Lanthanide(Tb3+, Eu3+)-functionalized a new one dimensional Zn-MOF composite as luminescent probe for highly selectively sensing Fe3+

Article abstract of DOI:10.1016/j.poly.2018.04.013

A new one dimensional zinc metal organic framework {[Zn(NDIC)·2H₂O]·2H₂O}_n (NDIC = 5-(5-Norbonene-2,3-dicarboximide)Isophthalic acid) has been synthesized under an hydrothermal condition and chosen as a parent framework to sensitize via encapsulating Tb³⁺ and Eu³⁺ cations in Zn-MOF. The obtained composite Tb(3+)@Zn-MOF shows excellent luminescence which performs a remarkable quenching effect in the luminescence emission of Tb³⁺ upon the introduction of Fe³⁺. Subsequently, Tb(3+)@Zn-MOF as a highly selective and sensitive sensor for Fe³⁺. Most importantly, the luminescence probe of Fe³⁺ shows a low detection limit (7.5 × 10^?6 M), a broad linear range (2.5 × 10^?6–7.5 × 10^?5). A paper strip coated with Tb(3+)@Zn-MOF material was also shown to be highly selective for Fe³⁺ and under the irradiation of UV light of 254 nm by the naked eyes. This is first example for detecting metal ions based on a lanthanide functionalized a new Zn metal–organic framework.

Full text of DOI:10.1016/j.poly.2018.04.013

Accepted Manuscript
3
+
3+
Lanthanide(Tb , Eu )-functionalized a newonedimensional Zn-MOF compo-
3
+
site as luminescent probe for highlyselectively sensing Fe
Yi Wang, Rui Huang, Jiaojiao Zhang, Gang Cheng, Huan Yang
PII:
S0277-5387(18)30181-5
https://doi.org/10.1016/j.poly.2018.04.013
POLY 13115
DOI:
Reference:
To appear in:
Polyhedron
Received Date:
Accepted Date:
13 February 2018
9 April 2018
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+
3+
Please cite this article as: Y. Wang, R. Huang, J. Zhang, G. Cheng, H. Yang, Lanthanide(Tb , Eu )-functionalized
3
+
a newonedimensional Zn-MOF composite as luminescent probe for highlyselectively sensing Fe , Polyhedron
2018), doi: https://doi.org/10.1016/j.poly.2018.04.013
(
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3
+
3+
Lanthanide(Tb , Eu )-functionalized a newonedimensional Zn-MOF composite as luminescent
3
+
probe for highlyselectively sensing Fe
1
2
1
1
2
Yi Wang , Rui Huang , Jiaojiao Zhang ,Gang Cheng , Huan Yang *
1
College of chemistry and Material Engineering, Gui Yang University, 550005, Guiyang, P.R. China
2
School of Material science and Engineering Han Shan Normal University, Chaozhou,521041, P.R. China
E-mail:yanghuanjx@163.com
A new one dimensional zinc metal organic framework {[Zn(NDIC)·2H O] ·2H O} ((NDIC =
2
2
n
5
-(5-Norbonene-2,3-dicarboximide)Isophthalic acid) has been synthesized under an hydrothermal
3+
3+
condition and chosen as a parent framework to sensitize via encapsulating Tb and Eu cations in
Zn-MOF. The obtained composite Tb(3+)@Zn-MOF shows excellent luminescence which performs a
3+
3+
remarkable quenching effect in the luminescence emission of Tb upon the introduction of Fe .
3
+
Subsequently, Tb(3+)@Zn-MOF as a highly selective and sensitive sensor for Fe . Most importantly,
3
+
-6
the luminescence probe of Fe shows a low detection limit (7.5×10 M), a broad linear
−
6
−5
range(2.5×10 –7.5×10 ). A paper strip coated with Tb(3+)@Zn-MOF material was also shown to be
3
+
highly selective for Fe and under the irradiation of UV light of 254 nm by the naked eyes. This is first
example for detecting metal ions based on a lanthanide functionalized a new Zn metal-organic
framework.
1
. Introduction
Metal−organic frameworks (MOFs) have emerged a crystalline hybrid materials obtained
constructed by the assembly of metal ions/clusters and organic linkers, and have been emerging as very
promising multifunctional materials, such as catalysis,[1-3] magnetism,[4,5] gas storage and
separation,[6-8] energy storage.[9-11]As a subfamily of MOFs reported, Ln-MOFs have been receiving
great attention due to their lots of fascinating luminescence properties such as high quantum yield,
relatively long life time, characteristic sharp-line emissions and large Stokes shifts.[12-14] The
combination of these excellent optical properties together with diverse structures and topologies of
MOFs offers an effective platform for chemical sensing.In the past decade, there are many researches
on luminescent Ln-MOFs for sensing,such as metal ions,[15-17] anions,[18,19] small molecules[20-23]
and temperature[24-26] have been reported. It is a great challenge to design and synthesis of the
targeted Ln-MOFs via direct synthesis due to the higher coordination number and various coordination
modes of lanthanide ions. Postsynthetic modification method of MOFs provides an way to exploit and
3
+
expand their unique properties. The conventional incorporation of photoactive Ln into the channels of
MOFs hosts may produce new luminescent signals at different positions. It will offer a new possibility
3
+
to realize the multiband emissions originated from different Ln and perform the similar luminescent
sensing function of lanthanide MOFs.[27,28]
3+
Fe ion is the most abundant transition element for either humans or other living organisms on
account of their significance in basic and essential biological processes and systems.[29,30] Either
3
+
deficient or excessive Fe from the normal permissible limit can lead to serious system disorder. The
damages to cells may further leading to many kinds of disorders, such as cancer, Parkinson’s diseases
3
+
3+
and Alzheimer’s disease. Moreover, Fe is also a common inorganic pollutant. Excessive Fe could
3+
result in lots of diseases related to human health. [31]Therefore, the selective detection of Fe is a very
necessary in biological research and the development of selective detection or sensing of iron over
other metal ions seems to be very important for human health. In fact, many works have been
3
+
successfully reported the sensing of Fe .However, there are only a few luminescent sensors selective

3+
for Fe , simultaneously, without the interference of other mixed metal ions via luminescence
quenching is still a challenge now.[32]
In this work, a new metal organic framework {[Zn(NDIC)·2H O] ·2H O} was designed and
2
2
n
obtained via solvothermal reactions. Subsequently, A novel luminescence hybird composite of
3+
lanthanide-doped Zn-MOF(Tb(3+)@Zn-MOF) was constructed through encapsulating Tb cations in
Zn-MOF. What is more, Tb(3+)@Zn-MOFis used as highly selective and sensitive luminescent sensor
3+
forFe among many other metal ions in ethanol solution. The possible sensing mechanisms were
discussed in detail. As expected, Tb(3+)@Zn-MOF is suitable for becoming one luminescent probe for
3+
Fe with high selectivity and sensitivity.
2
. Materials and methods
All the reagents and solvents were purchased from different companies, and directly used as received
without further purification.
Single crystal X-ray crystallography
A colorless single crystal of Zn-MOF was sealed in a capillary tube with the some mother liquor
inside in order to prevent desolvation of the crystal Data for the crystal was collected using graphite
monochromated Mo Ka radiation (λ=0.71073 A) at 293 K on Rigaku Oxford CCD diffractometer. The
absorption corrections were applied by using the multiscan program, the structure were solved by direct
2
methods and refined with on F by least-squares technique with the program SHELXTL-2016.The
refinement of structural model were performed with anisotropic displacement parameters restraints,
such as DFIX, SIMU, AFIX, ISOR for the benzene rings and solvent molecules. Graphics were
generated using Diamond 3.0.The crystallographic data and details of refinements and the selected
bond lengths and angles for Zn-MOF are listed in Table 1, 2 and S2.
IR absorption spectra of the Zn-MOF and Tb(3+)@Zn-MOF were performed on a IR Affinity-1
-
1
FT-IR spectrometerby dry KBr slices in the wavenumber range of 400–4000 cm . The amounts of
metal ions in Tb(3+)@Zn-MOF(Tb:Zn) and Eu(3+)@Zn-MOF(Eu:Zn)were determined by inductively
coupled plasma mass spectrometry (ICP-MS, Icap Qc, Thermo-Fisher, Germany) Powder X-ray
diffraction (PXRD) patterns were performed coupled with Cu Ka radiation (1.5418 Å) on a Rigaku
Miniflex 600 X-ray diffractometer at room temperature. Thermogravimetric analysis (TGA) was
-
1
measured under nitrogen protection from 50 ℃to 700 ℃ with a heating rate of 5 ℃ min on a Netzsch
sta 449f3. Luminescence spectra were recorded on Horiba ihr320 fluorescence spectrophotometer at
room temperature.The emission quantum yield was recorded on FLS980 Fluorescence
Spectrofluorometer at room temperature, the luminescent lifetime of Tb(3+)@Zn-MOF was recorded
on FLS920 Fluorescence Spectrofluorometer.
Synthesis of {[Zn(NDIC)·2H O] ·2H O} (Zn-MOF)
2
2
n
Zn(CH COO) (0.1mmol, 18.3 mg) and NDIC(0.05mmol,0.0165g)were dissolved in 3 mL DMF.
3
2
The mixture was sealed in 15 mL solvothermal vessel, and was subsequently heated at 80℃ for 3 days
then a gradual cooling procedure to room temperature. The resulting colorless prism crystals were
obtained in 65% yield based on NDIC.
3
+
3+
Preparation of lanthanide( Tb , Eu )@Zn-MOF
Powder of Zn-MOF (100 mg) is soaked in ethanol solution of Tb(NO ) ·6H O and
3
3
2
Eu(NO ) ·6H O(10 mL, 2 mmol) for 1 day respectively. The resulting white solid was then separated
3
3
2
3+
from the mixed dispersion by centrifugation and washing with ethanol to remove redundant Tb and
3+
Eu , the resulted white powder was dried at 60 ℃ for 6 h. The ratio of Tb:Zn and Eu:Zn is 1:16 and
:20, respectively.
1

Luminescence Sensing Experiment
mg powder of Tb(3+)@Zn-MOF were dispersed into ethanol solution (4 mL, 1×10 molL ) of
-
3
-1
2
n+
+
2+
2+
2+
+
2+
2+
2+
3+
M(NO ) (M = Ag , Pb , Mg , Cd , K , Zn ,Ni , Co , Fe ) at room temperature ,and then the
3
x
mixture was equilibrated thoroughly for 5 min by ultrasound processing.The mixtures were used for
luminescence measurements. All the luminescence data were recorded at the room temperature.
3
. Results and discussion
3
.1 Description of crystal structure
2
+
Zn-NDIC (1) crystallizes in the space group P21/c , and the asymmetric unit comprises one Zn ion,
2-
one bridging NDIC , two coordinated water molecules, and two guest water molecule. As shown in
2
+
2-
Figure 1, the Zn ion is five-coordinated by three carboxylate oxygen atoms from two NDIC
[Zn−
O1=1.907(9)Å, Zn−O4a=2.048(1)Å, Zn−O3a=2.417(2)Å] and two oxygen atoms of two coordinated
water molecules [Zn−O7=2.007(6)Å, Zn−O8=1.957(8)Å] to generate a distorted square pyramid
coordination geometry. The Zn centers are bridged by NDIC to forming one chain dimensional
structure (Figure 1b), chains are bridged byhydrogen bond (Table 2) forming three dimensional
structure (Figure 1c).
(a)
(
b)
c)
(
Figure 1 (a) Asymmetric unit of Zn-MOF (b) One-dimensional structure of Zn-MOF
c)Three-dimensional structure of Zn-MOF
Table 1. Crystal data and structure refinement for Zn-MOF.
(

Compound
Chemical Formula
Formula weight
Crystal system
Space group
a (Å)
Zn-MOF
C H17NO10Zn
17
462.75
Monoclinic
P2(1)/c
7.8480(8)
23.377(3)
12.2665(13)
90
b (Å)
c (Å)
α (°)
β (°)
126.687(7)
90
γ (°)
3
V (Å )
1804.7(4)
4
Z
3
D (g/cm )
c
1.703
-
1
μ (mm )
1.347
T (K)
293(2)
Wavelength (Å)
F(000)
1.54178
950
Crystal size (mm)
Absorption coefficient
Data / restraints
Parameters
0.21  0.08  0.07
-
1
2.445 mm
2677 / 6
262
F(000)
950
R1 indices [I > 2σ(I)]
0.0799
0.1015
0.2472
0.1682
wR indices [I > 2σ(I)]
2
R1 indices [all data]
wR indices [all data]
2
Table 2Hydrogen-bond geometry (Å)
d(D···A) ∠(DHA)
O10-H10B···O4#3
2.889(9) 166.9
2.820(8) 160.9
2.654(7) 167.4
2.884(8) 123.9
2.992(7) 126.8
O9-H9B···O3#1
O9-H9A···O7#3
O8-H8B···O5#2
O8-H8A···O2
Symmetry transformations used to generate equivalent atoms: #1 x+1,y,z+1;#2-x+2,-y+2,-z+1; #3
x-1,y,z.
3
.2 Purity and thermal stability
In order to explore application of Zn-MOF, the purity and thermal stability of the material were
investigated. Figure 2(a) shows the PXRD patterns of the Zn-MOF and Tb(3+)@Zn-MOF from 5° to
0°, the PXRD pattern of as prepared Zn-MOF(CCDC: 1819140) is well matched with the simulated
5
data, which indicates a high purity of the Zn-MOF. The PXRD pattern of the Tb(3+)@Zn-MOF and
Eu(3+)@Zn-MOF are also in agreement with the simulated Zn-MOF(Figure S2). The result shows that

the preparation of Tb(3+)@Zn-MOF and Eu(3+)@Zn-MOF are successful and the crystallinity of
Zn-MOF could retain still kept original crystal type.The Zn-MOF and Tb(3+)@Zn-MOF was
monitored by TG analysis. The TG curve of the Zn-MOF in Fig. 2b presents two events. The first
weight loss below 140℃ is ascribed to the release of the surface water molecules. The range from
1
40 ℃ to 400 ℃ corresponds to the loss of ligand. Afterwards, The final plateau from 540 ℃
corresponds to zinc oxide. The Tb@Zn-MOF was also monitored by TG analysis from 0 to 700 ℃
Figure 2b). The TGA of Tb@Zn-MOF exhibits two events of weight losses and shows good thermal
(
stability similar to Zn-MOF. The first step occurs below 140 °C is ascribed to the release of the
surface water molecules. The second weight loss from 150 °C to 400 °C corresponds to the
decomposition of the organic ligand. The final plateau from 540 °C corresponds to oxide.
(a)
(b)
Fig. 2 (a) Powder X-ray diffraction patterns of simulated Zn-MOF, prepared Zn-MOF and
Tb(3+)@Zn-MOF. (b) TGA of prepared Zn-MOF and Tb(3+)@Zn-MOF.
-
1
−1
As shown in Figure 3, the peaks that are located 1680 cm and 1359 cm are ascribed to the
absorption of υ in Zn-MOF. Subsequently, Zn-MOF was immersed in ethanol solution of Tb(NO3)3
c=o
3+
for Tb -encapsulation in the channels by connecting to the uncoordinated-COOH of Zn-MOF. the
3+
absorption band of Zn-MOF show a significant red-shift (about 10 nm) after connecting to Tb
,
3+
3+
indicating the interactions between the Tb and free-COOH of Zn-MOF. After incorporation of Tb
into the Zn-MOF, the hybrid composite not affect the crystalline integrity of Zn-MOF, as shown by the
PXRD patterns (Figure 2a).

Fig. 3 IR spectra of Zn-MOF and Tb(3+)@Zn-MOF
.3 Luminescence Properties of Tb(3+)@Zn-MOF
In Fig.4, when excited at 303 nm, the emission spectrum of the Tb(3+)@Zn-MOF exhibits
3
3
+
characteristic emission of Tb . The sharp lines located at about 489, 545, 592 and 612 nm can be
5
7
3+
ascribed to D → F (J = 3−6) transitions of Tb . Eu(3+)@Zn-MOF also exhibit the characteristic
4
J
3
+
5
7
emission bands of Eu ions at 580, 594 , 618 nm ( D → F )(J = 0−2) in the PL spectra(Fig. S3). [33,
0
J
3
4] Under UV-light irradiation, Tb(3+)@Zn-MOF and Eu(3+)@Zn-MOF shows strong green and red
luminescence which can be observed by naked eye,the results shows that the antenna effect occurs.The
emission quantum yield and average lifetime of Tb(3+)@Zn-MOF is 42.67% and 0.587 ms.
Fig. 4 The excitation (dashed) and emission (solid) spectra of the Tb(3+)@Zn-MOF.
3
.4 Detection of cations
To explore the potential of Tb(3+)@Zn-MOF for detection of metal ions, the responses of the
luminescene emission of Tb(3+)@Zn-MOF to different cations were investigated. The powder of
-
1
+
2+
Tb(3+)@Zn-MOF was dispersed in an ethanol solution of 0.001 mol L M(NO ) (M = Ag , Pb ,
3
x
2+
2+
+
2+
2+
2+
3+
Mg , Cd , K , Zn , Ni , Co , Fe respectively)and ultrasonicated over 5 min to form the metal ion
n+
incorporated(MOF-M )suspension. The luminescent intensities were recorded at room temperature in
Figure 5(a). Interestingly, the results are that the luminescent intensities of them are greatly dependent
on the metal ions. For example, as shown in Figure 5(b), the luminescence intensity at 545 nm is
2
+
+
+
2+
2+
+
2+
decreased when Zn , Na , K , Mg , Ni , Ag , Co are introduced. In the contrast, the luminescence
+
2+
2+
3+
intensity increased when Ag , Pb , Cd are introduced. Meanwhile, the Fe shows a significant
quenching effect on the luminescence intensity of Tb(3+)@Zn-MOF. The above results indicate that
3+
the Tb(3+)@Zn-MOF is promising chemical sensor for Fe .

(a)
(b)
Fig. 5 (a) Emission spectra and (b) The luminescence intensities at 545 nm of the Tb(3+)@Zn-MOF in
various metal ions
3
+
To better prove that the luminescence quenching by Fe , concentration-dependent studies in the
3+
luminescence intensities of Tb(3+)@Zn-MOF when concentration of Fe ions increased were carried
out. As shown in Figure 6a and 6b, the luminescence intensity of the Tb(3+)@Zn-MOF decreases with
3
+
−6
−5
2
the increase of Fe concentration from 2.5×10 –7.5×10 M.The linear correlation coefficient (R ) in
3
+
the Ksv curse of Tb@Zn-MOF with Fe is 0.99679, this quenching effect can be rationalized by the
Stern-Volmer equation:[35;36]
I /I = 1 + K [M]
0
sv
Where the values I and I represent the luminescence intensities of the Tb(3+)@Zn-MOF with and
0
3
+
3+
without the presence of Fe , respectively, [M] represents the Fe concentration. K is the quenching
sv
4
-1
constant, the value is calculated as 1.57×10 M , which reveals a strong quenching effect on the
-
6
Tb(3+)@Zn-MOF luminescence. The detection limit is about 7.5 ×10 M (ΔS/N=3). [37] The results
3
+
suggest that Fe also can be detected quantitatively using Tb@Zn-MOF.

(a)
(b)
3+
Fig. 6 (a) Stern–Volmer plots describe the dependency of the luminescent intensities on the Fe
−
6
−5
concentration over the range of 2.5×10 –7.5×10 M in ethanol solution. (b) Luminescence emission
spectra of Tb(3+)@Zn-MOF dispersed in ethanol upon incremental addition of
3+
−6
−5
Fe (2.5×10 –7.5×10 M ) ethanol solution(λ = 303 nm).
ex
3
+
As shown in Fig. 7, the Tb(3+)@Zn-MOF is dispersed in the solution containing Fe and other
+
2+
2+
2+
+
2+
2+
2+
metal ions, which include Ag , Pb , Mg , Cd , K , Zn , Ni , Co , respectively. When excited at
-
3
-3
3
03 nm, the Tb(3+)@Zn-MOF is immersed in the mixed ions (1×10 M other metal ions + 1×10 M
3+
Fe ), the measurement of the luminescence intensity shows that the luminescence is completely
3+
quenched, indicating that the selectivity for Fe is not interfered by the existence of other ions.

Fig. 7 Luminescence intensities at 545 nm of the Tb(3+)@Zn-MOF upon the addition of different
-
3
3+
-3
metal ions(1×10 M) (colors) and subsequent addition of Fe (1×10 M) (red) (λex= 303 nm).
3
.5 Engineering filter paper based sensor devices
The simple, rapid and naked eye detecting ability of the probe provided us the opportunity to
3
+
develop a user-friendly and low-cost detection device for the analysis of Fe .A luminescence test
paper was fabricated for rapid detection of cations. We prepared test paper by immersing a filter paper
2
-3
(
2. 0×1.0 cm ) in the ethanol solution of Tb(3+)@Zn-MOF (1×10 M) and drying it in air at room
3
+
temperature. For the detection of Fe , the paper was immersed in the ethanol solution of cations
-
3
+
2+
2+
2+
+
2+
2+
2+
3+
(
1×10 M , Ag , Pb , Mg , Cd , K , Zn ,Ni , Co , Fe ) and then dried in air. In Figure 8, under
the irradiation of UV light of 254 nm, the luminescent colors of the test paper changed from green to
dark green, and finally black with the different metal ions. Considering the results above, we can
distinguish the colors of different metal ions by our naked eyes.
-
3
Fig. 8 Luminescent response of Tb(3+)@Zn-MOF coated paper strips tovarious cations(1×10 M)
+
2+
2+
2+
+
2+
2+
2+
3+
under UV light (254nm) (left to right: Ag , Pb , Mg , Cd , K , Zn , Ni , Co , Fe ).
3
.6 Quenching mechanism
Up to date, the mechanisms for such quenching effects of cations is attributed to four reasons: (1) the
interaction between targeted metal ions and MOFs; (2) the exchange between lanthanide ions and
central metal ions of MOFs (3) the collapse of the crystal structure.(4) the energy competition between
linker and cations.[35, 38,39]Herein, to elucidate the possible sensing mechanism for the quenching
3
+
effect of Fe on the luminescence of Tb(3+)@Zn-MOF, the PXRD was employed to study on the
3+
structural data of the Tb(3+)@Zn-MOF with and without treated with Fe . As shown in Figure 9, the
3+
PXRD of Tb(3+)@Zn-MOF with and without treated with Fe is different, suggesting that the basic
frameworks of Tb(3+)@Zn-MOF changed. We speculate that the quenching effect of
3
+
Tb(3+)@Zn-MOF by Fe is attributed to the collapse of the framework.
Fig.9 PXRD patterns of simulatedZn-MOF and Tb(3+)@Zn-MOF treated with iron ions.
4
. Conclusions

In summary, a new one dimensional Zn-MOF{[Zn(NDIC)·2H O] ·2H O} has been prepared and
2
2
n
3
+
3+
chosen as host to sensitizeTb and Eu by uncoordinated-COOH group in its channels. This composite
has excellent luminescence property and thermostability. Studying of the luminescence properties
3+
reveals that Tb(3+)@Zn-MOF can develop as a highly selective and sensitive sensor for Fe (detection
-
6
3+
limit, 7.5×10 M) via luminescence quenching of Tb . Practically, luminescence test paper was
fabricated and treated with differentcations,the colors have changed from green to dark under the
irradiation of UVlight, respectively.The present results may provide a facile route todesign
luminescence Ln-MOF based on new Zn MOF for sensing and further studiesare currently under way.
Appendix A. Supplementary data
CCDC <1819140> contains the supplementary crystallographic data for Zn-MOF. These data can be
obtained 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.
Acknowledgements
The authors acknowledge the financial support of project of Guizhou youth science and technology
talents(20170695104), Chaozhou science and technology plan (2016GY22), Experimental Teaching
Demonstrating Center of Guizhou province(science and education Experimental Teaching
Demonstrating Center of Guiyang university).
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TOC
3
+
3+
Lanthanide(Tb ,Eu )-functionalized a new one dimensional Zn-MOF. The
composite Tb(3+)@Zn-MOF performs luminescence emission of Tb and shows a
remarkable quenching effect upon the introduction of Fe .
3
+
3
+
A new Zinc metal organic framework has been synthesized and chosen as a parent framework to
3
+
sensitize via encapsulating Tb cations in Zn-MOF. The obtained composite Tb(3+)@Zn-MOF shows
excellent luminescence which performs a remarkable quenching effect in the luminescence emission of
3+
3+
Tb upon the introduction of Fe .