Functional Two-Dimensional Coordination Polymer Exhibiting Luminescence Detection of Nitroaromatics

Article abstract of DOI:10.1021/acs.cgd.8b01640

A polyfluorinated-aromatic carboxylic acid has been designed and synthesized by the acylation reaction, tetrafluoro-bis(3,5-dicarboxyphenyl)terephthalamide (H₄ bdtfa), which assembled with Zn²⁺ ions in the mixed solvents of DMF, py, and H₂O under solvothermal conditions to produce a two-dimensional (2D) coordination polymer (CP), {[Zn₂(bdtfa)(py)₃(H₂O)]·2DMF}_n (1), (py = pyridine, DMF = N,N′-dimethylmethanamide). The final structure has been carefully characterized by various methods including single-crystal X-ray diffraction, powder X-ray diffraction (PXRD), infrared (IR) spectroscopy, and thermogravimetric analysis. Two types of four-coordinated Zn²⁺ centers present a 2D "sql"-type layer through bdtfa^4- ligands, and the adjacent layers are connected through hydrogen bonds and π?π stacking interactions to produce a three-dimensional supramolecular framework. Luminescent results reveal that CP 1 can be regarded as a highly sensitive sensor for detecting nitroaromatics based on the fluorescence quenching effect. Moreover, the reason for the luminescent response of CP 1 toward nitroaromatics has been investigated by theoretical calculations, which indicates that the reason for the quenching can be primarily due to the energy- and electron-transfer as well as the electrostatic interaction between nitroaromatics and CP 1.

Full text of DOI:10.1021/acs.cgd.8b01640

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Article
A Functional 2D Coordination Polymer Exhibiting
Luminescent Detection of Nitroaromatics
Zilong Tang, Hongjuan Chen, Yong Zhang, Baishu Zheng, Shaowei Zhang, and Peng Cheng
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b01640 • Publication Date (Web): 16 Jan 2019
Downloaded from http://pubs.acs.org on January 18, 2019
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A Functional 2D Coordination Polymer Exhibiting
Luminescent Detection of Nitroaromatics
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Published as part of a Crystal Growth and Design virtual special issue on Crystalline
Functional Materials in Honor of Professor Xin-Tao Wu
†
†
†
†
*,†,‡,§
Zilong Tang, Hongjuan Chen, Yong Zhang, Baishu Zheng, Shaowei Zhang,
and Peng
Cheng*
,‡
†Key Laboratory of Theoretical Organic Chemistry and Functional Molecule of the Ministry of
Education, Hunan Provincial Key Laboratory of Controllable Preparation and Functional
Application of Fine Polymers, Hunan Provincial Key Laboratory of Advanced Materials for New
Energy Storage and Conversion, School of Chemistry and Chemical Engineering, Hunan
University of Science and Technology, Xiangtan, Hunan, 411201, China.
‡College of Chemistry, Key Laboratory of Advanced Energy Material Chemistry (MOE), Nankai
University, Tianjin 300071, China.
§Henan Key Laboratory of Polyoxometalate Chemistry, College of Chemistry and Chemical
Engineering, Henan University, Kaifeng 475004, China.
KEYWORDS: Coordination polymer; Crystal structure; Luminescent sensor; Nitroaromatics
ABSTRACT: A polyfluorinated-aromatic carboxylic acid has been designed and synthesized by
the acylation reaction, tetrafluoro-bis-(3,5-dicarboxyphenyl)terephthalamide (H bdtfa), which
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assembled with Zn2+ ions in the mixed solvents of DMF, py and H O under solvothermal
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conditions to produce a 2D coordination polymer (CP), {[Zn (bdtfa)(py) (H O)]·2DMF} (1),
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n
(py = pyridine, DMF = N,N'-dimethylmethanamide). The final structure has been carefully
characterized by various methods including single-crystal X-ray diffraction, powder X-ray
diffraction (PXRD), infrared (IR) spectrum, and thermogravimetric (TG) analysis. Two types of
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4
four-coordinated Zn centers present a two-dimensional ‘sql’-type layer through bdtfa ligands,
and the adjacent layers are connected through hydrogen bonds and π···π stacking interactions to
produe a 3D supramolecular framework. Luminescent results reveal that CP 1 can be regarded as
a highly sensitive sensor for detecting nitroaromatics based on the fluorescence quenching effect.
Moreover, the reason for the luminescent response of CP 1 towards nitroaromatics has been
investigated by theoretical calculation, which indicates that the quenching reason can be
primarily due to the energy- and electron-transfer as well as electrostatic interaction between
nitroaromatics and CP 1.
INTRODUCTION
Nitroaromatic compounds, as one kind of important chemical raw material, have been used
extensively in various areas including leather and rubber, pharmaceuticals, explosives and so on.
however, the misuse of the nitroaromatic compounds could have a significant impact on the
environment, human health, and public safety because of their high toxicity and hazard.1-2
Although lots of instrument equipments have been developed to analyze nitroaromatic
compounds highly sensitive and selective, they usually require tedious pretreatment process,
high expenses, and cumbersome portability.3-5 As a result, it is meaningful to investigate
inexpensive and convenient probes with high selectivity and sensitivity to monitor nitroaromatic
compounds.
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On the other hand, coordination polymers (CPs) consist of metal ions/clusters and organic
ligands, constitute an interdisciplinary field that has expanded rapidly in the past decade. The
nearly limitless choices and combinations of organic linkers and metal centers allow to prepare
various structures with interesting properties including but not limited to, gas storage and
separation, catalysis, chemical sensing, as well as bioimaging and drug delivery.3-20 In particular,
luminescent CPs have recently bloomed out as promising candidates for sensing of numerous
analytes because of their inherent advantages over other traditional molecular sensors, such as
good crystallinity, defined crystal structure, high surface area and porosity, as well as adjustable
and modifiable structure-induced luminescence performance.3-5 More importantly, the porosity
of CPs could enhance the probability of host-guest interactions by adsorbing and pre-enriching
analytes, thus improving the detecting sensitivity and detection limit. In addition, the open metal
sites and Lewis acidic and basic sites of organic linkers are readily available for CPs by post-
synthetic modifications or pre-design of the structures, which may improve the detection
selectivity. As a result, lots of luminescent CPs based sensors have been prepared and employed
for detecting cations, anions, organic molecules, explosives, environmental toxins, pH,
temperature, and biomolecules, and so on.3-5,17-54
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In this contribution, we design and synthesize a new polyfluorinated-aromatic ligand,
tetrafluoro-bis-(3,5-dicarboxyphenyl)terephthalamide (H bdtfa) (Scheme 1), containing four
4
coordinated carboxylate groups and two functional amide groups by the acylation reaction of
2,3,5,6-tetrafluoroterephthalic acid and 5-aminoisophthalic acid, to assemble with Zn2+ to
construct luminescent CPs for the following considerations: (i) the H bdtfa ligand could act as a
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diisophthalic acid linker separated by a tetrafluoro- terephthalamide spacer, the special
orientation of isophthalate subunit is in favor of the isolation of porous structures, and the four
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carboxylate groups can allow to combine different metal ions to form multi-dimensional
structures. (ii) H bdtfa could be completely or partially deprotonated to produce abundant acid-
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
3
2

base-dependent anions varying pH values (bdtfa , Hbdtfa , H bdtfa , and H bdtfa ), and thus
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lead to various structures. Moreover, the deprotonated bdtfa , Hbdtfa , H bdtfa , and H bdtfa
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as well as the high electronegativity fluorine atoms can serve as hydrogen bonds donors and
acceptors, which are beneficial to generate supramolecular structures. (iii) Both tetrafluoro-
terephthalamide and isophthalate motifs are typical π-conjugate systems, which are favorable to
produce π···π stacking interactions, thereby enhance the stability of the framework. (iv) H bdtfa
4
is electron-rich and π-conjugated ligand with good electron-transfer capability, which may
improve the sensing ability through host-guest interactions because of hydrogen bonds and π···π
1
0
2+
interactions. Moreover, the d electronic configuration Zn ion and π-conjugated ligands are
usually applied to prepare fluorescent materials.
Scheme 1. The synthetic process of the H bdtfa ligand.
4
2
+
Based on the above considerations, we explored the reactions of H bdtfa and Zn ions by
4
regulating the rations of organic linkers and metal centers, reaction solvents, reaction
temperature and pH value, etc. Herein, a 2D CP was obtained under solvothermal conditions,
{
[Zn (bdtfa)(py) (H O)]·2DMF} (1), (DMF = N,N'-dimethylmethanamide, py = pyridine). The
2 3 2 n
structure has been measured by the single-crystal X-ray diffraction, which further determined by
PXRD, TG analysis and IR. The results demonstrate that the asymmetric skeleton of 1 has two
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kinds of Zn2+ centers, one bdtfa4– bridging ligand, three coordinated py molecules, one
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+
coordinated water molecule, and two uncombined DMF molecules. Two types of Zn centers
4–
interconnected through bdtfa present a ‘sql’-type 2D layer, the neighbouring layers interact
each other through hydrogen bonds and π···π interactions to from the 3D supramolecular architecture.
The luminescent experiment of 1 has been carried out, which reveal that 1 could act as an
excellent sensor to detect nitroaromatics on account of fluorescence quenching effect. Moreover,
the reason for the luminescent response of 1 towards nitroaromatics has been investigated by
theoretical calculation.
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EXPERIMENTAL SECTION
General Methods and Materials. Unless otherwise specified, all reagents are commercially
1
13
available and have been used directly. The H-NMR and C-NMR spectra are measured on a
Bruker AV-II 500 MHz NMR spectrometer. Elemental analyse data are obtained from a Perkin-
Elmer 2400-II CHNS/O analyzer. IR spectra are collected on a Nicolet 6700 spectrometer with

1
KBr pellets in 4000400 cm . TG curve is acquired from a NETZSCH TG 209 Setaram
1
apparatus with the heating rate of 10 ˚C·min under N atmosphere. PXRD spectra are carried
2
out on a Bruker D8 Advance instrument with Cu Kα radiation (λ = 1.54056 Å). The luminescent
experiments are finished on an F-4500 fluorescence spectrophotometer.
Synthesis of the H bdtfa ligand. 2,3,5,6-tetrafluoroterephthalic acid (2.0 g, 8.4 mmol) and
4
4
0.0 mL SOCl were added in a 100 mL round-bottomed flask, the mixture was heated to
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95 ˚C and stirred for 10 h. After cooling to room temperature, the excess SOCl in the
2
mixture was removed by reduced in the rotary evaporator to give the yellow oil. Then
4
0.0 mL THF was added into the above oil to harvest solution A. In another 500 mL
round-bottomed flask, 5-aminoisophthalic acid (3.1 g, 17.0 mmol) and 180.0 mL THF were
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added and stirred at 0 ˚C, then solution A was dropwise added, and a yellow precipitate
was produced almost immediately. Then 1.0 mL triethylamine was slowly added and
stirred for 12 h at ambient temperature. The volume of THF was reduced in the rotary
evaporator and then 80.0 mL 2 mol·L-1 HCl was added. The precipitate was filtrated and
washed with DMF, H O and CH OH, and dried under vacuum to give a yellow powder
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(Scheme 1). Yield: ca. 77% (based on 2,3,5,6-tetrafluoroterephthalic acid). Anal. calcd (%) for
1
6
C H F N O : C 51.08, H 2.14, N 4.96. Found: C 50.97, H 2.23, N 4.88. H-NMR (DMSO-d ,
2
4
12
4
2
10
5
00 MHz, δ/ppm): 13.39 (4H, COOH), 11.61 (2H, ArH), 8.55 (4H, ArH), 8.31 (2H, CONH)
1
3
6
(
Figure S1); C-NMR (DMSO-d , 125 MHz, δ/ppm): 166.14, 155.65, 143.63, 141.64, 141.54,
138.38, 132.14, 126.01, 123.99, 117.90 (Figure S2). IR (KBr pellets): 3429 (br), 1706 (s),
677 (s), 1624 (m), 1582 (s), 1479 (s), 1433 (m), 1403 (m), 1350 (m), 1267 (m), 1235
1
(
m), 994 (s), 948 (w), 782 (w), 759 (w), 679 (m) cm–1 (Figure S3)
.
Synthesis of {[Zn (bdtfa)(py) (H O)]·2DMF} (1). Zn(NO ) ·6H O (0.0592 g, 0.20
2
3
2
n
3 2
2
mmol) and H bdtfa (0.0282 g, 0.05 mmol) were added in a 5 mL mixed solvents
4
(
H O:py:DMF = 1:1:8) in a 20 mL vial. Colorless block crystals were obtained after
2
being placed in an oven at 80 ˚C for three days. Yield: ca. 62% (based on H bdtfa). Anal.
4
calcd (%) for C H F N O Zn : C 49.47, H 3.60, N 8.97. Found: C 49.59, H 3.68, N 9.03. IR
4
5
39
4
7
13
2
(KBr pellets): 3447 (br), 1686 (m), 1653 (s), 1622 (m), 1561 (m), 1474 (w), 1449 (m),
1
434 (w), 1384 (m), 1332 (m), 1202 (m), 1107 (m), 1070 (m), 1046 (m), 996 (m), 781
(m), 761 (m), 734 (m), 697 (m) cm–1 (Figure S3)
.
X-ray Crystallography. The crystal 1 was measured on a Bruker Apex-II CCD diffractometer
with monochromatic Mo Kα radiation (λ = 0.71073 Å) at 296(2) K, Absorption and scaling
correction were undertaken with SADABS program, and the direct method was used to resolve
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the crystal structure, except for hydrogen atoms, other atoms were refined by the full-matrix
least-square procedure employing the free Olex2 program embedded with SHELXL-2016.55-56
The refinement details for CP 1 have been explained in the .cif document, and the
crystallographic data and refinement parameters for 1 have been summarized in Table 1 (CCDC
no. 1852625).
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Table 1. Crystallographic Data and Refinement Parameters for 1.
1
formula
C H F N O Zn
45 39 4 7 13 2
-1
Mr (g mol )
1092.57
296(2)
T (K)
Cryst syst
space group
a (Å)
Triclinic
P-1
12.5194(14)
14.5007(16)
16.5672(19)
80.405(2)
70.320(2)
69.843(1)
2654.1(5)
2
b (Å)
c (Å)
α (°)
β (°)
γ (°)
V (Å3)
Z
-3
Dc (g cm )
1.367
-
1
μ (mm )
0.982
Rint
0.0482

14 ≤ h ≤ 14
17 ≤ k ≤ 17
19 ≤ l ≤ 19
limiting indices

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reflns collected
indep reflns
params
9300
6567
692
GOF on F2
1.057
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a
b
R wR [I>2σ(I)]
0.0715 0.0996
0.1915 0.2154
0.821/-0.635
1
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2
a
b
R wR [all data]
1
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2
Δρmax/Δρmin (e Å-3)
a
b
2
2 2
2 2 1/2
R = Σ||F |–|F ||/Σ|F |; wR = {Σ[w(F –F ) ]/Σ[w(F ) ]} .
1
o
c
o
2
o
c
o
Luminescent experiments. Nitrobenzene (NB) was diluted 100 times with DMF before used.
For other nitroaromatic compounds including 2,4,6-trinitrophenol (PA), 2,4-dinitophenol (BNP),
o-nitroaniline (oNA), o-nitrophenol (oNP), p-nitroaniline (pNA), p-nitrophenol (pNP), m-
2
1
nitroaniline (mNA), and m-nitrophenol (mNP), the corresponding 10 mol·L analyte solutions
were prepared with DMF, respectively. The concentration-dependent intensity test was executed
as shown below: soaking 3 mg CP 1 in 2.0 mL DMF to disperse evenly with ultrasound, then
2
1
adding the corresponding 10 mol·L solutions containing different nitroaromatic compounds
in the above suspension.
RESULTS AND DISCUSSION
Structural Descriptions. The as-synthesized bulky crystals 1 has a high phase purity, which
were proved by comparing the simulated PXRD pattern with the experimental one (Figure S4).
Moreover, when immersing 1 in DMF for three days, the experimental PXRD pattern is also
agreement with the simulated one (Figure S4), indicating the structure of 1 can maintain in DMF
at least three days.
Crystal structure results of 1 display that it belongs to the triclinic system with the space group
2
+
4–
P-1. In the asymmetric structure (Figure 1a), there are two Zn centers, one bdtfa ligand, three
coordinated py molecules, one coordinated water, and two unbounded DMF molecules, and the
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2+
formula as follows, {[Zn (bdtfa)(py) (H O)]·2DMF} (1). Both two independent Zn ions adopt
2
3
2
n
the four-coordinated tetrahedral geometry. Zn1 is defined by two carboxyl O atoms of two
4–
bdtfa through the bridging mode, one water molecule [Zn1-O: 1.941(4) – 1.976(3) Å], and one
1
1
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py molecule [Zn1-N: 2.030(5) Å]. Whereas Zn2 center is surrounded by two carboxyl O atoms
4–
of two bdtfa by the bridging mode [Zn2-O: 2.028(4) – 2.063(5) Å], and two py molecules
[
Zn2-N: 2.061(5) – 2.068(6) Å] (The selected bond lengths and angles, see Table S1 and S2). It
4–
is important to note that the bdtfa ligand also exhibits two kinds of coordinated orientations
because the amide bonds can rotate freely, resulting into two different angles between the two
2
+
sides of benzene rings and the tetrafluoro-benzene ring (Figure 1b, c). Neighboring Zn ions are
4–
bridged by bdtfa to produce a 2D layer containing two kinds of rectangular channels in the bc
plane, in which are occupied by the free DMF molecules (Figure 1d). To describe the 2D
5
7
architechture of 1 more clearly, the freely available program TOPOS 5.0 is used to analyze the
2
+
4–
topological structure. If every Zn ion is regarded as a node and each bdtfa serves as a linker,
CP 1 could simplify as the 4-connected ‘sql’-type topological structure, and the corresponding
4
2
Schläfli symbol is {4 ·6 } (Figure 1e).
It is worth noting that many C, N and O atoms, as well as the high electronegativity F atoms in
1
may be as hydrogen bonds donors and acceptors to produce supramolecular architecture.
Furthermore, the offset arrangements of benzene and pyridine in 1 is opposite to the edge-to-face
and face-to-face, which could form strong π···π stacking interactions. As a result, the
neighbouring layers could stack to give a supramolecular architecture (Figure 1f) by π···π
stacking interactions as well as inter- and intramolecular hydrogen bonds (Table S3).
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Figure 1. a) The thermal ellipsoids plot representation of the asymmetric skeleton of 1, H and
isolated DMF molecules are not shown for clarity; b) and c) The two kinds of coordinated
4–
orientations of bdtfa ligands in 1; d) The 2D network of 1, in which are occupied by isolated
DMF molecules presented as space-filling mode; e) The simplified 4-connected ‘sql’-type
topological structure of 1. f) The 3D supramolecular structure of 1.
10
Luminescent properties. CPs constructed from d electronic configuration metal centers and
π-conjugated organic ligands are generally chosen to evaluate their luminescent properties.58-59 In
the case of 1, H bdtfa is π-conjugated and electron-rich ligand with good electron-transfer
4
10
2+
ability, and is coordinate with d electronic configuration Zn ions, which encourages us to
explore its luminescent performance. Therefore, we measure the solid state emission spectrum of
1 at ambient temperature, and it shows one obvious emission band at ca. 458 nm when excited at
1
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56 nm (Figure S5). To explore the origin of the luminescent emission of CP 1, the solid state
luminescence spectrum of the free H bdtfa ligand has been also carried out at the same
4
conditions (Figure S5). The similar emission band at ca. 388 nm is presented by the H bdtfa
4
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0
58
ligand, which may be ascribed to the intra-ligand emission state of π* → π transition. By
comparing the emission spectra of 1 and H bdtfa, it can be seen that the emission signal of 1 is
4
neither ligand-to-metal charge transfer (LMCT) nor metal-to-ligand charge transfer (MLCT),
1
0
2+
which may be mainly ascribed to the d configuration Zn center is relatively difficult to reduce
or oxidize, and this phenomenon is usually encountered in previous reports.58 Thus, the
luminescent emission of 1 could be mainly due to the intra-ligand charge transfer transition.
Moreover, the luminescence intensity of 1 is slightly enhanced, which can be explained that the
ligand binds to mental center to increase the rigidity compared with the free H bdtfa ligand,
4
therefore decreasing the energy loss of radiation-less decay. In addition, the luminescent
emission spectrum of 1 is distinctly red-shifted compared with the free H bdtfa ligand,
4
2+
manifesting the existence of coordination interactions among the H bdtfa ligand and Zn
4
centers.59
Previous results suggest that the energy and electron could transfer from electron-donating
complex to high electron-withdrawing nitro-compound under photo-excitation, which usually
result in the fluorescence weaken or completely quenched.52-54,59 From the structural descriptions
of 1, the π···π interactions and hydrogen bonds could strengthen the interactions between
analytes and target compound, and thus improve the sensing ability. Therefore, the electron-
withdrawing nitroaromatic compounds containing NB, PA, BNP, oNA, oNP, mNA, mNP, pNA,
and pNP are chosen to assess the luminescent sensitivity of 1.
1
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Figure 2. The concentrations-dependent emission spectra (λ = 345 nm) and Stern-Volmer plots
ex
of 1 in DMF towards various concentrations of nitroaromatic compounds, NB (a and b), BNP (c
and d), and PA (e and f), respectively.
The luminescent experiments of concentration-dependent intensity are executed by slowly
adding different amount of nitroaromatic compounds into the well-dispersed suspensions of 1,
and the concentration-dependent intensity for NB is selected as a representative of the specific
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description. The emission intensity decreases as gradually adding NB, almost quenched when the
amount of NB attains 200 μL (1091 ppm) (Figure 2a), and the quenching efficiency is 93.4%.
The quenching effciency of NB can be assessed by employing the Stern-Volmer (S-V) equation,
1
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9
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8
9
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0
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2
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4
5
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8
9
0
59
I /I ‒ 1 = K [M], in which I and I are the emission intensities of maximum emission band
0
SV
0
before and after the addition of NB, respectively, [M] represents the molar concentration of the
-1
NB analyte (mM), and KSV is the S-V constant (M ). The maximum emission intensities at ca.
25 nm versus the concentration of NB analyte are plotted and presented in Figure 2b. When the
concentration of NB is lower than 0.02 mM, the S-V curve is nearly linear, and the detection
4
-7
1
limit can be calculated to be 9.15 × 10 mol·L by the equation 3σ/k, in which σ is the standard
deviation of luminescent intensities of 10 field blanks, k is the slope.60 However, when
concentration of NB is higher than 0.02 mM, the S-V curve is apparent deviation from linearity,
which may mainly due to the reason that the presence of self-absorption and/or the dynamic
quenching and static quenching resulted from the energy-transfer process.52-54 In order to assess
28
the whole concentration, we employ an exponential S-V formula, I /I = a*exp(k[M]) + b, in
0
which I and I are the maximum emission intensities before and after adding NB, respectively,
0
[M] represents the concentration of NB(mM), a, b, and k are constants. The results demonstrate
that the whole range could match well with the equation I /I = 1.167*exp(28.860[M]) ‒ 1.121
0
4
1
(
Figure 2b), and the quenching constant of NB is 3.368 × 10 L·mol calculated from the fitted
values of a and k.
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Figure 3. The concentrations-dependent emission spectra (λ = 345 nm) and Stern-Volmer plots
ex
of 1 in DMF toward various concentrations of nitroaromatic compounds, oNP (a and b), mNP (c
and d), and pNP (e and f), respectively.
Analogously, other nitroaromatic compounds have been analyzed by the same methods (Figure
2
9
c-f, 3, and 4), the quenching efficiencies are 98.7% (100 μL), 91.8% (40 μL), 93.0% (130 μL),
2.5% (300 μL), 90.9% (70 μL), 91.9% (500 μL), 93.0% (800 μL), and 92.7% (100 μL) for
1
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BNP, PA, oNP, mNP, pNP, oNA mNA and pNA, and the detection limits can be calculated to be
-7
-7
-6
-5
-6
-5
-5
1
.61 × 10 , 1.86 × 10 , 1.07 × 10 , 5.07 × 10 , 2.60 × 10 , 3.13 × 10 , 1.52 × 10 , and 8.55 ×
-6
1
10 mol·L , respectively. Furthermore, the quenching constants obtained from a and k values
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3
3
4
4
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4
4
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4
4
4
5
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5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
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2
3
4
5
6
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9
0
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3
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5
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7
8
9
0
1
2
3
4
5
6
7
8
9
0
4
4
3
3
by fitting the exponential S-V equation are 2.642 × 10 , 2.755 × 10 , 5.430 × 10 , 2.935 × 10 ,
3
3
3
4
1
9
4
.091 × 10 , 2.018 × 10 , 1.896 × 10 , and 1.694 × 10 L·mol , respectively (Figure 2c-f, 3, and
), which are comparatively high among the documented CP-based sensors for probing
nitroaromatic compounds (Table 2).52-54 Additionally, it is important to note that PA exhibits the
largest quenching efficiency of 87.9% at the same concentration (30 μL) in the selected
nitroaromatic compounds (87.0% for BNP, 72.6% for pNA, 70.0% for pNP, 54.5% for oNP,
3
1.6% for oNA, 30.5% for mNP, and 25.5% for mNA, respecitvely), namely, 1 could be
employed as an excellent sensor for detecting PA.
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Figure 4. The concentrations-dependent emission spectra (λ = 345 nm) and Stern-Volmer plots
ex
of 1 in DMF toward various concentrations of nitroaromatic compounds, oNA (a and b), mNA (c
and d), and pNA (e and f), respectively.
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Table 2. Selected CP-based sensors for the detection of nitroaromatics.
Quenching
constant
Limit
detection
of
Sensing Materiala
Target
(
K ,
sv
1
(mol·L )

1
L·mol )
1.18 × 102
15
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
BNP
pNP
PA
-
-
-
-
[Cd(ppvppa)(1,4-NDC)]n33
3
4
2.08 × 106
3.7 × 104
7.75 × 103
2.5 × 104
4.6 × 103
5.11 × 104
2.28 × 104
1.20 × 104
[Me NH ] [Zn (qptc) (trz) ]·6H O
2
2 4
6
3
4
2
1
35
[Cd(ndc)(L )] ∙H O
PA
2
2
7
7
36
1.62 × 10-2
[Tb(L )(HL )(H O) ]
BNP
NB
2
2 n
-
6
37
[
Eu (H L ) (H O) ]·21H O
2 2 3 2 2 2
pNP
BNP
pNA
oNA
-
3
8
2.87 × 10-6
{
(Me NH ) [Zn (TDPAT) (μ -O) Zn ]·G }
2 2 10 6 4 3 2 3 x n
1.75 × 10-7
-
3
9
[
Zn(bpba)(NO )]
3
mNA 3.1 × 102
-
NB
BNP
BNP
PA
1.73 × 103
5.3 × 104
3.3 × 104
2.9 × 104
4.9 × 104
9.4 × 103
1.8 × 104
5.8 × 104
6.39 × 104
7.18 × 104
3.8 × 104
4.7 × 104
-
4
0
2.28 × 10-7
[
{Cd (4-tp-3-lad)(1,4-BDC) }·2MeCN]
2 2 n
[
{Cd(ppene)(1,4-BDC)}·MeCN]n40
1.03 × 10-6
2
41
Zr O (OH) (L )
6
-
6
4
4
4
2
2.78 × 10-4
Zn (TZBPDC)(μ -OH)(H O)
2
PA
2
3
2
oNP
PA
-
4
3
[
Mg Zn (OH) (1,4-NDC) (H O) ]·6H O
2
2
2
3
2
2
2
-
4
44
Zr O (OH) (L )
6
PA
-
6
4
4
4
5
[Zn (TPT) (DMF) ]·0.5HNMe
PA
-
3
2
2
2
4
5
NH Me ·[Zn(TPT)]·DMF
PA
-
2
2
Tb(L5)246
Zr O (OH) (H O) (TTNA)
8/3
PA
5.0 × 10-8
-
4
7
pNP
6
4
8
2
4
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5.1 × 105
5.7 × 104
4.6 × 104
4.86 × 103
1.08 × 103
4.19 × 104
2.93 × 104
4.1 × 104
5.98 × 104
3.37 × 104
9.09 × 103
2.64 × 104
PA
-
NB
PA
-
48
1.29 × 10-8
[
[
[
Zn (ad) (BPDC) O·2Me NH ]·G
8
4
6
2
2
49
Zn (tptc)(apy)(H O)]·H O
NB
PA
-
-
-
-
2
2
2
0
1
2
3
4
5
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9
0
1
2
3
4
5
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9
0
1
2
3
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9
0
1
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9
0
1
2
3
4
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9
0
50
Zn (DMF)(Ur) (2,6-NDC) ]
4
2
4
PA
3
51
{
[Zn (L )(5-AIP) ]·3H O}
2 2 2 n
pNP
PA
+
52
Rh G@{(Me NH ) [Na (TATB) ](DMF) (H O) }
92 n
-
6
2
2
5
31
12
30
2
8 53
1.58 × 10-6
Pb O (L )
PA
3
2
9.15 × 10-7
2.60 × 10-6
1.61 × 10-7
NB
pNP
BNP
PA
{
[Zn (bdtfa)(py) (H O)]·2DMF} (This work)
2 3 2 n
2.76 × 104
1.69 × 104
1.86 × 10-7
8.55 × 10-6
pNA
a
ppvppa = N-(pyridin-2-yl)-N-(4-(2-(pyridin-4-yl)vinyl)phenyl)pyridin-2-amine; trz = 1,2,4-
triazole; 1,4-H NDC = 1,4-naphthalenedicarboxylic acid; H qptc = terphenyl-2,5,2′5′-
2
4
6
1
tetracarboxylic acid; H L = α-hydroxyphosphonic acid; L = 4-amino-3,5-bis(4-imidazol-1-
4
7
ylphenyl)-1,2,4-triazole; H L = 5-(imidazol-1-yl)isophthalic acid; H TDPAT = 2,4,6-tris(3,5-
2
6
dicarboxylphenylamino)-1,3,5-triazine; Hbpba = 4-(bis(4-(pyridin-4-yl)phenyl)amino)benzoic
acid; 4-tp-3-lad = 2,3,5,6-tetra(pyridin-4-yl)-bicyclo[2.2.0]hexane; 1,4-H BDC = benzene-1,4-
2
2
dicarboxylic acid; ppene = 4-pyrpoly-2-ene; H L = 2-phenylpyridine-5,4'-dicarboxylic acid;
H TZBPDC = 4'-(1Htetrazol-5-yl)-[1,1'-biphenyl]-3,5-dicarboxylic acid; apy = aminopyridine;
2'-amino-[1,1':4',1''-terphenyl]-4,4''-
dicarboxylate; ad = adenine; H TPT = p-terphenyl-3,4'',5-tricarboxylic acid; H TTNA = 6,6',6''-
2,4,6-trimethylbenzene-1,3,5-triyl)tris(2-naphthoic acid; BPDC= biphenyl dicarboxylic acid;
H tptc = terphenyl-3,3″,5,5″-tetracarboxylic acid; L = 3-pyridin-3-yl-N-[5-(3-pyridin-3-yl-
acryloylamino)-naphthalen-1-yl]-acrylamide; Ur = urotropin; H AIP = 5-amino isophthalic acid;
TATB = 4,4',4''-(1,3,5-triazine-2,4,6-triyl)tris-benzoate; H L = 4-(1H-tetrazol-5-yl)phenol;
2
3
5
4
L
=
3-bis(3-carboxyphenyl)imidazolium;
L
=
3
3
(
3
4
2
8
2
H ndc = 2,6-Naphthalenedicarboxylic acid.
2
In order to explore the reason for the fluorescence response of selected nitroaromatics, the
response reason of 1 towards selected nitroaromatics has been investigated. First, the quenching
probability caused by the structural breakage of 1 could be readily ruled out from PXRD
experiments and IR spectra (Figure S4 and S6). Considering that the luminescent signal of 1
1
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primarily comes from the intra-ligand charge transfer transition of the H bdtfa ligand. Therefore,
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the molecular orbitals of 1 are approximately computed with the H bdtfa ligand. The energy for
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highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO)
1
1
1
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of selected nitroaromatic compounds and H bdtfa ligand are calculated by the density functional
4
theory at the B3LYP level (Figure 5).52,59 The results suggest that the LUMO energy of the
selective nitroaromatic compounds is smaller, the quenching potency is larger. The quenching
potency of PA is highest among selected nitroaromatic compounds, which may be due to that the
excited state electrons are most easily transferred from the conduction bands of H bdtfa to the
4
LUMO orbital of PA since the lowest LUMO energy, However, the order of quenching constants
of selected nitroaromatic compounds is not completely consistent with the energy of LUMO
orbitals, manifesting the electron-transfer may be not the only factor of the luminescent response.
The electrostatic interactions and/or energy transfer may be other possible reasons and be
responsible for the luminescent response,52-54,59 which is also supported by the exponential S-V
curves. Indeed, many C, N, O and high electronegativity F atoms coexist in 1, which can serve as
hydrogen bonds acceptors and donors to increase the interactions between nitroaromatic
compounds and CP 1. Furthermore, the π···π stacking interactions in 1 also interact with
nitroaromatis through the host-guest interactions. Consequently, the electron transfer and
electrostatic interactions as well as energy-transfer can easily happen between nitroaromatic
compounds and the framework of 1, leading to the luminescent intensity weaken or even
quenching.
In addition, the possible reason that PA has the largest quenching constant among the selected
nitroaromatics can attribute to the following two aspects: firstly, the energy of LUMO for PA is
lowest, which permits electron and energy-transfer from the framework of 1 to PA molecules is
1
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59
easiest and make the luminescent response most obvious. On the other hand, the PA molecule
possessing more -OH and -NO groups could participate in the formation of hydrogen bonds
2
with 1 stronger than other nitroaromatic compounds, the host-guest interaction between 1 and PA
0
1
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may be stronger, therefore the electrostatic interaction can take place more easily.
Figure 5. a) and b) The energy of HOMO and LUMO for selected nitroaromatics and H bdtfa.
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CONCLUSIONS
In conclusion, a new polyfluorinated-aromatic carboxylic acid ligand was designed and
2
+
prepared by the typical acylation reaction, which was further employed to react with Zn ions to
construct a 2D CP under the solvothermal conditions. The crystal structure demonstrates that two
1
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2
+
4
kinds of tetrahedral Zn centers are bridged through bdtfa to produce a 2D ‘sql’ topological
structure, which further generate a 3D supramolecular architecture by π···π interactions and
hydrogen bonds. Importantly, CP 1 can be regarded as a highly sensitive probe for detecting
nitroaromatic compounds. Furthermore, the luminescent response of 1 towards nitroaromatic
compounds has been preliminarily investigated by the theoretical calculation, and the reason
could be primarily ascribed to energy- and electron-transfer and electrostatic interaction between
nitroaromatic compounds and CP 1.
ASSOCIATED CONTENT
Supporting Information
IR spectra, PXRD patterns, TG analysis and TG curve, and the solid-state emission spectra of 1
and the free H bdtfa ligand, as well as the information of bond lengths and angles of 1. This
4
material is available free of charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*E-mail: swzhang@hnust.edu.cn (S.Z.); pcheng@nankai.edu.cn (P.C.).
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
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This work was supported by the National Natural Science Foundation of China (21601058 and
1771112), 111 project (B12015), the Hunan Provincial Natural Science Foundation of China
2
(2018JJ3146), the Open Research Fund of Henan Key Laboratory of Polyoxometalate Chemistry
HNPOMKF1602), and Hunan University of Science and Technology (E51677, STZ2018007,
01810534039 and CX2018B672).
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