Polyiodine-Modified 1,3,5-Benzenetricarboxylic Acid Framework Zn(II)/Cd(II) Complexes as Highly Selective Fluorescence Sensors for Thiamine Hydrochloride, NACs, and Fe3+/Zn2+

Article abstract of DOI:10.1021/acs.inorgchem.0c00391

Four new complexes, [Zn(TIBTC)(DMA)]·[NH₂(CH₃)₂] (1), [Cd(TIBTC)(H₂O)]·[NH₂(CH₃)₂]·DMA (2), [Cd₂(TIBTC)(2,2′-bipy)₂(HCOO)] (3), and [Cd₂(DIBTC)(2,2′-bipy)₂(HCOO)] (4) (H₃TIBTC = 2,4,6-triiodo-1,3,5-benzenetricarboxylic acid, H₃DIBTC = 2,4-diiodo-1,3,5-benzenetricarboxylic acid, 2,2′-bipy = 2,2′-bipyridine, and DMA = dimethylacetamide), were successfully synthesized and characterized by elemental analysis, powder X-ray diffraction, infrared spectroscopy, ultraviolet-visible spectroscopy, and thermogravimetric analysis. Complexes 1 and 2 are three-dimensional supramolecular network structures, while complex 4 has a two-dimensional network structure. We preliminarily studied the fluorescence properties of the complexes and found that complexes 1-3 can detect thiamine hydrochloride, NACs, and Fe³⁺/Zn²⁺ with high sensitivity and selectivity.

Full text of DOI:10.1021/acs.inorgchem.0c00391

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Polyiodine-Modi�ed 1,3,5-Benzenetricarboxylic Acid Framework
Zn(II)/Cd(II) Complexes as Highly Selective Fluorescence Sensors for
3+
2+
Thiamine Hydrochloride, NACs, and Fe /Zn
Chun-Hong Liu, Qing-Lin Guan, Xiao-Dong Yang, Feng-Ying Bai,* Li-Xian Sun, and Yong-Heng Xing
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sı Supporting Information
ABSTRACT: Four new complexes, [Zn(TIBTC)(DMA)]·
[
[
NH (CH ) ] (1), [Cd(TIBTC)(H O)]·[NH (CH ) ]·DMA (2),
2 3 2 2 2 3 2
Cd (TIBTC)(2,2 �- bipy) (HCOO)] (3), and [Cd (DIBTC)(2,2 �-
2
2
2
bipy) (HCOO)] (4) (H TIBTC = 2,4,6-triiodo-1,3,5-benzenetri-
2
3
carboxylic acid, H DIBTC = 2,4-diiodo-1,3,5-benzenetricarboxylic
3
acid, 2,2 �- bipy = 2,2 �- bipyridine, and DMA = dimethylacetamide),
were successfully synthesized and characterized by elemental anal-
ysis, powder X-ray di�raction, infrared spectroscopy, ultraviolet−
visible spectroscopy, and thermogravimetric analysis. Complexes 1
and 2 are three-dimensional supramolecular network structures,
while complex 4 has a two-dimensional network structure. We pre-
liminarily studied the �uorescence properties of the complexes and
found that complexes 1−3 can detect thiamine hydrochloride,
3
+
2+
NACs, and Fe /Zn with high sensitivity and selectivity.
1
. INTRODUCTION
Scheme 1. Synthesis of 2,4,6-Triiodo-1,3,5-trimethylbenzene
Thiamine, vitamin B , is one of the important trace elements and
1
is essential for maintaining the normal life activities of humans
and animals. The lack of vitamin B can cause diseases such as
1
beriberi and neuritis. Humans cannot synthesize thiamine, so
thiamine can be obtained only in vitro; the main component of
the vitamin B drug on the market is thiamine hydrochloride
1
1
−9
(
TCL).
Therefore, establishing a sensitive method for
detecting thiamine hydrochloride is an urgent need. In addition,
nitroaromatic complexes (NACs) are important chemical
materials for the production of pesticides, explosives, and
Scheme 2. Synthesis of 2,4,6-Triiodo-1,3,5-
benzenetricarboxylic Acid
10−19
other substances.
For example, 2,4,6-trinitrophenol and
p-nitrophenol easily cause environmental pollution and have
an explosion risk. Therefore, the detection of NACs is essential
for environmental governance and ensuring military security.
Furthermore, zinc and iron are two kinds of trace elements that
are indispensable to the human body; they have physiological
functions such as promoting the growth and development of
the human body and enhancing its immunity. However, the
excessive intake of these two ions may cause serious harm to
the body; excessive consumption of zinc can cause vomiting,
absorption spectroscopy, voltammetry, spectrophotometry, and
37,38
chemiluminescence.
Among them, the chemiluminescence
20−28
headache, diarrhea, convulsions, etc.,
can occur when an excess of iron is ingested.
and iron poisoning
2
9−36
Received: February 7, 2020
Moreover, the
large-scale utilization of these two ions in industrial production
also causes serious environmental pollution problems. There-
fore, selective detection of zinc and iron ions is essential for
biology and environmental �elds. Scientists have developed
various methods for detecting these substances, including atomic
©
XXXX American Chemical Society
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A
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Scheme 3. Synthesis of 2,4-Diiodo-1,3,5-benzenetricarboxylic Acid
Scheme 4. Synthetic Routes of Complexes 1−4
3−
Figure 1. (a) Coordination environment of the Zn(II) ion in complex 1. (b) Coordination mode of TIBTC . (c) 1D chain structure of 1. (d) 2D
planar structure of 1. (e) 3D supramolecular network of 1.
method is widely used because of its convenience and speed, as
well as high sensitivity and selectivity.
Metal organic frameworks (MOFs) are easy to synthesize,
have an adjustable structure and a large surface area, and aid in
the formation of �uorescent sensors. To date, although many
MOF materials have been designed as single-function chemical
sensing compounds, multifunctional sensing research of
3
+
2+
thiamine hydrochloride, NACs, and metal ions (Fe /Zn ) is
B
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3
−
Figure 2. (a) Coordination environment of the Cd(II) atom in complex 2. (b) Coordination mode of the TIBTC . (c) 1D chain structure. (d) 2D
planar structure. (e) 3D structure. (f) 3D stacked pattern of complex 2 containing solvent molecules.
still in its infancy. Therefore, the study of using MOF material
simultaneously detecting these three types of substances is a
challenge. For luminescent MOFs, the types of organic ligands
a�ect the �uorescence properties of MOFs. Generally, organic
ligands are classi�ed into two major classes: poly(carboxylic
acid)s and nitrogen heterocycles. Among them, the most widely
reported organic ligands of poly(carboxylic acid)s can be classi�ed
into two types: aliphatic carboxylic acids and aromatic carboxylic
with symmetrically arranged carboxyl groups promotes the transfer
of electrons, so that the constructed complexes have some special
�uorescence properties. (2) Introduction of a halogen atom into
the aromatic ring to form a halogen bond may increase the size and
44
change electron cloud density of the organic skeleton. On the
basis of our research idea described above, we have reported several
lanthanide metal MOFs, including (i) [Ln(TIBTC)(DMF) ]
3
n
45
44
(Ln = Eu, Gd, Sm, or Nd) and (ii) [Pr(TIBTC)(DMF)3]n
(H TIBTC = 2,4,6-triiodo-1,3,5-benzenetricarboxylic acid). In this
3
9
acids. Aromatic carboxylic acid ligands have more advantages
and are loved by a majority of chemists. They exhibit the following
characteristics. On one hand, they have a rigid ring skeleton
ligand, which provides powerful conditions for the formation of
multidimensional structures; in these structures, there are often
holes, so that these assembled complexes have a novel topology.
On the other hand, the conjugated system of the aromatic ring can
facilitate the transfer ofelectrons, making the complex have special
3
work, as a part of our continued research, we developed four new
transition metal coordination complexes, [Zn(TIBTC)(DMA)]·
[NH
(2), [Cd
[Cd (DIBTC)(2,2 �- bipy)
conditions, and preliminarily explored their �uorescence proper-
(CH
)
2
] (1), [Cd (TIBTC)(H
(TIBTC)(2,2�-bipy)
(HCOO)] (4) under solvothermal
O)]·[NH
(HCOO)] (3), and
2
(CH ) ]·DMA
2
3
2
2
2 3 2
2
2
3
+
2+
ties to detect thiamine hydrochloride, NACs, and Fe /Zn .
40−43
properties such as magnetism, electricity, photocatalysis, etc.
For the reasons given above, we chose 2,4,6-triiodo-1,3,5-
2. EXPERIMENTAL SECTION
benzenetricarboxylic acid (H TIBTC) and 2,4-diiodo-1,3,5-
3
2
.1. Materials and Methods. More detailed information about the
benzenetricarboxylic acid (H DIBTC) as the ligands because
3
materials and methods is provided in the Supporting Information.
they have the characteristics of aromatic carboxylic acids described
above. In addition, (1) the conjugated system on the benzene ring
2
.2. Preparation of the Ligand and Complexes. 2.2.1. 2,4,6-
Triiodo-1,3,5-benzenetricarboxylic Acid (H TIBTC). The synthesis
3
C
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3−
Figure 3. (a) Coordination environment of the Cd(II) ion in complex 4. (b) Coordination mode of the DIBTC . (c) Building block. (d) 1D chain
structure. (e) 2D planar structure.
method of ref 46 has been improved, and the speci�c method is as
follows.
concentrated HCL. Finally, it was extracted with ethyl acetate (125 mL),
washed with water (20 mL), and then evaporated to give 2,4,6-triiodo-
1,3,5-benzenetricarboxylic acid (Scheme 2). Yield: 86%. Anal. Calcd for
C H I O (587.81): C, 18.39; H, 0.51; I, 64.77. Found: C, 18.32; H, 0.76;
2
.2.1.1. 2,4,6-Triiodo-1,3,5-trimethylbenzene (M-1). To a three-
neck �ask were added 1,3,5-trimethylbenzene (M) (12.0 g), iodine
38.8 g), HIO ·2H O (14.0 g), CH COOH (100 mL), and H O (20 mL).
9
3 3
6
−
1
(
I, 64.98. IR data (KBr, cm ): 3162, 1692, 1405, 1512, 1307, 1201.
4
2
3
2
After the mixture had been stirred, 3 mL of concentrated H SO was added
Mp: >280 °C.
2
4
dropwise. The mixture was heated to re�ux at 90 °C for 10 h, �ltered with a
vacuum line, repeatedly washed with distilled water, puri�ed with solvent
2.2.2. 2,4-Diiodo-1,3,5-benzenetricarboxylic Acid (H DIBTC). 2,4-
3
Diiodo-1,3,5-benzenetricarboxylic acid was synthesized by a reaction
similar to that for 2,4,6-triiodo-1,3,5-benzenetricarboxylic acid, except
with addition of 1,3,5-trimethylbenzene (12.0 g), iodine (31.0 g),
HIO ·2H O (14.0 g), CH COOH (100 mL), and H O (20 mL) to
acetone, and suction �ltered to yield 2,4,6-triiodo-1,3,5-trimethylbenzene
1
(
M-1) (Scheme 1). The IR spectra and H NMR spectra of M-1 are shown
−1
in Figures S1 and S3. Yield: 76%. IR data (KBr, cm ): 1525, 1372, 1322,
240, 940, 871, 595. H NMR (400 MHz, CDCl ): � 3.00 (d, 1H).
4
2
3
2
1
1
the three-neck �ask in the �rst step. The synthetic route is shown in
3
1
Mp: 205.5−207.1 °C.
Scheme 3. The IR spectra and H NMR spectra of 2,4-diiodo-1,3,5-
2
.2.1.2. H TIBTC. Triiodotrimethylbenzene (5.0 g), H O (25 mL),
trimethylbenzene (M-2) are shown in Figures S2 and S4. M-2. Yield:
3
2
−
1
and pyridine (70 mL) were added to a �ask, and the mixture was stirred
until the solid was completely dissolved to obtain a milky white liquid.
76%. IR data (KBr, cm ): 2995, 1516, 1376, 946, 864, 670, 608.
1
H NMR (400 MHz, CDCl ): �7.01 (s, 1H), 2.94 (s, 2H), 2.44 (s, 6H).
3
Then, the temperature was increasedto 90°C, and solid KMnO (10.0 g)
Mp: 120.2−123.5 °C. H DIBTC. Yield: 78%. Anal. Calcd for C H I O
4
3
9
4 2
6
was added at 1 h intervals a total of six times. After the mixture had been
heated for 10−12 h, it was �ltered while hot, the solid was washed
with a hot 5% KOH solution, and the pyridine solvent was removed
with a rotary evaporator. Then, 75 mL of distilled water was added to
remove insoluble species, and the �ltrate was adjusted to pH = 1 with
(461.89): C, 23.40; H, 0.87; I, 54.95. Found: C, 23.32; H, 0.74; I,
−
1
55.08. IR data (KBr, cm ): 3108, 1683, 1403, 1523, 1244, 1137.
Mp: >280 °C.
2.2.3. [Zn(TIBTC)(DMA)]·[NH (CH ) ] (1). Zn(CH COO) ·2H O
2
3 2
3
2
2
(0.0550 g, 0.25 mmol) was dissolved in a mixed solvent of C H OH
2
5
D
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Figure 4. PXRD spectra of complexes 1−4 before and after detection.
−
1
(
1 mL), and H TIBTC (0.0280 g, 0.05 mmol) was dissolved in a DMA
6.07. Found: C, 35.32; H, 1.65; N, 6.05. IR data (KBr, cm ): 3418,
1587, 1373, 1512, 1287, 1158.
3
solution (1.5 mL). Then, the two solutions were mixed, and 4 mol/L
HNO was used to adjust the pH of the solution to 3; then the solution
2.3. Luminescence Experiments. A powder sample of the
complex (5 mg) was dispersed into C H OH (5 mL) and sonicated
3
was stirred for 1 h until it turned into a yellow clear liquid at room
temperature and was transferred to a high-pressure glass bottle. After
being heated at 100 °C for 24 h, it was taken out and cooled for 2 h to
obtain colorless diamond-shaped bulk crystals. Yield: 42% (based on
Zn). Anal. Calcd for C H I N O Zn (783.38): C, 22.98; H, 2.17; N,
2 5
for 30 min to form a MOF suspension. Then, 2 mL of the suspension
was placed in a cuvette; various test solutions were gradually added to
form di�erent concentrations of the suspension, and the �uorescence
intensity at room temperature was measured and compared.
2.4. X-ray Crystallographic Determination. Speci�c X-ray
crystallographic methods are described in the Supporting Information.
Tables S1−S3 give the crystallographic details of complexes 1, 2, and 4,
respectively, and the selected bond lengths and angles. The CCDC
numbers of 1, 2, and 4 are 1951693, 1951692, and 1951592,
respectively.
1
5
17 3
2
7
−
1
3
1
.57. Found: C, 22.99; H, 2.16; N, 3.55. IR data (KBr, cm ): 3424,
595, 1389, 1520, 1304, 1198.
2
.2.4. [Cd(TIBTC)(H O)]·[NH (CH ) ]·DMA (2). Cd(NO ) ·4H O
2 2 3 2 3 2 2
(0.0308 g, 0.10 mmol), H TIBTC (0.0280 g, 0.05 mmol), water
3
(
2 mL), and DMA (1.5 mL) were mixed in a beaker (25 mL) and stirred
for 1 h. The mixed solution was placed in a high-pressure glass bottle,
adjusted to pH = 3 with HNO , heated at 100 °C for 1 day, and cooled
3
3
. RESULTS AND DISCUSSION
slowly at room temperature. After the product had been washed with
water, it was further dried under vacuum conditions to yield colorless
crystals. Yield: 46% (based on Cd). Anal. Calcd for C H I N O Cd
3.1. Synthesis. Complexes 1−4 are all synthesized by
1
5
19 3
2
8
using a solvothermal reaction in a high-pressure glass bottle
(
848.42): C, 21.22; H, 2.24; N, 3.77. Found: C, 21.24; H, 2.21; N, 3.76.
(
Scheme 4). For complexes 1 and 2, we �rst tried to opt for the
−
1
IR data (KBr, cm ): 3490, 1584, 1380, 1519, 1304, 1191.
best reaction solvents. It is found that the solvents that favored
the growth of crystals of the complex were a mixed solvent of
C H OH, CH OH, and DMA for complex 1 and a mixed
2
.2.5. [Cd (TIBTC)(2,2 �- bipy) (HCOO)] (3). The procedure for
2
2
obtaining crystals of complex 3 is similar to that for 2. The only di�er-
ence is the addition of a second ligand, 2,2 �- bipy (0.0170 g, 0.10 mmol),
and using C H OH instead of H O. Yield: 52% (based on Cd). Anal.
2
5
3
solvent of H O and DMA for complex 2. Next, we used di�erent
2
2
5
2
reaction temperatures (80, 100, and 120 °C) and found that tiny
crystals were obtained at 100 °C. Then, we adjusted the molar
ratio of the main reaction reagents (metal salt and ligand) and found
that at a metal:ligand ratio of 5:1 (complex 1) or 2:1 (complex 2),
we obtained ideal crystals of complex 1 or 2, respectively, for single-
crystal testing while adjusting the pH value of 3 and 4.
Calcd for C H I N O Cd (1180.09): C, 31.52; H, 1.44; N, 5.42.
3
1
17 3
4
8
2
−
1
Found: C, 31.53; H, 1.42; N, 5.41. IR data (KBr, cm ): 3440, 1576,
373, 1512, 1308, 1137.
1
2
.2.6. [Cd (DIBTC)(2,2�-bipy) (HCOO)] (4). The method for
2
2
obtaining the crystals of complex 4 is almost the same as the method
for 3, except that H DIBTC (0.0230 g, 0.05 mmol) is used instead
3
of H TIBTC in the starting reactant. Yield: 50% (based on Cd).
To extend crystalline state complexes with various structures
for comparison of structure and function, we introduced the
3
Anal. Calcd for C H I N O Cd (1054.09): C, 35.29; H, 1.71; N,
31
18 2
4
8
2
E
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Figure 5. Fluorescence spectra upon detection of TCL by complexes 1−4.
second ligand, 2,2 �- bipy, into the reaction system and obtained
the corresponding complexes 3 and 4 containing mixed ligands.
Through a large number of experiments, we found that when
structure, which is furthermore connected by a hydrogen bond
#8
[N2−H14A···O7, N2−H14B···O3 (#8: −x + 1, −y + 1, z −
1
/2)] from the free protonated dimethylamine cation to yield a
the mixed solvent consists of C H OH and DMA at 100 °C and
2
5
three-dimensional (3D) supramolecular network (Figure 1d,e).
pH = 3−4, we can obtain the perfect crystal of complex 4, but the
crystals of complex 3 that can be analyzed by X-ray single-crystal
di�raction have never been obtained in spite of our e�orts;
however, we characterized complex 3 by element analysis, IR,
and XRD. We are sure that the structure of complex 3 was
consistent with that of complex 4.
3
.2.2. [Cd(TIBTC)(H O)]·[NH (CH ) ]·DMA (2). One can
2 2 3 2
see from the structural analysis that complex 2 is a monoclinic
system in the P2 /c space group. The molecular structure of the
complex comprises a central metal Cd(II), a ligand TIBTC , a
coordinating water molecule, a free dimethylamine cation that
is from the decomposition of DMA, and a free DMA solvent
molecule. The Cd(II) coordinates with the carboxyl oxygen
atoms (O2−O6) from three TIBTC ions and the oxygen atom
O1) of a solvent water molecule to form an octahedral con�g-
1
3−
3
.2. Structural Descriptions. 3.2.1. [Zn(TIBTC)(DMA)]·
[
NH (CH ) ] (1). Complex 1 belongs to the orthorhombic system
3−
2
3 2
and Pca2 space group. The molecular structure of 1 includes
1
(
3
−
a central metal Zn(II), a ligand TIBTC , a coordinated DMA
molecule, and a free dimethylamine cation that come from the
decomposition of DMA. Figure 1a shows the coordination
environment around the central metal Zn(II). The central metal
Zn(II) is coordinated with four carboxylic acid oxygen atoms
3−
2
O
2
O
1
O
uration (Figure 2a). The TIBTC is connected in a � -� � �
3
manner, and the carboxyl oxygen atom in the structure adopts a
monodentate or bidentate coordination mode (Figure 2b). The
Cd−O bond length is 2.226(3)−2.584(4) Å, which is consistent
with the Cd−O bond length [2.272(6)−2.508(7) Å] in the
literature. The Cd···Cd distance is �10 Å.
Adjacent Cd atoms are connected by the COO of the
TIBTC along the a-axis to constitute a 1D chain structure
Figure 2c), which further extends along the b-axis to produce a
D layered structure (Figure 2d); the 2D layer in the structure
is stacked along the c-axis direction, and adjacent layers are
hydrogen-bonded [O1−H1A···O3 (#6 −x + 2, −y, −z),
O1−H1B···O7 (#7 −x + 2, y − /
(
O1, O2, O4, and O6) to form a tetrahedral structure, where O2,
48
3−
O4, and O6 are from three TIBTC ions and O1 is from solvent
DMA molecular coordination. The coordination mode of the
−
3−
3−
1
1
1
ligand TIBTC moiety is � -� � � (Figure 1b). The Zn−O
3
O
O
O
(
2
bond length is 1.948(9)−1.994(16) Å, which is close to the
47
Zn−O bond length [1.954(3)−1.973(3) Å] in the literature.
The Zn···Zn distance is �8.7 Å.
#6
−
The two carboxyl groups (COO ) in the ligand connect
#7
1
1
adjacent Zn atoms along the a-axis to form a one-dimensional
2
, −z + /
)] to form a 3D
2
(
1D) chain structure (Figure 1c). The 1D chain structure was
porous structure having a one-dimensional pore. The pores
extend in�nitely along the a-axis direction (Figure 2e). The
complex is an anionic backbone structure with a free protonated
−
extended along the c-axis by another carbonyl group (COO )
of the ligand to produce a two-dimensional (2D) network
F
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Figure 6. (a, c, and e) Fluorescence intensity after the addition of other amino acids to the suspension of complexes 1−3 containing TCL. (b, d, f) After
the addition of other amino acids, comparison of the intensity of the strongest �uorescence emission peak of the suspension of complexes 1−3
containing TCL.
dimethylamine cation and DMA solvent molecules �lled in one
dimension of the pores as shown in Figure 2f.
bidentate chelate coordination; two oxygen atoms on one
carboxylic acid group adopt bidentate coordination, and oxygen
atoms on another carboxylic acid group are in a monatomic
bridge coordination mode. The Cd−O bond distances (from
3
.2.3. [Cd (DIBTC)(2,2 �- bipy) (HCOO)] (4). This complex
2
2
crystallizes in the monoclinic P2 /c space group, which has
two Cd(II) centers, one DIBTC , two coordinated 2,2 �- bipy
ligands, and one coordinated HCOO in its molecular structure
1
3
−
3−
the DIBTC ligand) are in the range of 2.220(4)−2.393(2) Å,
−
and Cd−N bond lengths are 2.305(17)−2.309(5) Å. The Cd1···
Cd2 distance in the building block is 3.6516 Å.
(
HCOOH is from the decomposition of DMA). In the structure
of complex 4, the central Cd(II) has two coordination modes.
1) Cd(II) is six-coordinated with four oxygen atoms (O1, O5,
In complex 4, the structural unit [Cd O N ] (Figure 3c) is
2
7
4
3
−
(
linked in the c-axis direction by a carboxyl group in the DIBTC
ligand to form the 1D chain structure (Figure 3d), which is
joined in the b-axis direction by another ligand DIBTC to
extend into the 2D planar structure (Figure 3e).
3−
O3, and O2) from three DIBTC ions and two nitrogen atoms
3
−
(
N1 and N2) of one 2,2 �- bipy ligand to form an octahedral
geometry (Figure 3a). (2) Cd(II) is �ve-coordinated with O3,
O6, N3, N4, and O8 to form a distorted tetrahedral geometry
3.3. IR Spectra. Figure S5 and Table S4 give the infrared
spectral data of ligands and complexes. The infrared peaks
of complexes 1−4 are roughly similar. For the complexes, the
3−
(
O3 and O6 are from two DIBTC ions, N3 and N4 are from
−
one 2,2 �- bipy ligand, and O8 is from coordinated HCOO ).
2
O
1
1
1
1
−1
The connection mode of the ligand is � -� � � � �
O
peaks at 1576−1595 and 1373−1389 cm correspond to the
5
O
O
O
−
(Figure 3b). Two oxygen atoms on one carboxylic acid adopt
asymmetric and symmetry stretching vibrations of COO . A red
G
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Figure 7. Changes in the �uorescence intensity after the addition of four NACs to the C H OH solution of complex 1: (a) 2,4,6-trinitrophenol,
2
5
(b) p-nitrophenol, (c) 4-nitrotoluene, and (d) nitrobenzene. (e) Line graph of the �uorescence response of di�erent NACs to complex 1.
shift occurred in relation to �asCOO− and �sCOO− of the ligand,
3.5. PXRD. The simulated peaks were compared with
experimentally measured di�raction peaks in the PXRD pattern
(Figure 4), and the positions of the peaks were matched, indicating
that complexes 1−4 were pure phases.
3.6. Thermal Analysis. In the protective environment of N2,
thermogravimetry of the complex was performed at 30−800 °C
(Figure S7).
indicating that the metal coordinated with the ligand. In partic-
−
1
ular, for complexes 3 and 4, the peaks from 612 to 1019 cm
prove that 2,2 �- bipy participates in coordination.
3
.4. UV−Vis Spectra. The UV spectra were recorded for
solid samples at room temperature (Figure S6 and Table S5). The
absorption peaks at 217 and 283 nm of 1, 220 and 283 nm of 2, 216
and 281 nm of 3, and 219 and 280 nm of 4 are the �−�* and n−�*
electronic transitions of the ligand, respectively. The peaks at
For complex 1, the weight loss in the range of 30−169 °C was
2.02% (theoretical value of 2.12%), corresponding to the loss of
3
36 nm (1), 338 nm (2), 332 nm (3), and 330 nm (4) are from the
coordination H O molecules; the weight loss at 169−305 °C
2
charge transfer transition from the ligand to the central metal ion.
was 5.28% (theoretical value of 5.38%), which should be the loss
H
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Figure 8. Changes in the �uorescence intensity after the addition of four NACs to the C H OH solution of complex 2: (a) 2,4,6-trinitrophenol,
2
5
(b) p-nitrophenol, (c) 4-nitrotoluene, and (d) nitrobenzene. (e) Line graph of the �uorescence response of di�erent NACs to complex 2.
of free dimethylamine cations; and the weight loss at 305−
00 °C was 80.70% (theoretical value of 80.90%), which should
be the collapse of the ligand framework. The residue was the
residue of zinc oxide and organic framework carbon.
For complex 3, the �rst weight loss that occurred during the
371−414 °C interval was 26.65%, which was consistent with the
theoretical weight loss value (26.45%) of losing two 2,2 �- bipy
molecules; the weight loss during the heating process from 414
to 429 °C was �3.83%, which coincided with the theoretical
8
For complex 2, below 234 °C, the weight loss was 5.85%
theoretical value of 5.87%), which indicated the loss of free
−
(
weight loss value (3.81%) of the HCOO . In the third stage, the
dimethylamine cations. The weight loss at 234−330 °C was
1.05% (theoretical value of 11.10%), which indicated the
loss of coordination DMA molecules. The �nal weight loss at
weight loss during heating from 429 to 795 °C was �53.12%,
which was the destruction of the ligand skeleton (theoretical
value of 53.95%). The �nal residue was the residue of cadmium
oxide.
For complex 4, the �rst weight loss of 29.67% in the 336−418 °C
interval was the loss of two 2,2 �- bipy ligands (theoretical value of
1
3
30−800 °C was 63.50% (theoretical value of 63.95%), which
corresponded to the collapse of the ligand framework, and the
cadmium oxide was the �nal residue.
I
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Figure 9. Changes in the �uorescence intensity after the addition of four NACs to the C H OH solution of complex 3: (a) 2,4,6-trinitrophenol,
2
5
(b) p-nitrophenol, (c) 4-nitrotoluene, and (d) nitrobenzene. (e) Line graph of the �uorescence response of di�erent NACs to complex 3.
2
9.67%); in the range of 418−433 °C, the weight loss was 4.32%,
structure and then decreased the nonradiative transition energy
of the excited state in the ligand molecule, which changed the
luminescence band. The solid �uorescence lifetimes of the
complexes are 0.217 ± 0.003 (complex 1), 0.145 ± 0.001
(complex 2), 0.167 ± 0.002 (complex 3), and 0.186 ± 0.001
(complex 4).
−
which was ascribed to the loss of HCOO (theoretical value of
.27%); and the �nal residue correponded to the collapse of the
49
4
skeleton of the ligand in the range of 433−800 °C with a weight
loss of 40.92% (theoretical value of 41.59%). The �nal residue
corresponded to cadmium oxide.
3
.7. Solid State Photoluminescence Property and
We �rst explored the photoluminescence properties of
complexes in several solvents. Five milligrams of the complex
powder was added to 5 mL of various solvents and sonicated for
30 min to achieve a uniform dispersion of the MOF. It was found
that the complex had the best �uorescence e�ect in C H OH
Solvent Selection. For the emission spectrum, upon excitation
at 270 nm, the H TIBTC ligand has an emission peak at
52 nm, which is derived from the �−�* transition of the ligand
Figure S8), while complexes 1−4 showed emission peaks at
57, 359, 363, and 358 nm, respectively. The complexes showed
3
3
(
3
2
5
(Figure S9), and because C H OH was less toxic and environ-
2 5
red shifts of 2, 7, 11, and 6 nm, respectively, compared to the
mentally friendly, C H OH was chosen as the solvent for the
2 5
emission peak of H TIBTC. This may be due to the coor-
next �uorescence experiment.
3
dination between the metal and the ligand that changed the
density distribution of the electron cloud in the molecular
3.8. Fluorescence Detection Applications. 3.8.1. Detec-
tion of Thiamine Hydrochloride (TCL). We �rst investigated the
J
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Figure 10. Changes in the �uorescence intensity after the addition of four NACs to the C H OH solution of complex 4: (a) 2,4,6-trinitrophenol,
2
5
(b) p-nitrophenol, (c) 4-nitrotoluene, and (d) nitrobenzene. (e) Line graph of the �uorescence response of di�erent NACs to complex 4.
ability of complexes 1−4 to sense thiamine hydrochloride
TCL). The speci�c experimental procedure was as follows. The
C H OH solution of the solid powder of the complexes was
Table 1. Comparison of Photoluminescence Properties of
2,4,6-Trinitrophenol Detected by Complexes 1−4
(
2
5
Ksv (M−1
sample
)
LOD (�M)
sonicated for 30 min (1 mg/mL); 2 mL of the suspension
described above was added to the cuvette, and then an aqueous
solution of thiamin hydrochloride (TCL) (1 mM) was gradually
added and the �uorescence intensity tested as shown in Figure 5.
We observed that as the concentration of TCL increased,
the �uorescence intensity of complexes 1−3 was signi�cantly
quenched; however, the e�ect on the �uorescence intensity of
complex 4 was very weak, so complex 4 was not suitable for
complex 1
complex 2
complex 3
complex 4
1.22 × 105
0.77
0.81
0.80
0.01
5
1.66 × 10
8.85 × 105
6
4.35 × 10
−
1
quenching constant (M ), and [Q] is the molar concentration
of the detected TCL. The K values of complexes 1−3 with
sv
5
4
detection of TCL. The Stern−Volmer equation is I /I = 1 +
respect to TCL were calculated to be 1.48 × 10 , 8.69 × 10 , and
4
0
−1
K [Q], where I is the initial �uorescence intensity of the
1.35 × 10 M , respectively (Figure S10). The detection limit is
sv
0
complex 1−3 suspension, I is the �uorescence intensity of the
calculated by the formula D = 3�/K (where D is the detection
sv
complex suspension after the addition of TCL, K represents the
limit and � represents the standard deviation of the initial
sv
K
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Figure 11. Fluorescence intensity response of di�erent metal ions to complexes 1−4.
Figure 12. Fluorescence spectra of complexes 1−4 with a concentration gradient of Fe or Zn2+.
3+
L
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Figure 13. In the presence of Fe3+ and other metal ions, the �uorescence spectra of (a) complex 1 and (c) complex 2. Comparison of the strongest
3
+
emission intensity with and without the addition of Fe to the suspension of complexes containing other metal ions: (b) complex 1 and (d) complex 2.
luminous intensity of 20 groups of blank MOF suspensions).
The calculated detection limits are 0.97 �M (for complex 1),
aqueous solutions of amino acids were added to the C H OH
2 5
suspension of the complexes, and then 200 �L (10 mM) of a
TCL solution was added. After the �uorescence test had been
conducted, it was found that other competing amino acids did
not interfere with the results of TCL detection of complexes
1−3 (Figure 6).
1
.54 �M (for complex 2), and 5.52 �M (for complex 3), which
50
are much lower than that of [In (OH) (H TTHA)(H O) ] .
2
2
2
2
2 n
We found that complexes 1−3 are promising as �uorescent
sensors for detecting thiamine hydrochloride. By comparison,
the �uorescence quenching performance decreased in the fol-
lowing order: 1 > 2 > 3. The possible reason for the quenching
of the �uorescence intensity of complexes 1−3 with respect
to thiamine hydrochloride (TCL) is that a weak interaction
including hydrogen bond and electrostatic interaction between
the TCL and ligand moiety of the complexes reduces the
nonradiative transition between the ligand and the central metal,
furthermore weakening the �uorescence intensity. The �uorescence
quenching performance decreases in the following order: 1 > 2 > 3.
This may be due to the di�erence in the strength of the weak
interaction formed by TCL and complexes as well as the struc-
tural change of complexes 1−3.
Biological small molecules mainly include vitamins, water,
amino acids, nucleotides, monosaccharides, and lipids. In the
process of bio�uorescence detection, the presence of several
other small biological molecules may a�ect the experimental
results. A good �uorescent probe should have high selectivity,
and other substances should not interfere with the test results.
Therefore, we initially tested several amino acids (Gly, DL-Ala,
Arg, Lys, Leu, Ser, Asp, and Val) in interference experiments for
detecting TCL. First, 200 �L (10 mM) portions of di�erent
3.8.2. Detection of NACs. We further investigated the
�uorescent properties of complexes 1−4 in the presence of NACs
by gradually adding four NACs (2,4,6-trinitrophenol, p-nitrophenol,
nitrotoluene, and nitrobenzene) at 0.1 mM to the C H OH solution
2
5
containing complexes 1−4 (1 mg/mL). Figures 7−10 show that
increasing the concentration of NACs decreases the �uorescence
intensity of complexes 1−4; in particular, the solution con-
taining 2,4,6-trinitrophenol has the largest decrease in �uo-
rescence intensity. By comparison, it can be found that the
quenching e�ciency decreases in the following order: 2,4,6-
trinitrophenol > p-nitrophenol > 4-nitrotoluene > nitrobenzene.
This is consistent with the order of polarity of the four NACs:
2,4,6-trinitrophenol > p-nitrophenol > 4-nitrotoluene > nitro-
benzene; therefore, the �uorescence intensity of complexes 1−4
is quenched by NACs, which is related to the polarity of NACs,
and the greater the polarity of the NACs, the better the �uo-
rescence quenching e�ect on the complexes.
According to the equations I /I = 1 + K [Q] and D = 3�/K ,
0
sv
sv
the K and the detection limit of 2,4,6-trinitrophenol detected
sv
by complexes 1−4 were calculated (Figure S11 and Table 1);
from Table 1, we can see that complexes 1−4 all have the higher
M
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Figure 14. In the presence of Zn2+ and other metal ions, the �uorescence spectra of (a) complex 3 and (c) complex 4. Comparison of the strongest
2
+
emission intensity with and without the addition of Zn to the suspension of complexes containing other metal ions: (b) complex 3 and (d) complex 4.
Ksv values and lower detection limits for detecting 2,4,6-
trinitrophenol, and among them, complex 4 has the best detection
e�ect.
D = 3�/K , the detection limits were calculated to be 3.45 �M
sv
(complex 1), 5.51 �M (complex 2), 4.16 �M (complex 3), and
9.67 �M (complex 4). The results show that the detection
3
+
2+
3
.8.3. Detection of the Metal Ion. The �uorescence
of Fe for complexes 1 and 2 and the detection of Zn for
complexes 3 and 4 have good selectivity and high sensitivity.
Complexes 1 and 2 with a single ligand have a �uorescence
intensities of complex suspensions containing di�erent metal
ions were determined, and we could see that their �uorescence
intensity is a�ected by the type of metal ion. For single-ligand
complexes 1 and 2, adding Fe3 can signi�cantly weaken their
3
+
quenching e�ect on Fe ions, while complexes 3 and 4 with
mixed ligands have a �uorescence enhancement e�ect on Zn ,
+
2+
�
uorescence intensity, while for mixed ligands complexes 3 and
which may be attributed to the structures in the complexes,
which is di�erent from the cause of the di�erence in �uorescence
performance.
2
+
4, adding Zn can signi�cantly enhance their �uorescence
intensity (Figure 11).
To further investigate the sensitivity of complexes 1 and 2 to
To test whether the e�ect of the complexes in detecting
Fe3 ions and complexes 3 and 4 to Zn ions, we gradually
+
2+
Zn or Fe ions is a�ected by other metal ions, we initially
conducted the following experiments. After di�erent metal ion
aqueous solutions (1 mM, 160 mL) had been added to a 2 mL
2+
3+
3+
added an aqueous Fe solution (1 mM) to the MOF suspen-
2
+
sion of complexes 1 and 2 and added an aqueous Zn solution
1 mM) to the MOF suspension of complexes 3 and 4. As shown
3
+
2+
(
C H OH suspension of the complex, additional Fe or Zn
2 5
3+
2+
in Figure 12, as the concentration of the Fe or Zn solution
in the system gradually increased, the �uorescence intensities of
complexes 1 and 2 gradually decreased while the �uorescence
intensities of complexes 3 and 4 gradually increased. According
to the equation I /I = 1 + K [Q] [where I is the initial �uo-
solution (1 mM, 160 mL) was added and the �uorescence
intensity was measured. Figures 13 and 14 show that the com-
3
+
2+
plexes can still detect Fe or Zn normally under the complex
conditions in the presence of other metal ions.
3.8.4. Cycle Test Experiment. As a �uorescence sensor,
recycling is also very important. Therefore, we collected the
complex powder after the �uorescence sensing test, washed it
with C H OH, and performed �ve cycles of experimental deter-
0
sv
0
rescence intensity of the complex suspension, I is the �uores-
cence intensity of the complex suspension after the addition of
3
+
−1
Fe , K represents the quenching constant (M ), and [Q] is
sv
2
5
3+
the molar concentration of the detected Fe ], the K for 1 is
mination on it. The experimental results show that the �uores-
cence quenching/enhancing of the complex is basically unchanged
even if �ve cycles are used as described above, showing that the
�uorescence detection has good recoverability (Figure S13).
sv
4
−1
4
−1
9
.71 × 10 M and the K for 2 is 2.43 × 10 M . According to
sv
51
4
−1
the same equation, the K for 3 is 1.79 × 10 M and the Ksv
sv
3
−1
for 4 is 6.60 × 10 M (Figure S12). According to the equation
N
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Figure 15. Comparison of the UV−vis spectra of the MOF suspension after the addition of the test substance with the original MOF suspension.
Figure 16. Changes in lifetimes before and after detection of Zn2+ by (a) complex 3 and (b) complex 4.
3
.8.5. Fluorescence Response Mechanism. To further
Table 2. Fluorescence Lifetimes of Complexes 3 and 4 before
and after the Addition of Zn2+
explore the mechanism of �uorescence sensing, we measured
the PXRD spectra of complexes after the addition of three
analytes (Figure 4). It was found that the PXRD spectra of the
complexes after immersion in the three test solutions for 24 h
remained unchanged, eliminating the possibility of �uorescence
lifetime (nm)
3+
suspension
Zn @complex
3
4
0.617 ± 0.002
0.586 ± 0.001
1.008 ± 0.003
0.672 ± 0.002
52,53
quenching caused by collapse of the skeleton.
The UV−vis absorption spectra after the addition of the guest
species to the MOF suspension were recorded and compared
with the UV−vis absorption spectra of the MOF suspension
of 200−410 nm, and the overlap in the UV−vis absorption
region indicates that the detector absorbs the excited state
photons of the complexes and reduces the extent of transfer of
energy from the ligand to the central metal ion, which causes
�uorescence quenching when the complex detects TCL, 2,4,6-
2
+
(
Figure 15); we found that in addition to the detection of Zn ,
the detection solution of complexes that detected TCL, 2,4,6-
trinitrophenol, and Fe3 showed strong absorption in the range
+
trinitrophenol, and Fe .
3+ 54
O
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The lifetimes of the suspensions of 3 and 4 were determined
Qing-Lin Guan − College of Chemistry and Chemical
2
+
before and after the addition of the test substance Zn . After the
Engineering, Liaoning Normal University, Dalian 116029, P. R.
China
2+
addition of the test substance Zn , the luminescence lifetimes of
the complexes increased (Figure 16 and Table 2), implying that
the interaction between the detection substance and the com-
plexes led to the more e�cient transfer of energy to the metal
center, thereby increasing the luminescence intensity.
Xiao-Dong Yang − College of Chemistry and Chemical
Engineering, Liaoning Normal University, Dalian 116029, P. R.
China
Li-Xian Sun − Guangxi Key Laboratory of Information Materials,
Guilin University of Electronic Technology, Guilin 541004, P. R.
China
4
. CONCLUSIONS
Yong-Heng Xing − College of Chemistry and Chemical
Engineering, Liaoning Normal University, Dalian 116029, P. R.
China; orcid.org/0000-0002-7550-2262
We synthesized four new complexes, [Zn(TIBTC)(DMA)]·
[
(
[
NH (CH ) ] (1), [Cd(TIBTC)(H O)]·[NH (CH ) ]·DMA
2 3 2 2 2 3 2
2), [Cd (TIBTC)(2,2�-bipy) (HCOO)] (3), and
2
2
Cd (DIBTC)(2,2 �- bipy) (HCOO)] (4). Fluorescence experi-
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.inorgchem.0c00391
2
2
ments show that complexes 1−3 can quickly and sensitively
3+
2+
detect TCL, NACs, and metal ions (Fe and Zn ). Other amino
acids do not interfere with the result of detecting TCL. Interestingly,
complexes 1 and 2 with a single ligand showed a �uorescence
quenching e�ect on Fe3 ions, whereas complexes 3 and 4 with
the mixed ligands showed a �uorescence enhancement e�ect on
Notes
The authors declare no competing �nancial interest.
+
ACKNOWLEDGMENTS
�
2+
Zn ions. The results show that complexes 1−3 may be candidates
for multifunctional �uorescent sensors for thiamine hydrochloride,
This work was supported by grants from the National Natural
Science Foundation of China (21571091) and the Guangxi
Key Laboratory of Information Materials, Guilin University of
Electronic Technology (Project 191001-K).
3+
2+
NACs, and Fe and Zn that have high sensitivity and selectivity.
This work provides a new idea for extending the application of
MOF materials as multiresponse sensors.
REFERENCES
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.inorgchem.0c00391.
�
�
(
1) Gong, F. C.; Zou, W.; Wang, Q.; Deng, R.; Cao, Z.; Gu, T.
*
Polymer nanoparticles integrated with excited-state intramolecular
proton transfer-fluorescent modules as sensors for the detection of
vitamin B1. Microchem. J. 2019, 148, 767−773.
(
2) Grataco s� -Cubarsí, M.; Sa r�r aga, C.; Clariana, M.; García Regueiro,
Crystallographic data, bond lengths and angles, and hydro-
J. A.; Castellari, M. Analysis of vitamin B1 in dry-cured sausages by
hydrophilic interaction liquid chromatography (HILIC) and diode
array detection. Meat Sci. 2011, 87, 234−238.
gen bond data for complexes 1, 2, and 4 (Tables S1−S3,
1
respectively); IR and H NMR spectra of ligand
intermediates M-1 and M-2 (Figures S1−S4, respectively);
(
3) Yu, Y.; Ching, Y. J.; Tan, Y. N. A Simple and Fast Fluorimetric
IR spectra, UV−vis spectra, and thermal analysis of
3+
Method for Thiamine (Vitamin B1) Detection by Au Mediated
Formation of Thiochrome. Austin Journal of Biosensing & Bioelectronics
2015, 1, 1004−1008.
H TIBTC, H DIBTC, and complexes 1−4 (Figures S5−
3
3
S7, respectively) and the corresponding data assignments
Tables S4 and S5); solid state emission spectra of
(
(4) Wu, Y.; Li, S.; Wang, W.; Zhang, D. Associations of dietary vitamin
B1, vitamin B2, niacin, vitamin B6, vitamin B12 and folate equivalent
intakes with metabolic syndrome. Int. J. Food Sci. Nutr. 2020, 1−12.
complexes 1−4 and �uorescence intensities in di�erent
solvents (Figures S8 and S9, respectively); SV-�tted graphs
of �uorescence detection for complexes (Figures S10−
S12); quenching/enhancing e�ciency of �uorescence for
complexes after �ve cycles of experiments (Figure S13)
(
5) Paerl, R. W.; Sundh, J.; Tan, D.; Svenningsen, S. L.; Hylander, S.;
Pinhassi, J.; Andersson, A. F.; Riemann, L. Prevalent reliance of
bacterioplankton on exogenous vitamin B1 and precursor availability
Microbiology]. Proc. Natl. Acad. Sci. U. S. A. 2018, 115, E10447−
E10456.
[
(PDF)
(
6) DiNicolantonio, J. J.; Liu, J.; O’Keefe, J. H. Thiamine and
Accession Codes
Cardiovascular Disease: A Literature Review. Prog. Cardiovasc. Dis.
CCDC 1951592 and 1951692−1951693 contain the supple-
mentary crystallographic data for this paper. These data can be
obtained free of charge via www.ccdc.cam.ac.uk/data_request/
cif, or by emailing data_request@ccdc.cam.ac.uk, or by
contacting The Cambridge Crystallographic Data Centre, 12
Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
2
(
018, 61, 27−32.
7) Goyer, A. Thiamine in plants: aspects of its metabolism and
functions. Phytochemistry 2010, 71, 1615−1624.
(
8) Jenc o� , J.; Krc m� ova ,� L. K.; Solichova ,� D.; Solich, P. Recent trends in
determination of thiamine and its derivatives in clinical practice. J.
Chromatogr. A 2017, 1510, 1−12.
(
9) Menzri, R.; Ghizellaoui, S.; Tlili, M. Calcium carbonate inhibition
AUTHOR INFORMATION
Corresponding Author
Feng-Ying Bai − College of Chemistry and Chemical Engineering,
Liaoning Normal University, Dalian 116029, P. R. China;
orcid.org/0000-0001-6202-054X;
by green inhibitors: Thiamine and Pyridoxine. Desalination 2017, 404,
47−154.
10) Vu, A.; Phillips, J.; Bu �h lmann, P.; Stein, A. Quenching
�
1
(
Performance of Surfactant-Containing and Surfactant-Free Fluoro-
phore-Doped Mesoporous Silica Films for Nitroaromatic Complex
Detection. Chem. Mater. 2013, 25, 711−722.
Email: baifengying2003@163.com
(
11) Mauricio, F.; Silva, J.; Talhavini, M.; Ju n� ior, S.; Weber, I.
Luminescent sensors for nitroaromatic complex detection: Inves-
tigation of mechanism and evaluation of suitability of using in screening
test in forensics. Microchem. J. 2019, 150, 104037−104046.
(12) Chen, Y.; Wang, M.; Fu, H.; Qu, X.; Zhang, Z.; Kang, F.; Zhu, D.
Spectroscopic and molecular modeling investigation on inhibition
Authors
Chun-Hong Liu − College of Chemistry and Chemical
Engineering, Liaoning Normal University, Dalian 116029, P. R.
China
P
https://dx.doi.org/10.1021/acs.inorgchem.0c00391
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
pubs.acs.org/IC
Article
effect of nitroaromatic complexs on acetylcholinesterase activity.
(31) Wang, L.; Xu, W.; Li, W. Y.; Xie, M.; Zheng, Y. Q. A Water-Stable
Uranyl Organic Framework as a Highly Selective and Sensitive
Bifunctional Luminescent Probe for Fe and Tetracycline Hydro-
Chemosphere 2019, 236, 124365−124373.
3
+
(13) Huang, W. H.; Ren, J.; Yang, Y. H.; Li, X. M.; Wang, Q.; Jiang, N.;
Yu, J. Qi.; Wang, F.; Zhang, J. Water-Stable Metal-Organic Frameworks
chloride. Chem. - Asian J. 2019, 14, 4246−4254.
3
+
with Selective Sensing on Fe and Nitroaromatic Explosives, and
Stimuli-Responsive Luminescence on Lanthanide Encapsulation. Inorg.
Chem. 2019, 58, 1481−1491.
(32) Yu, L.; Wang, C.; Hu, C. J.; Dong, W. W.; Wu, Y. P.; Li, D. S.;
Zhao, J. A bifunctional luminescent Tb(III)-metal-organic framework
3
+
by a tetracarboxylate ligand for highly selective detection of Fe cation
2
−
(14) Hu, Y.; Joung, J. F.; Jeong, J. E.; Jeong, Y.; Woo, H. Y.; She, Y.;
and Cr O anion. J. Solid State Chem. 2018, 262, 282−286.
2
7
Park, S.; Yoon, J. 2-(Benzothiazol-2-yl)pyren-1-ol, a new excited state
intramolecular proton transfer-based fluorescent sensor for nitro-
aromatic complexs. Sens. Actuators, B 2019, 280, 298−305.
(33) Zhang, Y.; Yang, X.; Zhou, H. C. Direct synthesis of
functionalized PCN-333 via linker design for Fe detection in aqueous
3
+
media†. Dalton Trans. 2018, 47, 11806−11811.
(15) Liang, Y. A silicon-cored tetraphenyl benzene derivative with
(34) Bhamore, J. R.; Jha, S.; Singhal, R. K.; Kailasa, S. K. Synthesis of
Water Dispersible Fluorescent Carbon Nanocrystals fromSyzygium
aggregation-induced emission enhancement as a fluorescent probe for
nitroaromatic complexs detection. Spectrochim. Acta, Part A 2019, 216,
3
+
cumini Fruits for the Detection of Fe Ion in Water and Biological
Samples and Imaging of Fusarium avenaceum Cells. J. Fluoresc. 2017,
27, 125−134.
3
(
95−403.
16) Gungor, S. A.; Sahin, I.; Gungor, O.; Kariper, S. E.; Tumer, F.;
Kose, M. Pamoic Acid Esters and Their Xanthene Derivatives:
Flourimetric Detection of Nitroaromatic Complexs and Non-linear
Optical Properties. Sens. Actuators, B 2018, 255, 3344−3354.
(35) Zhang, Y.; Chen, Y.; Jiang, H.; Wang, X. Selective and Sensitive
3
+
Detection of Fe Ion in Drinking Water Using L-Glutathione
Stabilized Red Fluorescent Gold Nanoclusters. J. Nanosci. Nanotechnol.
2016, 16, 12179−12186.
(17) Zhang, X. D.; Zhao, Y.; Chen, K.; Guo, J. H.; Wang, P.; Wu, H.;
Sun, W. Y. Cucurbit[6]uril-based supramolecular assemblies incorpo-
rating metal complexes with multiaromatic ligands as structure-
directing agent for detection of aromatic amines and nitroaromatic
complexs. Sens. Actuators, B 2019, 282, 844−853.
(36) Wang, P.; Liu, X.; Fu, J.; Chang, Y.; Yang, L.; Xu, K. Synthesis and
fluorescence spectral studies of novel quinolylbenzothiazole-based
3
+
sensors for selective detection of Fe ion. Can. J. Chem. 2018, 96, 835−
841.
(18) Du, J. L.; Zhang, X. Y.; Li, C. P.; Gao, J. P.; Hou, J. X.; Jing, X.;
(37) Zhao, X.; Wang, S.; Zhang, L.; Liu, S.; Yuan, G. 8-
Hydroxyquinolinate-Based Metal-Organic Frameworks: Synthesis,
Tunable Luminescent Properties, and Highly Sensitive Detection of
Small Molecules and Metal Ions. Inorg. Chem. 2019, 58, 2444−2453.
(38) Zhu, H.; Fan, J.; Wang, B.; Peng, X. Fluorescent, MRI, and
colorimetric chemical sensors for the first-row d-block metal ions.
Chem. Soc. Rev. 2015, 44, 4337−4366.
(39) Himo, F.; Demko, Z. P.; Noodleman, L.; Sharpless, K. B.
Mechanisms of Tetrazole Formation by Addition of Azide to Nitriles. J.
Am. Chem. Soc. 2002, 124, 12210−12216.
Mu, Y. J.; Li, L. J. A bi-functional luminescent Zn(II)-MOF for
detection of nitroaromatic explosives and Fe3 ions. Sens. Actuators, B
+
2
(
018, 257, 207−213.
19) Karthik, P.; Pandikumar, A.; Preeyanghaa, M.; Kowsalya, M.;
Neppolian, B. Amino-functionalized MIL-101(Fe) metal-organic
framework as a viable fluorescent probe for nitroaromatic complexs.
Microchim. Acta 2017, 184, 2265−2273.
(20) Gan, X.; Sun, P.; Li, H.; Tian, X.; Zhang, B.; Wu, J.; Tian, Y.;
Zhou, H. A conveniently prepared and hypersensitized small molecular
fluorescent probe: Rapidly detecting free zinc ion in HepG2 cells and
Arabidopsis. Biosens. Bioelectron. 2016, 86, 393−397.
(40) Zhao, X.; Xiao, B.; Fletcher, A. J.; Thomas, K. M.; Bradshaw, D.;
Rosseinsky, M. J. Hysteretic Adsorption and Desorption of Hydrogen
by Nanoporous Metal-Organic Frameworks. Science 2004, 306, 1012−
1015.
(21) Wang, K.; Wang, W.; Pan, S.; Fu, Y.; Dong, B.; Wang, H.
Fluorescent self-propelled covalent organic framework as a microsensor
for nitro explosive detection. Appl. Mater. Today 2020, 19, 100550−
(41) Kitagawa, S.; Kitaura, R.; Noro, S. Functional porous
coordination polymers. Angew. Chem., Int. Ed. 2004, 43, 2334−2375.
(42) Zhang, N.; Xing, Y. H.; Bai, F. Y. A Uranyl-Organic Framework
Featuring Two-Dimensional Graphene-like Layered Topology for
Efficient Iodine and Dyes Capture. Inorg. Chem. 2019, 58, 6866−6876.
(43) Zhang, N.; Sun, L. X.; Xing, Y. H.; Bai, F. Y. A Double-Walled
Thorium-Based Metal-Organic Framework as a Promising Dual-
Function Absorbent for Efficiently Capturing Iodine and Dyes. Cryst.
Growth Des. 2019, 19, 5686−5695.
100556.
(
22) Chang, M. J.; Lee, M. H. A highly selective dual-channel
2
+
fluorescent probe for the detection of Zn ion and pyrophosphate in
micelle. Dyes Pigm. 2018, 149, 915−920.
(
23) Erdemir, S.; Tabakci, B. Highly sensitive fluorometric detection
2+
of Zn ion by calix[4]arene derivative appended 4-biphenylcarboni-
trile. Dyes Pigm. 2018, 151, 116−122.
(
24) Shahid, M.; Srivastava, P.; Razi, S. S.; Ali, R.; Misra, A. Detection
2+
of Zn ion on a reusable fluorescent mesoporous silica beads in
(44) Sun, Y.; Bai, F. Y.; Wang, X. M.; Wang, Y.; Sun, L. X.; Xing, Y. H.
A new stable porous Pr-organic framework constructed by multi-
iodine-substituted aromatic polycarboxylates: Synthesis, character-
ization and selective adsorption of dyes. J. Coord. Chem. 2019, 72,
1560−1578.
aqueous medium. J. Inclusion Phenom. Macrocyclic Chem. 2013, 77,
2
(
41−248.
25) Lin, H. Y.; Chen, T. Y.; Liu, C. K.; Wu, A. T. A fluorescent
chemosensor based on naphthol for detection of Zn. Luminescence
016, 31, 236−240.
26) Chae, J. B.; Lee, H.; Kim, C. Determination of Zinc Ion by a
Quinoline-Based Fluorescence Chemosensor. J. Fluoresc. 2020, 30, 347.
27) Ullmann, S.; Schnorr, R.; Handke, M.; Laube, C.; Abel, B.;
2
(
(45) Wang, Y.; Xing, S. H.; Zhang, X.; Liu, C. H.; Li, B.; Bai, F. Y.;
Xing, Y. H.; Sun, L. X. A family of functional Ln-organic framework
constructed by iodine-substituted aromatic polycarboxylic acid for
2
+
(
turn-off sensing of UO2 . Appl. Organomet. Chem. 2019, 33, e4898−
2
+
Matysik, J.; Findeisen, M.; Ru �g er, R.; Heine, T.; Kersting, B. Zn -Ion
Sensing by Fluorescent Schiff Base Calix[4]arene Macrocycles. Chem. -
Eur. J. 2017, 23, 3824−3827.
e4911.
(46) Wang, B.; Lv, X. L.; Feng, D.; Xie, L. H.; Zhang, J.; Li, M.; Xie, Y.;
Li, J. R.; Zhou, H. C. Zr(IV)-based metal-organic frameworks for the
detection and removal of antibiotics and organic explosives in water. J.
Am. Chem. Soc. 2016, 138, 6204−6216.
(47) Wu, C. D.; Lu, C. Z.; Yang, W. B.; Zhuang, H. H.; Huang, J. S.
Hydrothermal synthesis, structures, and magnetic properties of three
novel 5-aminoisophthalic acid ligand bridged transition metal cation
complexes. Inorg. Chem. 2002, 41, 3302−3307.
(48) Yu, C.; Xu, W. T.; Xiong, W.; Zhou, Y. F.; Huang, D. C.
Syntheses, structures and photoluminescent properties of Cd (II)
polymeric complexes based on 5-Aminoisophthalic acid and bipyridine
Co-ligands. Struct. Chem. 2017, 36, 143−152.
(
28) Ghosh, K.; Dey, S.; Halder, S.; Bhattacharjee, A.; Rizzoli, C.; Roy,
2
+
P. A turn-on fluorescent chemosensor for Zn ion: X-ray structure and
application in cell imaging study. J. Mol. Struct. 2016, 1118, 325−334.
(29) Lv, R.; Chen, Z.; Fu, X.; Yang, B.; Li, H.; Su, J.; Gu, W.; Liu, X. A
highly selective and fast-response fluorescent probe based on Cd-MOF
3
+
3+
for the visual detection of Al ion and quantitative detection of Fe
ion. J. Solid State Chem. 2018, 259, 67−72.
(30) Liu, W.; Xie, J.; Zhang, L.; Silver, M. A.; Wang, S. A hydrolytically
stable uranyl organic framework for highly sensitive and selective
detection of Fe3+ in aqueous media. Dalton Trans. 2018, 47, 649−653.
Q
https://dx.doi.org/10.1021/acs.inorgchem.0c00391
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
pubs.acs.org/IC
Article
(49) Zhang, L.; Zhang, Y.; Wang, R.; Kang, Z.; Liu, X.; Sun, D.; Meng,
Q. Solvent modulated assembly of two Zn Metal-Organic Frameworks:
syntheses, luminescent, and gas adsorption properties. CrystEngComm
2
(
015, 17, 6591−6597.
50) Du, N.; Song, J.; Li, S.; Chi, Y. X.; Bai, F. Y.; Xing, Y. H. A Highly
Stable 3D Luminescent Indium-Polycarboxylic Framework for the
2
+
3+
Turn-off Detection of UO2 , Ru , and Biomolecule Thiamines. ACS
Appl. Mater. Interfaces 2016, 8, 28718−28726.
(51) Fan, T. E.; Xia, T. F.; Zhang, Q.; Cui, Y. J.; Yang, Y.; Qian, G. D. A
porous and luminescent metal-organic framework containing triazine
2
+
group for sensing and imaging of Zn . Microporous Mesoporous Mater.
018, 266, 1−6.
52) Liu, W.; Dai, X.; Bai, Z.; Wang, Y.; Yang, Z.; Zhang, L.; Xu, L.;
2
(
Chen, L.; Li, Y.; Gui, D.; Diwu, J.; Wang, J.; Zhou, R.; Chai, Z.; Wang, S.
Highly Sensitive and Selective Uranium Detection in Natural Water
Systems Using a Luminescent Mesoporous Metal−Organic Framework
Equipped with Abundant Lewis Basic Sites: A Combined Batch, X-ray
Absorption Spectroscopy, and First Principles Simulation Investigation.
Environ. Sci. Technol. 2017, 51, 3911−3921.
(53) Liu, W.; Dai, X.; Wang, Y.; Song, L.; Zhang, L.; Zhang, D.; Xie, J.;
Chen, L.; Diwu, J.; Wang, J.; Chai, Z.; Wang, S. Ratiometric Monitoring
of Thorium Contamination in Natural Water using a Dual-Emission
Luminescent Europium Organic Framework. Environ. Sci. Technol.
2
(
019, 53, 332−341.
54) Feyisa Bogale, R.; Ye, J. W.; Sun, Y.; Sun, T. X.; Zhang, S. Q.;
Rauf, A.; Hang, C.; Tian, P.; Ning, G. L. Highly selective and sensitive
detection of metal ions and nitroaromatic complexs by an anionic
europium(III) coordination polymer. Dalton Trans. 2016, 45, 11137−
11144.
R
https://dx.doi.org/10.1021/acs.inorgchem.0c00391
Inorg. Chem. XXXX, XXX, XXX−XXX