A family of functional Ln-organic framework constructed by iodine-substituted aromatic polycarboxylic acid for turn-off sensing of UO22+

Article abstract of DOI:10.1002/aoc.4898

With the rapid development of nuclear energy, one of the main constraints restricting the development of nuclear energy is the long-term safe disposal of strong uranium waste. Here it is a great significance that we use four new synthetic Ln (III)-based coordination polymers to test the uranium solution. In this study, four three-dimensional coordination polymers 1–4 (CPs-(1–4); Ln?=?Eu, Gd, Sm, Nd) were successfully synthesized through 1:1 complexation of Ln (NO₃)₃·6H₂O with poly-carboxylic acid ligand H₃TIBTC (2,4,6-Triiodo-1,3,5-benzene tricarboxylic acid) which contains substituents of the carboxylic acid group and halogen atom, respectively. Based on the ligand being excellent fluorescent properties in the solution, it prompted us to further study the fluorescence properties of the coordination polymers. Experimental results show that the coordination polymers are favorable materials for the simultaneous selective detection uranium solution from water, being potentially useful in monitoring water quality and treating uranium-wastewater.

Full text of DOI:10.1002/aoc.4898

Received: 22 November 2018
DOI: 10.1002/aoc.4898
Revised: 14 February 2019
Accepted: 16 February 2019
F U L L P A P E R
A family of functional Ln‐organic framework constructed
by iodine‐substituted aromatic polycarboxylic acid for turn‐
2+
off sensing of UO2
Yu Wang1† | Shang‐Hua Xing2† | Xu Zhang1 | Chun‐Hong Liu1 | Bing Li1 | Feng‐Ying Bai1 |
Yong‐Heng Xing1
| Li‐Xian Sun3
1 College of Chemistry and Chemical
Engineering, Liaoning Normal University,
Huanghe Road 850#, Dalian 116029,
People's Republic of China
2 State Key Laboratory of Inorganic
Synthesis and Preparative Chemistry,
College of Chemistry, Jilin University,
Changchun 130012, People's Republic of
China
3 Guangxi Key Laboratory of Information
Materials, Guilin University of Electronic
Technology, Guilin 541004, People's
Republic of China
With the rapid development of nuclear energy, one of the main constraints
restricting the development of nuclear energy is the long‐term safe disposal
of strong uranium waste. Here it is a great significance that we use four new
synthetic Ln (III)‐based coordination polymers to test the uranium solution.
In this study, four three‐dimensional coordination polymers 1–4 (CPs‐(1–4);
Ln = Eu, Gd, Sm, Nd) were successfully synthesized through 1:1 complexation
of Ln (NO3)3·6H2O with poly‐carboxylic acid ligand H3TIBTC (2,4,6‐Triiodo‐
1,3,5‐benzene tricarboxylic acid) which contains substituents of the carboxylic
acid group and halogen atom, respectively. Based on the ligand being excellent
fluorescent properties in the solution, it prompted us to further study the fluo-
rescence properties of the coordination polymers. Experimental results show
that the coordination polymers are favorable materials for the simultaneous
selective detection uranium solution from water, being potentially useful in
monitoring water quality and treating uranium‐wastewater.
Correspondence
Feng‐Ying Bai and Yong‐Heng Xing,
College of Chemistry and Chemical
Engineering, Liaoning Normal University,
Huanghe Road 850#, Dalian 116029,
People's Republic of China.
Email: baifengying2003@163.com;
xingyongheng2000@163.com
KEYWORDS
2,4,6‐Triiodo‐1,3,5‐benzene tricarboxylic acid, coordination polymers, luminescence sensor,
luminescent property, uranyl
Funding information
Commonweal Research Foundation of
Liaoning province in China, Grant/Award
Number: 20170055; Guangxi Key Labora-
tory of Information Materials, Guilin
University of Electronic Technology, P.R.
China, Grant/Award Number: 151002‐K;
National Natural Science Foundation of
China, Grant/Award Number: 21571091
1 | INTRODUCTION
crystal material‐‐‐organic–inorganic hybrid coordination
polymer (coordination polymer).[1–9] And the metal–
At the end of the twentieth century, with the rapid devel-
opment of inorganic materials as the main body of the
crystallization, which promote the birth of a new type of
organic materials have continued to expand in the
fields of biochemistry, green chemistry and pharmaceuti-
cal chemistry.[10–13] Therefore, the design synthesis,
mechanispolymerm and performance research of metal
organic coordination polymers have developed rapidly
into interdisciplinary research hotspots. At the same time,
The authors declare no competing financial interest.
†These authors contributed equally.
Appl Organometal Chem. 2019;e4898.
wileyonlinelibrary.com/journal/aoc
© 2019 John Wiley & Sons, Ltd.
1 of 13
https://doi.org/10.1002/aoc.4898

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WANG ET AL.
environmental problems that endanger human health
and social sustainable development have become increas-
ingly concerned and urgent issues to be solved, such as
water pollution, air pollution, industrial waste pollution,
etc.[14] Over the past few years, the use of nuclear power
generation has greatly alleviated the demand for electric-
ity, but in uranium water treatment, uranium enrichment
and nuclear fuel reprocessing process will produce a lot of
uranium‐containing wastewater, which brought unprece-
dented pressure to the global environment and human
survival safety.[15–19] Nowadays, governments and scien-
tists have invested a lot of manpower, material and finan-
cial solution to the uranium‐containing environmental
problems. At present, the commercial methods used to
test uranium contaminants and the instruments based
on science and technologies are expensive and poor ver-
satility. Therefore, develop a new and efficient method
which has the ability to detect the uranium pollutant is
extremely urgent need.
In recent years, porous coordination polymers crystal-
line material is an important branch, it has shown a cer-
tain value in the uranium detection and absorption,
causing the scientific workers are widely concerned about
it and research it.[20,21] Using different interactions
between host and guest, coordination polymers have been
developed in terms of molecular recognition and fluores-
cent probes, and many well‐known scientists have made
outstanding contributions in this field.[22–25] Coordina-
tion polymers materials for chemical testing must have
a suitable conversion signal, the chemical effect into
measurable physical quantities in which fluorescence is
a very good signal[26–29] and it usually has the character-
istics of the naked eye can be observed. Due to the unique
luminescent properties of rare earth ions, lanthanide
coordination polymers have been used as fluorescent
probes.[30–35] In addition, a suitable signal conversion
medium immobilized on the framework of the fluores-
cent coordination polymers material is also important,
which should have a specific recognition at the molecular
level with analytical and can continuously affect the sig-
nal change.[36] In the past, a large number of studies
based on coordination polymers have focused on the
application of single signal conversion media, unsatu-
rated metal centers or Lewis base sites, and they have
excellent responsiveness to individual components of
organic molecules, metal ions or explosives. A variety of
pre‐functionalization and post‐synthesis methods facili-
tate the introduction of different signal conversion media
into the bulk coordination polymers material, the struc-
ture of a variety of organic ligands and easy functional-
ized pore surfaces to provide further possibilities for the
introduction of different signal conversion media, which
is beneficial to produce coordination polymers based
HIGHLIGHTS
• Four isostructural 3D network lanthanide
coordination polymers
• 2,4,6‐Triiodo‐1,3,5‐benzene tricarboxylic acid
(H3TIBTC)
2+
• Effective fluorescence detection of UO2
fluorescence sensors with multiple response recognition
capabilities.[37,38]
Coordination polymers based on carboxylic acid
ligands have always been a hotspot for coordination
chemists.[39–41] Relative to other nitrogen‐containing
ligands (such as pyridine, schiff base, imidazole), carbox-
ylic acid ligands have great advantages. Since carboxylic
acids are extremely sensitive to pH, the different
degree of deprotonation of the carboxyl groups at differ-
ent pH values results in different coordination modes
(Figure 1).[42] Carboxylic acid groups have a strong ability
to bridge, which can take either double‐dentate bridging
or single‐dentate bridging. Among many reported coordi-
nation polymers, the carboxyl groups have taken the
coordination of multiple atoms in the case of a single
ligand coordination mode, with the exception of a few
auxiliary ligands (or water molecules) involved
mode.[43,44] A wide range of coordination modes for
poly‐carboxylic acids can meet the needs of coordination
and pattern of different metal ions and coordination
angles. In addition, the carboxylic acid can also form
the strong hydrogen bonds in the molecular packing.
Depending on the degree of deprotonation, a carboxyl
group can be used as a donor for hydrogen bonds or as a
hydrogen bond. Sometimes a number of carboxyl groups
in
a polycarboxylic acid ligand may be partially
deprotonated, and in this case in the supramolecular
weak force or coordination of the bond force driven by
self‐assembly, it can be provided as hydrogen donor and
acceptor at the same time.[45] The poly‐carboxylic acid
ligand includes an aromatic carboxylic acid and an
aliphatic carboxylic acid, and the aromatic carboxylic acid
has the following characteristics with respect to the
aliphatic carboxylic acid: i) Because it has the aromatic
ring and does not have the rotation make it has an aro-
matic ring rigid, rigid ligand is more conducive to crystal
growth than flexible ligand. ii) Due to the rigidity of the
ligand itself, it is easier to connect metal ions to form a
high‐dimensional structure. The structure usually accom-
panied by the existence of holes, so these coordination
polymers tend to have a novel topology. iii) The presence
of conjugated systems in aromatic rings favors the

WANG ET AL.
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FIGURE 1 Carboxylic acid with
different coordination modes: (a) Single
tooth; (b) Bridge double teeth; (c) Bridging
single and double teeth; (d) Chelate
bidentate; (e) Chelating bridge combined
with double teeth; (f) Bridging single
tooth; (g) Bridge double monocular; (h)
Bridge type four tooth type
transmission of electrons, resulting the coordination poly-
mers often have some special properties such as electrical
and magnetic properties. Therefore most of them have
great research value.[46] Trimesic acid is one of the most
widely used and most studied ligands in the construction
of new structures for the coordination polymers. The
majority chemists love it the main reason not only
because the above‐mentioned aromatic carboxylic acid
has the characteristics, but also its symmetrical arrange-
ment of three carboxyl and benzene ring in the same
plane. At the same time we independently synthesized
this ligand on the basis of the trimesic acid which intro-
duced iodide atoms and the conjugate system is condu-
cive to electronic transfer, making the coordination
polymers have some special properties in the field of fluo-
rescence.[47–49] Because of the unique structure and prop-
erties of rare earth ions, lanthanide coordination
polymers have wide application prospect in light, electric-
ity, magnetism and catalysis. The luminescence of it has
the advantages of long life, strong strength and pure
color. In recent years, people have great interest in it
and it has been becoming an active research field.
In this work, we have chosen a functional organic
ligand (Scheme 1) containing both a polycarboxylic acid
group and a halogen atom based on the following three
points: i) Rigidity is advantageous for constructing the
pore structure; ii) Overcoming the effect by the antenna
effect that the rare earth ion absorption coefficient is
low, easy to sensitize the light; iii) The conjugate
ring can use the Lewis base site can be a variety of
host and guest interaction to enhance its ability to
detect. Using the solvent thermal reaction method, we
successfully designed and synthesized four new rare
earth‐organic coordination polymers, and constructed a
multi‐responsive fluorescence sensor. It has a good fluo-
rescence quenching response to uranium solution. To
our knowledge, structures and properties of poly [tris
(dimethylformamide)(μ3–2,4,6‐triiodol‐1,3,5‐benzene tri-
carboxylic acid)‐lanthanide (III)] [Ln (TIBTC)(DMF)3]n
(H3TIBTC = 2, 4, 6‐Triiodo‐1, 3, 5‐benzene tricarboxylic
acid) are reported rarely. In the work, we not only research
synthesis and structure, but also investigate selective
2+
UO2
ion detection firstly. The experimental results
indicate that the coordination polymers can be used as
candidate materials for selective detection of uranium.
2 | EXPERIMENTAL SECTION
2.1 | Materials and methods
All chemicals purchased commercially were analytical
grade or better and used without further purification. Sol-
vents were purified according to the standard methods.
The ligand 2,4,6‐triiodo‐1,3,5‐benzene tricarboxylic acid
(H3TIBTC) was prepared as reported previously and
appropriately modified the methods. Elemental analyses
of C, H, and N were conducted on a Perkin‐Elmer 240C
automatic analyzer at the analysis center of Liaoning
Normal University. All IR measurements were obtained
using a Bruker AXS TENSOR‐27 FT‐IR spectrometer with
pressed KBr pellets in the range of 400–4000 cm−1 at
room temperature. UV–Vis–NIR spectra for the coordina-
tion polymer and ligand were recorded on a JASCO V‐570
UV/VIS/NIR microspectrophotometer (200–2500 nm, in
form of solid sample). Thermogravimetric analysis (TG)
was performed on a Perkin Elmer Diamond TG/DTA
under atmosphere from room temperature to 800 °C
with a heating rate of 10 °C/min. The morphology of
the coordination polymer was investigated using
SCHEME
1
The structure of 2,4,6‐Triiodo‐1,3,5‐benzene
tricarboxylic acid

4 of 13
WANG ET AL.
scanning electron microscope and X‐ray analyzer (SEM,
SU8010). X‐ray powder diffraction patterns were
obtained on a Bruker Advance‐D8 equipped with Cu‐Kα
radiation, in the range 5° < 2θ < 55°, with a step size of
0.02° (2θ) and an count time of 2 s per step. The
photoluminescent spectra of the coordination polymers
were measured on a HORIBA Fluoromax‐4‐TCSPC spec-
trofluorometer equipped with Spectra LED Pulsed LED
sources at room temperature (200–1000 nm). Solid‐state
circular dichroism (CD) measurements were performed
on MOS‐500/ALX300 (50160HZ 250 W) (Scheme 2).
22.80; H, 2.22; N, 4.44%. Found: C, 22.86; H, 2.22; N,
4.44%. IR data (KBr, cm−1): 3417, 3123, 2925, 2357,
1656, 1589, 1397, 1307, 1111, 932, 736, 676, 509.
2.3 | X‐ray crystal structure
determination
A single crystal of suitable dimensions for the coordina-
tion polymer was mounted on glass fibers for the X‐ray
structure determinations. Reflection data were collected
at room temperature on a Bruker AXS SMART APEX II
CCD diffractometer with graphite monochromatized Mo‐
Kα radiation (λ = 0.71073 Å). A semiempirical absorption
correction was applied by the program SADABS.[51] The
program suite SHELXTL‐97 was used for space‐group
determination (XPREP), direct method structure solution
(XS), and least‐squares refinement (XL).[42,53] All non‐
hydrogen atoms were refined with anisotropic displace-
ment parameters. The positions of the hydrogen atoms
around the carbon atoms were included using a riding
model. Hydrogen atoms of coordination water molecules
and lattice water molecules were found in the difference
Fourier map. The details of the crystal parameters, data
collection, and refinement for the CPs‐(1–4) are summa-
rized in Table 1, and selected bond lengths and angles with
their estimated standard deviations are listed in Table S1‐
S4. Hydrogen bond lengths (Å) and angles (°) for the
CPs‐(1–4) are listed in Table S5. Further details are pro-
vided in the Supporting Information.
2.2 | Synthesis
2,4,6‐Triiodo‐1,3,5‐benzene tricarboxylic acid was synthe-
sized on the basis of the modified method in related
literature.[50] Specific synthetic steps are given in the
supporting information.
[Ln (TIBTC)(DMF)3]n (Ln = Eu, Gd, Sm, Nd) (CPs‐
(1–4)). The CP‐1 was synthesized by blending Ln
(NO3)3·6H2O (0.0250 g, 0.05 mmol), H3TIBTC (0.0250 g,
0.04 mmol) and added solvent (DMF: EtOH = 1: 1)
2 ml. The mixture solution was placed in a 20 ml Pyrex
vial and stirred for 1 hr at room temperature and then
heated statically at 85 °C for 3 days. Slowly cool down
and green crystals of the CP‐1 were obtained after filtra-
tion and washing thoroughly with absolute ethanol
(EtOH). The solution pH was 5 before the reaction and
5 at the end. And the CPs‐(2–4) were synthesized in the
same manner. Detailed analysis data are as follows:
[Eu (TIBTC)(DMF)3]n (CP‐1) Yield: 55% (based on
H3TIBTC), anal. Calc. for C18H21I3N3O9Eu (956.05): C,
22.61; H, 2.21; N, 4.40%. Found: C, 22.66; H, 2.25; N,
4.44%. IR data (KBr, cm−1): 3410, 3126, 2924, 2395,
1645, 1580, 1389, 1310, 1108, 939, 740, 675, 515.
[Gd (TIBTC)(DMF)3]n (CP‐2) Yield: 55% (based on
H3TIBTC), anal. Calc. for C18H21I3N3O9Gd (961.33): C,
22.49; H, 2.20; N, 4.37%. Found: C, 22.53; H, 2.26; N,
4.41%. IR data (KBr, cm−1): 3415, 3126, 2922, 2350,
1651, 1583, 1387, 1305, 1111, 940, 738, 671, 506.
[Sm (TIBTC)(DMF)3]n (CP‐3) Yield: 55% (based on
H3TIBTC), anal. Calc. for C18H21I3N3O9Sm (954.44): C,
22.65; H, 2.22; N, 4.40%. Found: C, 22.68; H, 2.26; N,
4.45%. IR data (KBr, cm−1): 3405, 3128, 2925, 2370,
1656, 1581, 1380, 1313, 1109, 935, 738, 678, 506.
3 | RESULTS AND DISCUSSION
3.1 | Structure descriptions
X‐ray diffraction analysis revealed that the CPs‐(1–4)
crystallized in the cubic system and the space group are
all P213. CPs‐(1–4) have the same structure, here we
choose the CP‐1 [Eu (TIBTC)(DMF)3]n as an example
to discuss. The molecular structure of the CP‐1 consisted
of one Eu atom, three H3TIBTC ligands, three coordi-
nated DMF ligands. The coordination pattern of the
center metal is shown in Figure 2a. In the structure, the
1-
linking pattern of ligand H3TIBTC is μ3‐ηO1ηO1ηO
ηO1ηO1ηO1, where two oxygen atoms on each carboxyl
group take the coordination mode of bidentate chelating
(Figure 2b), and coordinating DMF as a terminal ligand
prevents the unit linkage in other directions. The Eu
[Nd (TIBTC)(DMF)3]n (CP‐4) Yield: 55% (based on
H3TIBTC), anal. Calc. for C18H21I3N3O9Nd (948.32): C,
SCHEME 2 Synthesis route of ligand
1,3,5‐Triiodo‐2,4,6‐trimethylbenzene

WANG ET AL.
5 of 13
TABLE 1 Crystallographic data for the CPs‐(1–4)
Coordination polymers
CP‐1
CP‐2
CP‐3
CP‐4
Chemical formula
C18H21I3N3O9Eu
956.05
C18H21I3N3O9Gd
961.33
C18H21I3N3O9Sm
954.44
C18H21I3N3O9Nd
948.32
M (g mol−1
)
Crystal system
Space group
a (Å)
cubic
cubic
cubic
cubic
P2(1)3
P2(1)3
P2(1)3
P2(1)3
14.1345 (2)
14.1345 (2)
14.1345 (2)
90
14.1149 (2)
14.1149 (2)
14.1149 (2)
90
14.1171 (2)
14.1171 (2)
14.1171 (2)
90
14.1918 (3)
14.1918 (3)
14.1918 (3)
90
b (Å)
c (Å)
α (deg)
β (deg)
γ (deg)
V (Å3)
90
90
90
90
90
90
90
90
2823.85(7)
4
2812.12(7)
4
2813.43(7)
4
2858.33(10)
4
Z
Dcalc (g·cm−3
)
2.249
2.271
2.253
2.204
Crystal size (mm)
F (000)
0.51 × 0.40 × 0.31
1776
0.51 × 0.41 × 0.30
1780
0.51 × 0.42 × 0.30
1772
0.50 × 0.41 × 0.30
1764
μ (Mo–Kα) (mm−1
)
5.547
5.698
5.426
5.102
θ (deg)
2.04–31.26
19701
2.04–31.31
19616
2.04–31.30
19627
2.03–31.28
19947
Reflections collected
Independent reflections
Parameters
2929(2504)
106
2915(2587)
106
2939(2609)
105
2992(2765)
106
Rint
0.0354
0.0340
0.0333
0.0227
Δ(ρ) (e Å−3
)
0.697 and − 0.629
0.702 and − 0.640
2.144 and − 1.075
0.858 and − 0.648
Goodness of fit
1.016
1.034
1.040
1.037
Ra
0.0224 (0.0341)b
0.0411 (0.0442)b
0.0256 (0.0338)b
0.0563 (0.0595)b
0.0342 (0.0427)b
0.0857 (0.0901)b
0.0203 (0.0246)b
0.0425 (0.0441)b
a
wR2
aR = Σ||Fo|–|Fc||/Σ|Fo|, wR2 = [Σw (Fo2–Fc2)2/Σw (Fo2)2]1/2; [Fo > 4σ(Fo)].
bBased on all data.
atom is nine‐coordinated by three oxygen atoms (O1)
from the DMF ligand with bond lengths of Ln‐O bond
length is 2.534 Å, six oxygen atoms (O2, O3) from the
three coordination H3TIBTC ligands with the bond
lengths are 2.574 Å and 2.644 Å, forming a LaO9 irregular
tetradecahedron which has the chirality (Figure 2c). The
contact of Eu‐Eu bond distance is 10.0039 (2) Å. All these
bond lengths are similar to the relevant literature, which
is shown they are in a reasonable range.[37] For the struc-
tural unit [Eu (COO)3(DMF)3] in the CP‐1, when viewed
along the direction, five structural units form a ring‐
shaped twisted pores (Figure 2d), these twisted pores are
connected by the C‐bonding of the H3TIBTC ligand to
extend the dimensionality, yielding a 3D cage structure
(Figure 2e). In consideration of the complexity of the
structure, we try to interpret the framework topologically
and the ligands being viewed as nodes, respectively. The
simplified structure is shown in Figure 2f. Each Eu is sim-
plified as a 3‐connected node, and each ligand is also sim-
plified as a 3‐connected node, and the whole structure is a
3, 3‐connected srs topology. Although one related CP‐3
have been previously reported,[54] its detailed molecular
structural descriptions are not specific enough, especially
its functional properties have not been well studied.
Therefore, it is necessary for us to carry out a systematic
study of the properties of the coordination polymers.
3.2 | IR spectra
The IR spectra of the CPs‐(1–4) are similar to each other,
shown in Figure S1. Here we take the IR spectra of the
CP‐1 to discuss. The broad absorption bands appearing
at 3417 cm−1 of coordination polymer indicates the

6 of 13
WANG ET AL.
FIGURE 2 Structure of the CP‐1: (a) coordination environment of Eu3+ ion (#1: 1‐z, x + 0.5, 1.5‐y; #2: y‐0.5, 1.5‐z, 1‐x); (b) connection
fashions of H3TIBTC ligand; (c) rotationally symmetric EuO9 tetradecahedron; (d) a ring‐shaped twisted pore structure formed by five
metal ions and five ligands; (e) 3D cage structure of the CP‐1 (f) simplified topology of the CP‐1. Symmetry transformations used to generate
equivalent atoms: A = x, y, z; B = 1/2‐x, −y, 1/2 + z; C = 1/2 + x, 1/2‐y, −z; D = −x, 1/2 + y, 1/2‐z; E = z, x, y; F = y, z, x; G = 1/2‐z, −x, 1/
2 + y; H = −y, 1/2 + z, 1/2‐x; I = 1/2 + z, 1/2‐x, −y; J = 1/2‐y, −z, 1/2 + x; K = −z, 1/2 + x, 1/2‐y; L = 1/2 + y, 1/2‐z, −x
presence of water molecules. The peaks around 1645 and
1397 cm−1 are assigned to the asymmetrical stretching
vibration (νasCOO−) and symmetrical stretching vibration
(νsCOO−) of C=O bond, and 1310, 1589 and 2925 cm−1
(νs of C=C and C–C bonds) are attributed to the skeletal
vibrations of the organic aromatic rings. And the peaks
at the position of 937–740 cm−1 can be assigned to char-
acterization vibration of δ=C‐H in the 1,2,4‐position substi-
tution on the benzene ring, respectively. Table S6 shows
the attribution of IR (cm−1) for ligand and CPs‐(1–4).
randomly selected single crystals of the CP‐1 were used
for the CD spectrum. As shown in Figure S2 that single
crystal structure of the CP‐1 is homochiral and the bulk
sample may be a pure chiral crystal.
3.4 | UV–vis assignment
The UV–Vis spectrum of the ligand H3TIBTC and CP‐1 is
shown in Figure S3, to be recorded in the form of solid
sample. And the characteristics data of UV–Vis spectra
is listed in Table S7. CP‐1 presented three peaks, the peak
at 218 nm was attributed to the π → π* transition of the
H3TIBTC ligand, the peak of 292 nm was attributed to
the n → π* transition of the H3TIBTC ligand. At the same
time, the broad peak at around 353 nm for the coordina-
tion polymer should be attributed to LMCT.
3.3 | Chiral analysis
Studying shown that achiral ligands can form pure chiral
crystals under certain chiral induction factors. In this
work, we use the ligand tri‐iodophthalic acid belongs to
a kind of achiral substance, and the X‐ray single crystal
diffraction data show that the crystal has a chiral struc-
ture. Solid‐state circular dichroism (CD) measurements
were performed on solid material in KBr plates to illus-
trate the chiral nature of the CP‐1, and groups of
3.5 | Thermal properties
The thermogravimetric analysis of the coordination poly-
mer generally refers to dynamic thermogravimetric

WANG ET AL.
7 of 13
analysis, which is performed according to a pre‐
programmed procedure. The weight of the sample was
recorded while the sample was heated at a constant speed
varying temperature. The thermal stability of the coordi-
nation polymer is an important means of characterizing
the properties of the coordination polymer. The heat of
the coordination polymer system stability includes the
removal of guest molecules, ligand substitution, isomeri-
zation, conversion of coordination structures, thermal
dissociation, thermal decomposition and many other pro-
cesses. Therefore, by analyzing the thermogravimetric
properties of the coordination polymer, the structural
important information of the coordination polymer can
be derived.
To examine the thermal stability of the coordination
polymers, thermal gravimetric analysis (TG) was carried
out at a heating rate of 10 °C min−1 under a N2 atmo-
sphere with the temperature range from 30 to 800 °C,
and the thermalgravimetric curves of the CPs‐(1–4) are
shown in Figure S4. The TG curves of the coordination
polymers are similar to each other. Take the CP‐1 as an
example. The TG curve of the CP‐1 is divided into two
steps. The CP‐1 shows a first weight loss between 200
and 400 °C attributable to the loss of three coordinating
DMF molecules (obsd: 22.39%; calcd: 23.21%). The second
loss (obsd: 40.00%) between 400 and 600 °C corresponds
to the decomposition of the whole organometallic coordi-
nation polymer frame structure collapses (calcd: 40.19%),
the residual mass of the final metal oxide residue is 37%
of the original weight.
experiment the CP‐1 is added to the prepared acidic
potassium permanganate solution, the partial decolo-
ration of the solution and the change in color of the
crystals were evident to the naked eye (Figure 3), finally,
almost complete decoloration of the solution was
detected after 6 hr (in which KMnO4 has been undergone
a substantial change, the CP‐1 have changed to another
black material). We tried to separate the new material
from the solvent, but unfortunately, this idea failed to
be realized because in practice we found that it was diffi-
cult to completely separate the newly formed material
from the solution. The absorbance curves of potassium
permanganate with time were shown in Figure 3.
In general, we have synthesized a rigid water‐stable 3D
coordination polymers. The coordination polymer is a
good example of a coordination polymers based material,
which is effective to reduce the environmental pollution
of potassium permanganate. This work requires us to fur-
ther explore it in detail.
3.7.2 | General fluorescent property of the
coordination polymer
The fluorescence of inorganic–organic coordination poly-
mers has been currently drawing significant attention in
the development of fluorescent materials. Here we take
the CP‐1 as an example. Regarding the luminescence
properties of europium, CP‐1 was studied at an excitation
wavelength of 390 nm with slit width (1:1) and Figure 4
gives the excitation spectrum and emission spectrum of
5
7
CP‐1. The characteristic D0 → FJ (J = 1–4) transitions
of Eu (III) ion at 591, 615, 650, and 693 nm show efficient
ligand to‐Eu energy transfer. The fairly weak emission
3.6 | PXRD analysis
band 5D0
→
7F0 at 581 nm is attributed to the
In order to confirm whether the crystal structures were
truly representative of the bulk materials, the PXRD
patterns of the coordination polymers were recorded
(Figure S5). Comparing with the corresponding simulated
single‐crystal diffraction data, all the peaks present in the
measured patterns closely match the simulated patterns
generated from single crystal diffraction data, which indi-
cated that coordination polymer in the pure phase.
3.7 | Application and exploration
3.7.1 | Coordination polymer for the
reduction of potassium permanganate
Based on the synthesized three‐dimensional skeleton
single‐crystal coordination polymer having a halogen
atom such as iodine, we sought to harness the halogen
atom of the coordination polymer to discolor the acidic
potassium permanganate solution. In this part of the
FIGURE 3 Visible potassium permanganate color change chart
and the absorbance of potassium permanganate curve with time
(the arrows indicate the change in the absorption spectra with time)

8 of 13
WANG ET AL.
FIGURE 4 Luminescent spectra of the
CP‐1 (λex = 390 nm) in the solid state
symmetry‐forbidden emission of the Eu (III) ions in the
Eu3+ ion. Compared with lifetime values of the
previously reported lanthanide coordination polymers,
the lifetime value of the CP‐1 is longer than those
of Tb (PBI)3(DPEPO) (where HPBI = 3‐phenyl‐4‐ben-
zoyl‐5‐isoxazolone, DPEPO = bis(2‐(diphenylphosphino)
phenyl), lifetime = 168 μs),[55] [Eu3(bpydb)3(HCOO)(μ3‐
OH)2(H2O)]·(x solvent) (where bpydbH2 = (4,4′‐(4,4′‐
bipyridine‐2,6‐diyl) dibenzoic acid, lifetime = 258 μs)[56]
and Eu(L)3(H2O)2](H2O) (where HL = 4‐(Dipyridin‐2‐yl)
aminobenzoic acid), lifetime = 428 μs).[57]
CP‐1. The emission band 5D0
→
7F1 pertained to the
prominent magnetic dipole transition, which is almost
influenced by the coordination environment. On the
5
7
other hand, the outstanding D0 → F2 emission band,
possessing strong electric dipole character, is hypersensi-
tive to the coordination environment. Herein Eu (III) ions
luminescence can act as a sensitive probe of the lantha-
nide coordination environment. In particular, the ratio
of the intensity (5D0 → 7F2): (5D0 → 7F1) transition is very
sensitive to the symmetry of the Eu (III) ion center. In the
spectrum, it can be obviously seen that the intensity of
5
7
the electric dipole transition D0 → F2 is much stronger
3.7.4 | Fluorescence quenching response
to metal cations
5
7
than that of the magnetic dipole transition D0 → F1,
which implies that the Eu (III) ions in CP‐1 are located
in a lower symmetric coordination environment. This
can be confirmed by analysis of the single crystal diffrac-
In terms of the CPs‐(1–4) have the 3D network frame-
work with evenly arranged porous and excellent chemical
stability, the CPs‐(1–4) were explored for the application
in the detection of metal ions in a solvent system based
on fluorescent sensing. It was found that their emissions
are strong and almost not affected by solvent effect. The
CPs‐(1–4) all show intense fluorescent emissions in
water. The high water stability together with good fluo-
rescent performance of the four coordination polymers,
thus prompt us to explore their fluorescent sensing prop-
erties in water. CPs‐(1–4) are structurally similar, here we
select CP‐1 as a representative to describe its fluorescence
efficacy.
To explore the ability of sensing a trace quantity of
metal ions and UO22+ ion, the grounded powder samples
of the CP‐1 (10 mg) were immersed in 30 ml of deionized
water and ultrasonicated over 30 min to form a steady
turbid suspension. Then, 2 ml of the as‐made CP‐1 sus-
pension was added to a cuvette containing 2 ml of
5
7
tion data. Among these emission lines, the D0 → F2
transition is almost striking, indicating intense red lumi-
nescence of CP‐1.
3.7.3 | Fluorescence lifetime
In order to explore Luminescent characterization, we
tested the fluorescence lifetime of solid CP‐1 and the
test chart as is shown in Figure S6. The measured fluores-
cence lifetime of CP‐1 is approximately 670 μs. At the
same time, after the metal and the ligand were mixed
and ground in the same ratio, the fluorescence lifetime
value of the sample was measured (171 μs). It can be
seen that the metal and the ligand undergo a reaction
coordination to greatly improve the fluorescence lifetime.
It is shown that the energy of ligand efficiently transfer to

WANG ET AL.
9 of 13
1 mM aqueous solutions of 14 different metal ions of
suspension. Then, 2 ml of the as‐made CP‐1 suspension
was added to a cuvette containing 2 ml of aqueous solu-
tions of 10 different concentrations of uranium solution
to form the suspensions for fluorescence studies. The
fluorescent intensities of these CP‐1 suspensions were
recorded at room temperature and compared (Figure 7).
Interestingly, it was found that the fluorescent intensities
are greatly dependent on the identities of the concentra-
tions of uranium solution. The CP‐1 has obvious fluores-
cence quenching effect for different concentrations of
uranium solution.
Co2+, Ni3+, Cu2+, Zn2+, Cd2+, Mn2+, Mg2+, K+, Ca2+
,
Na+, Ba2+, Fe2+, Fe3+, Al3+, and UO2 ion respectively,
to form the metal ion incorporated CP‐1‐Mn+ suspensions
for fluorescence studies. The fluorescent intensities of
these CP‐1 suspensions were recorded at room tempera-
ture and compared (Figure 5). Interestingly, it was found
that the fluorescent intensities of them are greatly depen-
dent on the identities of the metal ions. For the CP‐1,
2+
Co2+, Ni3+, Cu2+, Zn2+, Cd2+, Mn2+, Mg2+, K+, Ca2+
,
Na+, Ba2+, Fe2+ show negligible effects on its fluores-
cence, and Fe3+ and Al3+ exhibits a moderate degree of
quenching, whereas Fe3+ gives the quenching with the
efficiency as 27.40%, Al3+ is about 9.96%. They are much
2+
The detection limit of the CP‐1 for the UO2 ions is
calculated by following equation:
2+
Detection limit ¼ 3 σ=k
(1)
lower than that of UO2 ion (Figure 6).
Where, k represents the slope between the lumines-
cence intensity vs. log[UO22+]; σ represents the standard
deviation of blank determination. The detection limit of
the CP‐1 is calculated to be 0.011 mM (5.54 mg/L) for
2+
3.7.5 | Selective UO2 ion detection based
on fluorescence quenching
2+
UO2 ions detection, which is lower than the MOF‐76
High energy efficiency, low pollution and low cost, these
advantages allow nuclear energy to develop well through-
out the world. China's nuclear power development report
pointed out that “China's nuclear power has formed a
large‐scale development pattern”. In the development
process of nuclear energy industry, one of the main con-
straints restricting the development of nuclear energy is
the long‐term safe disposal of strong uranium waste. So,
here we use the new compounds to test the uranium solu-
tion will be a great significance.
reported to detect uranyl ions in solution carried out by
Sun et al. with the poor detection limits of 23.8 mg/
L.[58] The lower detection limits indicate the feasibility
and sensitivity of the CP‐1 to detect biological molecule
2+
of UO2 ions.
To furthermore understand the luminescence sensitiv-
ity, the quenching efficiency was quantified using the
Stern‐Volmer (SV) equation:
I0=I ¼ KSV½Qꢀ þ 1
(2)
In experiment the powder samples of the CP‐1 (10 mg)
were immersed in 30 ml of deionized water and
ultrasonicated over 30 min to form a steady turbid
Where, I0 is the initial emission peak intensity, I is the
emission peak intensity after the addition of the analytes
FIGURE 5 Fluorescence intensity
curves of CP‐1 for different metal ions
2+
and UO2

10 of 13
WANG ET AL.
FIGURE 6 Comparison of quenching
efficiency of CP‐1 for different metal ions
2+
and UO2
FIGURE
7
Quenching curves of CP‐1 for different
concentrations of uranium solution
FIGURE 8 Fluorescence intensity curve of CP‐1 for different
concentrations of uranium solution
2+
(UO2 ions), [Q] is molar concentration of the analytes
(quencher), and KSV is the quenching constant, which
was used to quantitatively evaluate the performance of
In addition, further experiments also showed that the
quenching efficiency of the CP‐1 toward UO2 ions can
almost reach the maximum value within 1 min. This
2+
the CP‐1 as a UO2 ions sensing material.[38] As shown
2+
in Figure 8, the quenching efficiency of the CP‐1 in differ-
ent concentrations of uranium ion solution (20 μM,
40 μM, 60 μM, 100 μM, 200 μM, 400 μM, 600 μM,
800 μM, 1000 μM, 2000 μM) is different. The quenching
constant (KSV) was 4 × 103 M−1. The greater KSV values
revealed an extremely high sensitivity, which made the
CP‐1 one of the best sensitive luminescence based
metal–organic detectors of different concentrations of
uranium solution.
rapid response is quite appealing and may be attributed
to the fact that UO2 ions can rapidly diffuse into the
channels of the CP‐1 and interact with luminophores on
the pore surface.
The forbidden f‐f transition of rare earth ions result in
its low molar absorption coefficient.[59] In order to over-
come the shortcoming of low molar absorption coeffi-
cient, organic iodine substituted polycarboxylic acid
ligands, which possess electron conjugate induction
2+

WANG ET AL.
11 of 13
effect, are introduced to coordinate with rare earth ions.
The energy of the organic ligand is transmitted to the rare
earth ions through the antenna effect and so that the rare
earth ions are sensitized. For CP‐1, the luminescence of
the rare earth ion Eu3+ is mainly in suspension derived
from the energy transfer of the ligand. However, it is
found that the energy of the ligand is not well transferred
to Eu3+ in the aqueous solution. That is to say, the emis-
sion peaks of both ligands and metal ions appear, and the
peak of the ligand is slightly stronger than the character-
istic peak of the metal ion, when detecting uranium ions.
Therefore, we have further studied the luminescence
sensing properties of CP‐1 for the detection of uranium
ions by monitoring the characteristic peak intensity of
the ligand in the aqueous solution. Meanwhile, the main
factor affecting the energy transfer is the energy differ-
ence of the triplet state of the ligand and the excited state
of the rare earth ion Eu3+. So, the reason why the ura-
nium ion affects the fluorescence intensity of the ligand
is that the interaction between the uranium ion and the
ligand of the coordination polymer lead to the change of
2+
FIGURE 10 Quenching efficiency of the CP‐1 for UO2 in
repetitive experiments
2+
triplet energy level of the ligand. The UO2 ions may
enter the channels of the CP‐1 and interact with the
iodine atoms on the ligand when the uranium solution
was added. The SEM micrographs of the CP‐1 before
and after detection may further confirmed (Figure S7‐
S8). Thereby iodine substitution absorbs a part of the
excited state energy of the ligand, so that the energy
transfer from the ligand to the rare earth ions is weak-
ened, resulting in fluorescence quenching. In other
words, it is inferred from the Figure 9 that there may be
both static quenching and dynamic quenching processes.
FIGURE 11 PXRD before and after methanol washing
2+
The interaction between the UO2 ions and the CP‐1 is
the cause of static quenching. The dynamic quenching
3.7.6 | Repetitive experiment
can be attributed to the energy and electron transfer pro-
cesses between the UO2 ions and the CP‐1.
As a sensor, it is necessary to be able to use it stably.
Therefore, we also investigated the fluorescent properties
of regenerated CP‐1, which was simply obtained by wash-
ing with methanol. It was found that the quenching effi-
2+
2+
ciencies of CP‐1 for UO2 ions are basically unchanged
up to six cycles, demonstrating its good stability for the
detection applications (Figure 10). At the same time we
tested the crystals with methanol washing for PXRD
and found that the purity of the crystal structure did not
change significantly (Figure 11).
4 | CONCLUSIONS
In this work, we have successfully synthesized four
porous structure coordination polymers [Ln (TIBTC)
(DMF)3]n (Ln = Eu, Gd, Sm, Nd) (CPs‐(1–4)) under
the hydrothermal condition by using a poly‐carboxylic
acid H3TIBTC which contains carboxylic acid group
FIGURE 9 Linear relationship of I0/I ratio and the concentration
of uranium

12 of 13
WANG ET AL.
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new coordination polymers possessed a fascinating 3D
network framework. Fluorescence experiments have
shown that the coordination polymers exhibited good
fluorescence quenching effects in the fluorescence detec-
tion experiments of uranium solutions. This finding
could open up a new avenue to address the issues for
uranium fuel waste treatment and detection in an aque-
ous solution.
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Selected bond lengths (Å) and angles (deg) for CPs‐(1–4)
are listed in Table S1‐S4. Hydrogen bond lengths (Å)
and angles (°) for the CPs‐(1–4) are listed in Table S5.
Table S6 shows the attribution of IR (cm−1) for ligand
H3TIBTC and CPs‐(1–4). And the characteristics data of
UV–Vis spectra is listed in Table S7. Infrared spectra of
the ligand H3TIBTC and CPs‐(1–4) are shown in Figure
S1. Solid dichroism of CP‐1 and its isomeric crystal coor-
dination polymers are shown in Figure S2. UV–vis spec-
trum of the ligand H3TIBTC and CP‐1 is shown in
Figure S3. The TG curves of the CPs‐(1–4) are shown in
Figure S4. PXRD patterns for the CPs‐(1–4) are shown in
Figure S5. The fluorescence lifetime of the CP‐1 is shown
in Figure S6. The EDAX spectra of the CP‐1 before and
after detection are shown in Figure S7. The SEM micro-
graphs of the CP‐1 before and after detection are shown
in Figure S8. CIF files have also been deposited at the
Cambridge Crystallographic Database Centre and may
be obtained from http://www.ccdc.cam.ac.uk by citing
CCDC for the CP‐1: 1554191; CP‐2: 1554192; CP‐3:
1554195; CP‐4: 1554193.
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ACKNOWLEDGEMENTS
This work was supported by the grants of the National
Natural Science Foundation of China (No. 21571091),
Commonweal Research Foundation of Liaoning province
in China (No. 20170055), and Guangxi Key Laboratory of
Information Materials, Guilin University of Electronic
Technology, P.R. China (Project No. 151002‐K) for finan-
cial assistance for financial assistance.
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ORCID
Yong‐Heng Xing https://orcid.org/0000-0002-7550-2262
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