L·DMSO and BIPT-1·3H O·DMF, which can be obtained free from Cambridge Crystallographic Data
2
2
Center.
3
3
. Results and discussion
.1 Description of crystal structure
Bis-(3-carboxy-phenyl)furan-2,5-dicarboxamide (H L), as a semirigid ligand, provides BIPT-
2
1
·3H O·DMF with a strong fluorescence effect due to its intrinsic π electron system. In addition, it can adjust
2
the conformation to meet the requirements of the center ions. Single-crystal X-ray diffraction analysis reveals
that H L·DMSO crystallizes in the monoclinic space group P2 /c with the lattice parameters a= 13.2710(10)
2
1
3
Å, b= 14.9631(12) Å, c= 12.4821(9) Å, β= 115.792(2)°, V= 2231.7(3) Å . Figure S1 displays the crystal
structure of H L generated from the Diamond software, which is consistent with the structure of the target
2
ligand. This result indicates that the desired ligand has been successfully synthesized with high purity.
Single crystal X-ray diffraction analysis exhibits that BIPT-1·3H O·DMF crystallizes in the orthorhombic
2
space group Ccca and shows a non-interpenetrated 2D porous structure. The asymmetric unit of BIPT-
2
-
1
·3H O·DMF is composed of half crystallographically independent Zn (II) center, half L ligand, one and a
2
half coordinated water molecules, one and a half guest water molecules and half guest DMF molecule. As
shown in Figure 1, each Zn (II) center adopts a six-coordinated environment to form an octahedron geometry.
Four oxygen atoms from four coordinated water with Zn–O bond lengths are in the range of 2.239–2.343 Å,
other two oxygen atoms from two individual organic linkers with Zn–O bond lengths are in the range of
2
.044–2.132 Å. The adjacent Zn (II) is connected by O atoms of the coordinated water to generate 1D infinite
chain structures with the distances between adjacent Zn(II) in the range of 4.083–4.156 Å. Moreover, the
2
-
adjacent identical Zn-chains are connected together through L ligand to form a 2D layer framework. The
2
D layer exhibits 1D quadrangular channels along the [0,0,1] direction with dimensions of ∼16.1 Å × 11.9
Å. The adjacent two-dimensional networks were further packed by hydrogen bonds to form three-
dimensional structures. And the size of 1D channels are reduced to ∼8.5 Å × 11.9 Å due to the furan ring of

the ligand in one 2D layer inserting the other 2D layer. However, the whole structure is not interpenetrated.
The solvent-accessible volume of BIPT-1·3H O·DMF was calculated by PLATON to be 26.6% per unit cell
2
squeezed the solvent [22]. However, the N and CO sorption measurements of activated sample were nearly
2
2
no adsorption.
Figure 1 The 1D chain-like structure of BIPT-1·3H
2
O·DMF viewed along the a axis (a), the 2D network structure (b), the 3D
2
structure with hydrogen bonds (c) and 3D structure (d) of BIPT-1·3H O·DMF viewed along the c axis.
Powder X-ray diffraction (PXRD) analysis
Figure S2 exhibits the simulated and experimental powder X-ray diffraction (PXRD) patterns of BIPT-
1
·3H O·DMF which confirms the phase purity of the samples. Almost all the peak positions of simulated
2
and experimental patterns are in well matching with each other. The differences in diffraction intensity may
be due to the preferred orientation of the powder sample.
3
.2 Thermogravimetric analysis
The thermogravimetric analysis of BIPT-1·3H O·DMF measured under air atmosphere exhibits dual steps
2
of weight loss (Figure S3). The initial weight loss of 28.08% from 30 to 180°C can be attributed to the loss

of free guest molecules and coordinated water molecules (calculated 28.27%). The second step of weight
loss starts at 380°C and corresponds to the decomposition of organic ligand H L. The final residual weight
2
of BIPT-1·3H O·DMF is about 12.92%, which indicated the formation of ZnO (calculated 12.71%).
2
3
.3 Photoluminescence measurements
Since BIPT-1·3H O·DMF is composed of d metal ion and conjugated organic ligand, it becomes
1
0
2
promising to act as a suitable candidate for MOF-based probe in fluorescence sensing [23]. As shown in
Figure 2, the fluorescence measurement indicates BIPT-1·3H O·DMF shows a strong blue emission with a
2
broad peak observed at 440 nm (λ = 372 nm), which can be ascribed to the H L ligand-based emission (π*
ex
2
→
π and π*→n transitions) due to the free H L molecules presenting the emission band centered at 435 nm
2
(λex= 366 nm) [24]. The slight red shift of emission wavelength of MOFs, compared with the wavelength of
2
-
ligands, is caused by the coordination of L to the center ion [25]. Meanwhile, the enhancement in the
fluorescent intensity of BIPT-1·3H O·DMF can be observed and explained in two reasons: 1. Zn (II)
2
promotes the π* → π transitions of electrons in the ligands [26]; 2. Aggregation induced fluorescence
enhancement effect. The rigidity of the crystal skeleton limits the vibrations of the ligand molecules, which
reduces the energy released in the framework through a nonradiative manner [27]. Notably, the samples
exhibits intense blue fluorescence under UV lamp in the solid state and this visible color is consistent with
the CIE chromaticity coordinates of (0.19, 0.21).
Figure 2 (a) The excitation spectrum for H
emission spectrum for H L (λex = 366 nm) and BIPT-1·3H
digital image for BIPT-1 under UV lamp.
2
L (λem =435 nm) and BIPT-1·3H
2
O·DMF (λem =440 nm). (b) Fluorescence
2
2
O·DMF (λex = 372 nm), inset: CIE chromaticity diagram and

3
.4 Luminescence sensing of Fe3+
In view of the luminescence and activity sites of MOFs, the selective recognition capability of MOFs for
different metal ions was investigated. Before the luminescent measurement, BIPT-1·3H O·DMF was
2
dispersed in DI water overnight to estimate the stability of framework. The PXRD patterns indicated that
BIPT-1·3H O·DMF retains its original skeleton after being soaked in DI water as shown in Figure S5.
2
-2
Further, 3 mg of BIPT-1·3H O·DMF was immersed in 3 mL aqueous solution of MCl (1×10 mol / L;
2
x
+
2+
2+
2+
2+
2+
2+
2+
2+
2+
3+
3+
M = K , Co , Cd , Cu , Ba , Mg , Mn , Ni , Pb , Ca , Fe , Al ) and then sonicated for 3 min to
obtain a suspension of M@ BIPT-1·3H O·DMF in water. As shown in Figure 3, the results indicated that
2
the fluorescence intensities of BIPT-1·3H O·DMF mainly depend on the nature of the metal ions. The
2
introduction of different ions affects the fluorescence intensity of MOF to a certain extent. For instance, Al3+
2
+
2+
2+
and Cd slightly enhance the fluorescence intensity, whereas Cu and Pd slightly reduce the fluorescence
intensity. However, only Fe3+ reveals a remarkable quenching effect, which also can be observed by naked
eyes. Then BIPT-1·3H O·DMF was immersed in aqueous solution of FeCl for 24 h to testified stability of
2
3
framework. The PXRD patterns show that the framework of BIPT-1·3H O·DMF remains its stability as
2
exhibited in Figure S6. These results indicated that BIPT-1·3H O·DMF may become an effective
2
3
+
fluorescence probe for selectively sensing of Fe in water.

Figure 3 (a) The fluorescence emission spectra of BIPT-1·3H
2
O·DMF dispersed in aqueous solutions containing different
O·DMF containing
metal ions at the same concentration. (b) The fluorescence intensity of the emulsion of BIPT-1·3H
2
-2
2
different metal ions with the same concentration (10 M) (λex=372 nm, λem=440 nm). (c) Photographs of BIPT-1·3H O·DMF
under UV lamp after immersed in different metal ions solution.
To further examine the detection sensitivity toward Fe3+ in more detail, BIPT-1·3H O·DMF was well-
2
3
+
-6
-2
dispersed in aqueous solutions with gradually increased the concentration of Fe from 10 ~10 mol/L. The
corresponding emission spectra were measured at the same excitation wavelength (372 nm) and same
temperature (298 K). As shown in Figure 4, the fluorescent intensity of BIPT-1·3H O·DMF gradually
2
3
+
decreased with the increased concentration of Fe . The quenching efficiency can be defined by using the
formula [(F -F)/F ] ×100% (F is the initial fluorescent intensity and F is the fluorescent intensity after adding
0
0
0
3
+
analytes). When the concentration of Fe was 0.15 mmol /L, the quenching efficiency was more than 50%.
3
+
After that, fluorescence quenching rate gradually slowed down. When the concentration of Fe reached 2.5
mmol / L, the quenching efficiency of the system has exceeded 94% (Figure 5a).
2
Figure 4 (a) Fluorescence titration of BIPT-1·3H O·DMF dispersed in DI water with the addition of different concentrations
of Fe3+ (excitation wavelength was 372 nm). (b) Plot of the maximum fluorescence emission of BIPT-1·3H
O·DMF
2
dispersed in DI water at different concentrations of Fe3+ (emission intensities at 440 nm were selected).
Figure 5a displays the relationship between the fluorescence quenching efficiency of BIPT-1·3H O·DMF
2
and the Fe3+ content in the aqueous solution. When the Fe3+ content in the detection system was lower than
3
+
0
.15 mmol / L, the quenching efficiency of BIPT-1·3H O·DMF was linear with that of Fe concentration
2
2
(
R = 99.4%). By detecting the change in fluorescence intensity, it is possible to accurately measure the

amount of Fe3+ in the solution. The increase in the quenching efficiency of BIPT-1·3H O·DMF presents a
2
first-order exponential form, which is a diffusion control driven by concentration.
Figure 5 (a) The fluorescence quenching efficiency curve of BIPT-1·3H
2
O·DMF dispersed in aqueous solution with different
3
+
3+
concentrations of Fe , inset: linear relation between the quenching efficiency and concentrations of Fe (in the range of 0-
0
.15 mmol / L). (b) The dose–response graph monitored at 440 nm showing the luminescence quenching of BIPT-
·3H
O·DMF by Fe3+ based on the Stern–Volmer equation.
1
2
Stern–Volmer constant (K ) is commonly used to quantitatively evaluate the quenching effect of MOFs
sv
for luminescent sensing in liquid medium, which can be obtained from the following Stern–Volmer equation,
I /I=1+ K [M], where I and I are the fluorescence intensities of LMOFs before and after the addition of
0
sv
0
analytes. K is the Stern–Volmer constant and [M] stands for the concentration of analytes [28]. As shown
sv
in Figure 5b, in this case, the result of fluorescence titration can be well fitted into the equation I /I – 0.89=
0
3
+
2
3
-1
K [Fe ] (R =98%), which is very close to the standard equation and the value of K is 5.04×10 M . This
sv
sv
high value of Ksv indicated that BIPT-1·3H O·DMF can serve as an excellent sensor for selective
2
3
+
identification and quantification of Fe through a fluorescence quenching process.
As shown in Figure 4, the intensity change of the fluorescence can still be obviously distinguished from
3
+
-6
the emission spectrum as the Fe content in the solution is reduced to 5×10 mol/L, which indicated that the
3
+
-6
detection limit of BIPT-1·3H O·DMF for Fe can reach 10 mol/L theoretically. This result can also be
2
determined by the IUPAC criteria of 3σ / k [29], in which σ is the standard deviation of blank measurement
and k is the plot of fitting calibration curve). It can be seen from Table S3 that this recognition limit is not
only superior to numerous MOFs constructed from transition metal, but also better than MOFs made of rare

3
+
earth elements, which fully indicated that BIPT-1·3H O·DMF can detect trace Fe with high sensitivity. In
2
addition, the use of water as a liquid medium also endows BIPT-1·3H O·DMF with more values for
2
commercial application.
Chemical sensors for practical use are required to own not only good sensitivity plus rapid response, but
also high selectivity to targeted metal ions. Therefore, the fluorescent responses of BIPT-1·3H O·DMF
2
3
+
which immersed in various metal ions aqueous solutions (before and after adding Fe ) were recorded to
evaluate the sensitivity. As shown in Figure 6, the initial fluorescent intensity of BIPT-1·3H O·DMF only
2
3
+
exhibits negligible changes upon the addition of different metal ions. While, after the addition of Fe to the
above solutions, a noticeably fluorescent quenching can be easily observed and the quenched degree was
similar to the control group, which revealed that the presence of interference (i.e., different metal ions) does
3
+
not affect the sensing results and BIPT-1·3H O·DMF has the capability to specifically identify Fe .
2
Figure 6 The histogram of the fluorescence intensity of BIPT-1·3H
2
O·DMF dispersed in different metal ion solutions (red)
and subsequent addition of Fe3+ (olive). The monitored emission peak located at 440 nm.
3
+
Furthermore, the recycling performance of BIPT-1·3H O·DMF was evaluated by centrifuging Fe @
2
3
+
BIPT-1·3H O·DMF from the Fe aqueous solutions, and then washed with ethanol for several times. It is
2

interesting to note that simple washing can only restore part of fluorescence intensity of BIPT-1·3H O·DMF.
2
Only when it was immersed in ethanol for a long time, the fluorescence intensity can be gradually restored
over time and remained stable after 24 hours. The fluorescence intensity of the regenerated MOFs basically
reached the level of the as-synthesized MOFs (Figure S7a). After five cycles of experiment, the quenching
efficiency of BIPT-1·3H O·DMF can be maintained above 80%, which proves that it can be used for multiple
2
3
+
recognitions of Fe (Figure S7b). In addition, the PXRD analysis confirmed that the skeleton is still retained
after five cycles (Figure S8).
Although the scientists have paid great efforts [30], the fluorescence recognition mechanism of MOFs still
needs further explorations. According to the result of PXRD analysis (Figure S6), BIPT-1·3H O·DMF
2
3
+
remained stable in the Fe aqueous solution, which confirms that the fluorescence quenching does not come
from the collapse of the crystal structure [31]. Since the fluorescence of BIPT-1·3H O·DMF is derived from
2
the ligand (H L), the fluorescence response of the H L to various ions was investigated in order to deeply
2
2
3
+
understand the reasons of fluorescence quenching induced by Fe . The fluorescence detection of the ligand
and BIPT-1·3H O·DMF with various metal ions was measured under the same experimental conditions. As
2
shown in Figure 7, the H L ligand exhibits a similar luminescent sensing behavior compared with BIPT-
2
3
+
1
·3H O·DMF. Therefore, the fluorescence quenching behavior of BIPT-1·3H O·DMF in Fe solution can
2 2
be attributed to the competitive absorption of excitation energy and different degrees of interaction between
3
+
H L and Fe ions. The efficiency of the absorption of external energy by the ligand is greatly decreased
2
which leads to a significant inhibition of fluorescence intensity of MOFs because BIPT-1·3H O·DMF
2
generates ligand-based luminescence.

2
Figure 7 The fluorescence intensity of the emulsion of ligand H L containing different metal ions with the same concentration
(
10-2 M) (λex=366 nm, λem=435 nm).
However, it should be noted that although the ligand can also be used to identify the metal ions by the
quenching effect, the quenching efficiency of the ligand is only 65%, whereas the quenching efficiency of
3
+
BIPT-1·3H O·DMF exceeds 90% at the same Fe concentration (1 mM) (Figure 3b and Figure 7). This
2
result fully reflects that BIPT-1·3H O·DMF has a superior detection sensitivity and limit (Table 1), which
2
can be explained by the following reasons: 1. the larger specific surface area of MOFs is beneficial to capture
analytes; 2. the pores in the MOFs are capable of pre-concentrating the analytes so that the concentration of
analytes within the crystal is higher than external environment [23b, 32].
2
Table 1 Analytical parameters of Fe(III) for BIPT-1 and H L
Probe
Analyte
LOD (μM)
Linear Range
μM)
LOQ (μM)
(
BIPT-1
FeCl
FeCl
3
5
17.5
5-150
17.5-125
5
17.5
H
2
L
3
LOD limit of detection, LOQ limit of quantification
In order to verify the above fluorescence quenching mechanism, the UV-Vis absorption spectra of twelve
metal ion aqueous solutions (1 mM) were tested. As shown in Figure S9, only Fe3+ has a strong absorption

peak in the wavelength range of 300-450 nm, which overlaps the excitation wavelength of the ligand and
BIPT-1·3H O·DMF (Figure 2a), indicating the reliability of the competitive absorption of excited energy
2
mechanism as mentioned above [11c, 27b, 33].
In addition, recently, many MOFs fluorescent probes used to identify metal ions based on the host-guest
interaction between the Lewis basic sites (such as amide, pyridyl, anionic sulfonate, carboxyl sites) and metal
ions have been widely reported [34]. The N, O elements on the functional groups of the ligands can bind to
the metal ions, resulting in electron transfer and energy transfer from ligand to metal [35]. It has been
mentioned that the fluorescence intensity of M@BIPT-1·3H O·DMF can only be recovered in a small range
2
after the simple rinse, whereas a complete restoration of the fluorescence intensity can be observed after
M@BIPT-1·3H O·DMF was immersed in ethanol overnight. This phenomenon shows that there may be an
2
3
+
3+
effective interaction between Fe and the amide bond on the framework. Washing can only remove the Fe
attached to the surface of MOFs, the completely removal of Fe3+ by solvent molecules can only occur after
long-term soaking. In order to further check the results, the XPS studies of O 1s were performed on BIPT-
3
+
1
1
·3H O·DMF and Fe @BIPT-1·3H O·DMF. The O1s peak from free oxygen atoms at 531.97 eV in BIPT-
2 2
3
+
·3H O·DMF is shifted to 532.06 eV after the addition of Fe (Figure S10), indicating the weak bond
2
3
+
3+
between oxygen atoms and Fe in Fe @BIPT-1·3H O·DMF. To further confirm the host-guest interaction,
2
3
+
the decay curves of BIPT-1·3H O·DMF in both DI water and Fe aqueous solution were measured, as
2
3
+
shown in Figure S11. The luminescent lifetimes of BIPT-1·3H O·DMF in DI water and Fe aqueous
2
solution are 12.35 μs and 8.93 μs, respectively, and the quantum yields of the fluorescence emission intensity
was changed from 3.9% to 1.8%, which indicated the ineffectively energy transfer from H L to Zn (II). Part
2
3
+
of the energy absorbed by the ligand is directly transferred to Fe and released in a non-radiative way which
is consistent with our speculation [36]. In summary, the competitive absorption of excited energy between
metal ions and the ligand as well as the impediment of energy transfer between ligand and central ions by
3
+
3+
Fe make trace Fe can effective inhibit the fluorescence properties of BIPT-1·3H O·DMF.
2
3
.5 Selectively absorb and separate methylene blue (MB+)
The ability of BIPT-1·3H O·DMF to selectively absorb and separate organic dyes has also been
2
investigated due to the porosity of crystals and Lewis base sites within the frameworks. Six organic dyes with
-
different charges were selected for the experiments, including anionic dyes (methyl orange, MO and Congo

-
+
red, CR ), neutral dyes (solvent yellow 7, SY7 and Sudan I, SD) and cationic dyes (methylene blue, MB and
+
crystal violet, CV ), of which the molecular structures are shown in Scheme S1. The finely ground BIPT-
1
·3H O·DMF (10 mg) was transferred to the EtOH solutions which contains different organic dyes (20 mg/L)
2
as mentioned above and monitored by UV-vis spectra after certain time intervals at room temperature.
Ethanol is selected as solvent for the experiment because the neutral dyes are difficult to dissolve in water.
As shown in Figure 8, with the increase of the contact time of MOFs with the colored solution, BIPT-
1
·3H O·DMF did not exhibit obvious absorption effect on the anionic dyes and the neutral dyes. The small
2
changes on absorbance may be due to the fact that trace amount of dye molecules were attached to the surface
of the porous material as well as the experimental errors. In contrast, the crystals immersed in the cationic
dye solutions gradually change from colorless to blue (purple) and the corresponding solutions gradually
+
faded. Especially for MB , when BIPT-1·3H O·DMF dispersed into the solution for 24 hours, the
2
+
characteristic absorption peak (about 664 nm) of the MB almost completely disappeared (up to 99%) and
+
the adsorption capacity of BIPT-1·3H O·DMF for MB is calculated as 26mg/g [37], which indicated that
2
+
BIPT-1·3H O·DMF has the capacity to efficiently adsorb MB from liquid mediums.
2

+
+
-
-
Figure 8 Change of UV-Vis spectra in EtOH solutions of MB (a), CV (b), SY7 (c), SD (d), MO (e), CR (f) containing
BIPT-1·3H O·DMF with the time past; the inset photographs for the color changes of supernatants toward the corresponding
dyes solution before and after BIPT-1·3H O·DMF immersed in solutions.
2
2
The patterns of PXRD analysis demonstrated that BIPT-1·3H O·DMF remained stable in the above six
2
+
dye solutions, which indicated that the selective absorption of MOFs to MB was achieved by the interaction
between host and guest (Figure S12). To further validate whether BIPT-1·3H O·DMF possesses the capacity
2
to separate different kinds of dyes, the selective adsorption and separation experiments were designed. The
dye molecules with different charges were chosen as represents to verify the selective uptake ability of BIPT-
+
-
+
1
·3H O·DMF, which included MB & MO as well as MB & SY7. The samples were immersed in the EtOH
2
+
+
-
solutions containing MB &SY7 (40 mg/L & 40 mg/L, 2.5 mL & 2.5 mL) as well as MB &MO (40 mg/L &
4
0 mg/L, 2.5 mL & 2.5 mL) under the same condition. From the UV-Vis absorption spectra, it can be seen
-
that the intensity of the characteristic absorption peak of SY7 (about 348 nm) or MO (about 466 nm) in the
mixed dye solution remained unchanged after 24 hours, wheras the characteristic absorption peak of MB+
(about 664 nm) disappeared completely (Figure 9). Meanwhile, with the increase of the soaking time, the
-
color of the mixed solution gradually changes to the color of the pure solution of SY7 and MO , respectively.
+
The high selectivity and stability of BIPT-1·3H O·DMF are crucial to the MB adsorption application.
2
+
+
-
2
Figure 9 UV-Vis spectra changes of dye mixture in the presence of BIPT-1·3H O·DMF: (a) MB &SY7; (b) MB &MO . The
inset photographs are supernatants of dry solutions before and after adsorption.
+
In addition, desorption experiments of MB @BIPT-1·3H O·DMF were performed and monitored by UV-
2
vis spectra. In general, there are two common methods to release the adsorbed dyes from MOFs: 1. the

dye@MOFs are dispersed into the pure solvent to allow the fully exchanged process occurred between dye
molecules and solvent molecules to regenerate MOFs. This method is generally applicable to dyes adsorbed
to MOFs by physical adsorption; 2. the dye@MOFs are placed in a saturated solution of LiCl or NaCl (usually
+
+
with organic solvent), then the Li (Na ) diffused into the skeleton of MOFs to replace the absorbed dyes to
regenerate MOFs, of which this approach is primarily applicable to dyes (such as cationic dyes and anionic
MOFs) immobilized in MOFs by Coulomb force.
+
In this work, the MB @BIPT-1·3H O·DMF was dispersed into pure EtOH and a saturated EtOH solution
2
+
of LiCl, respectively. As shown in Figure S13a, the release of MB was not observed in the pure solvent, in
contrast, the loaded dyes could be rapidly released in the saturated solution of LiCl. It should be noted that
the PXRD result shows that the crystal structure of BIPT-1·3H O·DMF after immersion in LiCl solution has
2
been completely destroyed, which means that it is still necessary to find a suitable method for the recycling
of BIPT-1·3H O·DMF (Figure S13b).
2
Although the use of reported methods failed to achieve the reuse of MOFs, the desorption experiments
+
indirectly proved that the adsorption of MB by neutral skeleton of BIPT-1·3H O·DMF does not belong to
2
the classic host-guest interaction. Therefore, the mechanism of selective adsorption maybe due to the
interaction of the dye molecules and framework of BIPT-1·3H O·DMF via electrostatic interaction. Some
2
carboxyl groups, which are coordinated to zinc ions, are present in the form of carboxylic anion due to
+
+
structural defect [38]. In addition, although with the same charge, the size of CV is greater than MB , the
+
size exclusion led to the weakening of the absorption capacity of MOFs on CV [25, 38].
4
. Conclusion
In summary, a multifunctional Zn(II) MOF (BIPT-1·3H O·DMF) was successfully synthesized based on
2
a novel dicarboxylic acid ligand (H L) via solvothermal method. The luminescent analysis implies that
2
BIPT-1·3H O·DMF could be employed as a potential fluorescent sensor for fast and sensitive detection of
2
3
+
Fe through a strong fluorescence quenching process, which can be explained by the competitive absorption
of excited energy mechanism and the impediment of energy transfer mechanism. Beneficially, this porous
material can be used reversibly and its luminescence quenching can be directly observed by naked eyes. In
addition, BIPT-1·3H O·DMF exhibits the ability to selective adsorption of cationic dyes (especially for
2
+
MB ). Further studies based on organic ligand H L are under way in our research group.
2

Acknowledgments
This work was financially supported by the NSFC of China (21501012, 51573020, 51503019), the
Training Program Foundation for Excellent Talents by Beijing Municipal Committee of CPC Organization
Department (2015000020124G063), Beijing Science and Technology Project of Beijing Municipal
Education Commission (KM201610017006) and Beijing Natural Science Foundation (2172022, 2162014).
Appendix A. Supplementary data
Crystallographic data (Table S1, S2), Comparison of the detective sensitivity (Table S3), Conformation
of free ligands and coordinated ligands (Figure S1), PXRD patterns (Figure S2, S5, S6, S8, S12), TG curve
(Figure S3), IR spectrum (Figure S4), Luminescence (Figure S7, S11), UV-Vis spectra (Figure S9, S13) XPS
spectra (Figure S10) and various organic dyes (Scheme S1). CCDC 1561706-1561707 contains the
supplementary crystallographic data for H L·DMSO and BIPT-1·3H O·DMF. These data can be obtained
2
2
free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge Crystallographic
Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail:
deposit@ccdc.cam.ac.uk.
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A new Zn-MOF (BIPT-1) has been synthesized based on a new amide-inserted
3
+
dicarboxylate ligand, which can be used for sensing Fe ions in water medium and dye
absorption.