Luminescent coordination polymer with conjugated lewis acid sites for the detection of organic amines

Article abstract of DOI:10.1021/acs.cgd.5b01026

A stable three-dimensional coordination polymer, [Eu₃(bcbp)₃(NO₃)₇(OH)₂]_n (1) (H₂bcbp2Cl = 1,1′-bis(4-carboxyphenyl)-(4,4′-bipyridinium) dichloride), was prepared by the solvothe

Full text of DOI:10.1021/acs.cgd.5b01026

Article
pubs.acs.org/crystal
Luminescent Coordination Polymer with Conjugated Lewis Acid Sites
for the Detection of Organic Amines
†
†
,†,‡
,†
†
Jian-Jun Liu, Ying-Fang Guan, Mei-Jin Lin,* Chang-Cang Huang,* and Wen-Xin Dai
†
College of Chemistry, Fuzhou University, Fuzhou 350116, China
‡
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences,
Fuzhou 350002, China
*
S Supporting Information
ABSTRACT: A stable three-dimensional coordination polymer,
[
Eu (bcbp) (NO ) (OH) ] (1) (H bcbp·2Cl = 1,1′-bis(4-carbox-
3
3
3 7
2 n
2
yphenyl)-(4,4′-bipyridinium) dichloride), was prepared by the
solvothermal reaction of Eu(NO ) ·6H O and H bcbp·2Cl in
3
3
2
2
methanol, which was characterized by infrared spectroscopy,
single-crystal X-ray diffraction, powder X-ray diffraction, and
thermogravimetric analyses. In the solid state, 1 consists of an
unusual trinuclear Eu(III) unit (Eu (CO ) (NO ) (OH), Eu −
3
2 6
3 7
3
SBU), which further connects to six neighboring ones through six
bcbp ligands to form a three-dimensional network. As expected, 1 exhibits a strong red-light emission at ambient temperature.
Due to the presence of the electron-deficient bipyridinium moiety in the conjugation, this emission is selectively quenched by
electron-rich organic amine compounds with high sensitivity and exhibits a prominent visual color change.
INTRODUCTION
electron-deficient quenchers, such as 2,4,6-trinitrotoluene
■
30−32
(
TNT).
However, few reports have dealt with electron-
The development of selective sensing materials for the
detection of amines has received considerable attention in the
fields of environmental and industrial monitoring, quality
control of food, and medical diagnosis because organic amines
have been widely used in the polymer, dye, and pharmaceutical
33−35
rich amines.
amines to unsaturated metal ions.
Among them, most are based on coordinating
36,37
In addition, although
these materials can measure very low concentrations of amines,
they are air/water sensitive and subject to degradation at room
38,39
1
−5
temperature.
Electron transfer is a common strategy to
industries.
However, most of these amines are colorless,
making their differentiation via visual inspection difficult.
Among the approaches employed toward the detection of
amines, such as gas chromatography coupled with mass
spectrometry, surface enhanced Raman spectroscopy, nuclear
quadruple resonance, energy dispersive X-ray diffraction, and
achieve fluorescent quenching. On the basis of the fact that
amines always act as electron donors, luminescent CPs
containing electron-deficient building blocks are anticipated
to realize fluorescent quenching by amines.
4,4′-Bipyridinium derivatives are an attractive class of
6
−9
cyclic voltammetry, there is a requirement for very expensive
instruments, and they are not easily accessible in most cases. A
sensitive, optical detection method would be simpler, quicker,
and less expensive and could be potentially employed both in
electron-deficient (Lewis acid) molecules containing an electri-
40−43
cally charged moiety in the conjugation.
Although there
are several reports of coordination polymers based on
bipyridinium derivatives, none of these CPs exhibits strong
10,11
solution and the solid phase.
Fluorescent sensing or
44−47
emission.
Considering the weak fluorescence of such
probing has proved to be an expedient detection technique
on account of the high signal output and detection
ligands, we selected luminescent Eu(III) as the metal cation.
Moreover, to achieve porous CPs, a rigid pyridinium containing
two positive charges, 1,1′-bis(4-carboxyphenyl)-(4,4′-bipyridi-
1
2−16
simplicity.
Although much success has been achieved in
producing fluorescent probes for organic pollutant sens-
1
7−23
nium) dichloride (denoted H bcbp·2Cl, Scheme 1), was used
2
ing,
the detection of amines still remains challenging
in this article. As expected, the obtained crystalline three-
dimensional (3D) porous CPs, {Eu (bcbp) (NO ) (OH) }
2 n
because the sensory materials that meet the requirements for
fluorescent probes, including intense emission in the solid state,
rapid response, and a high sensitivity and selectivity, are
3
3
3 7
(
1), exhibited strong red-light emission at ambient temperature.
2
4
Importantly, this emission is indeed selectively quenched by
electron-rich organic amines with high sensitivity.
limited.
Fluorescent coordination polymer (CP) sensors have had a
profound influence on modern sensing systems because of their
25−29
extremely high sensitivity and ease of signal transduction.
Received: July 19, 2015
For example, fluorescent quenching of CPs via an electron-
transfer “turn-off” mechanism showed very high sensitivities to
Revised: August 22, 2015
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.cgd.5b01026
Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design
Article
Scheme 1. Synthesis of Ligand H bcbp·2Cl
2
EXPERIMENTAL SECTION
assumed to contain 10 MeOH molecules (calcd: C, 40.47; H, 3.62; N,
■
−1
7
.46%). IR data (KBr, cm ): 3419 (m), 3113 (w), 3049 (w), 1632
Materials and Measurements. All chemicals and reagents were
used as received unless otherwise stated. NMR spectra were recorded
with a Bruker Avance 400 MHz NMR spectrometer. Chemical shifts
are given in parts per million (ppm) and referred to TMS as an
(
(
m), 1611 (s), 1569 (m), 1405 (s), 1300 (s), 1221 (m), 1030 (m), 853
m), 782 (s), 703 (m), 650 (m), 507 (w), 470 (m).
Fluorescence Experiments. In a 1 cm quartz cuvette, 2 mg of
compound 1 was added to 3 mL of MeOH and sonicated for 1 h; then,
the fluorescence response upon excitation at 395 nm was measured in
situ after incremental addition of freshly prepared analyte solutions in
the range 550−750 nm. To maintain homogeneity, the fluorescence
measurement was performed while the analyte was added and stirred
after another 1 min.
1
internal standard. H coupling constants J are given in hertz (Hz).
Fourier transform infrared (FT-IR) spectra were recorded from KBr
discs on a Perkin-Elmer Spectrum 2000 FT-IR spectrometer. Powder
X-ray diffraction (PXRD) intensities were recorded on a Rigaku
MiniFlex-II X-ray diffractometer, and high-resolution mass spectra
were recorded on a Thermo Fisher Scientific Exactive Plus system.
TGA measurements were performed on a TG-209 system with a
X-ray Diffraction Analysis. A suitable single crystal of complex 1
was mounted on a glass fiber for X-ray measurements. Diffraction data
was collected on a Rigaku-AFC7 equipped with a Rigaku Saturn CCD
area-detector system. The measurement was made using graphite
monochromatic Mo Kα radiation (λ= 0.71073 Å) at 293 K. The frame
data were integrated, and absorption correction was calculated the
Rigaku CrystalClear program package. All calculations were performed
heating rate of 10 °C/min under a N atmosphere. UV−vis diffuse
2
reflectance spectra were recorded at room temperature on a Varian
Cary 500 UV−vis spectrophotometer equipped with an integrating
sphere using BaSO as a white standard in the range 200−800 nm.
4
Luminescence measurements were made with an Edinburgh Instru-
ment FLS 980 luminescence spectrometer on powdered crystal
material of the compound. Elemental analyses of C, H, and N were
carried out on a Vario EL III elemental analyzer. The electron spin
resonance (ESR) measurements were obtained on a Bruker A300
instrument operating in the X-band at room temperature. The gas
sorption studies were performed on Micromeritics ASAP 2020
adsorption equipment.
49
with the SHELXTL-97 program package, and structures were solved
2
by direct methods and refined by full-matrix least-squares against F .
All non-hydrogen atoms were refined anisotropically, and hydrogen
atoms of the organic ligands were generated theoretically onto the
specific atoms. The diffraction data were treated by the SQUEEZE
method, as implemented in PLATON, to remove diffuse electron
50
density associated with these badly disordered solvent molecules.
Synthesis. Preparation of 1,1′-Bis(4-carboxyphenyl)-(4,4′-bipyr-
The crystal data and structure refinements are summarized in Table 1.
Crystallographic data have been deposited with the Cambridge
Crystallographic Data Center as supplementary publication number
CCDC 1412259. These data can be obtained free of charge from The
idinium) Dichloride (H bcbp·2Cl). Ligand H bcbp·2Cl was prepared
2
2
48
in two steps using modified literature procedures. As shown in
Scheme 1, a solution of 4,4′-bipyridine (3.6 g, 23 mmol) and 2,4-
dinitrochlorobenzene (16.5 g, 81 mmol) in acetonitrile (70 mL) was
heated under reflux for 72 h. The hot reaction mixture was filtered, and
the filtered cake was refluxed with ethanol (300 mL). After the solid
was dried under vacuum, 1,1′-bis(2,4-dinitrophenyl)-(4,4′-bipyridi-
Table 1. Crystal Data and Structure Refinement Parameters
for 1
1
nium) dichloride was collected as a white solid (6.0 g, 50%). H NMR
complex
1
(
400 MHz, CD OD): 9.68 (d, J = 6.4 Hz, 2H), 9.34 (d, J = 2.4 Hz,
3
1
8
H), 9.12 (d, J = 6.4 Hz, 2H), 8.97 (dd, J = 8.4 Hz, J = 2.4 Hz, 2H),
.43 (d, J = 8.8 Hz, 1H).
A suspension of 1,1′-bis(2,4-dinitrophenyl)-(4,4′-bipyridinium)
empirical formula
formula weight
crystal system
space group
a (Å)
Eu C H N O
3 72 48 13 35
1
2
2111.11
monoclinic
C2/c
dichloride (2.80 g, 5 mmol) and 4-aminobenzoic acid (1.50 g, 11
mmol) in anhydrous ethanol (60 mL) was heated under reflux for 84
h. After being cooling to room temperature, the obtained solid was
filtered and recrystallized from H O. The collected brown crystals
were washed with ice water and dried, affording H bcbp·2Cl (1.97 g,
8
23.068(5)
19.934(4)
22.714(5)
115.85(3)
9400(3)
4
b (Å)
2
c (Å)
2
−1
β (deg)
V (Å3)
5%). IR data (KBr, cm ): 3345 (m), 3213 (m), 3128 (m), 3059
(
(
m), 1643 (m), 1611 (s), 1533 (s), 1374 (s), 1215 (m), 1167 (m), 851
m), 776 (s); H NMR (400 MHz, CD OD): 9.65 (d, 2H, J = 4.0 Hz),
1
Z
3
8
.96 (d, 2H, J = 4.0 Hz), 8.38 (d, 2H, J = 8.0 Hz), 7.99 (d, 2H, J = 8.0
T (K)
173(2)
+
ρcalc (g/cm3)
1.492
Hz); HRMS (ESI) calcd for C H ClN O [M − Cl], 431.0950;
found, 431.0803.
Preparation of {Eu (bcbp) (NO ) (OH) } (1). A mixture of
24
18
2
4
μ (Mo Kα) (mm−1
)
2.062
3
3
3 7
2 n
F(000)
4160
Eu(NO ) ·6H O (0.1 mmol, 44.6 mg), H bcbp·2Cl (0.05 mmol, 24
3
3
2
2
collected reflections
unique reflections
no. of observations
goodness-of-fit on F
39 322
mg), and methanol (5 mL) was stirred for 30 min in air and then
transferred to and sealed in a 23 mL Tefon-lined autoclave, which was
heated in an oven at 100 °C for 72 h and cooled to room temperature
at a rate of 10 °C/h to form yellow block-shaped crystals, which were
collected by filtration, washed with MeOH, and dried in air (ca. 63%
yield based on ligand). Elemental analyses of C, H, and N are 40.45,
10 777 (0.0706)
9018
2
1.112
a
b
R1 , wR2 (I > 2σ(I))
0.0706, 0.1676
0.0873, 0.1776
a
b
R , wR (all data)
1 2
3
.53, and 7.54%, respectively. On the basis of the results of TGA and
a
R = ∑∥F | − |F ∥/∑|F |. wR = [∑w(F − F ) /∑w(F )]1/2.
b
2
2
2
2
PLATON from crystallographic data, each smallest structural unit is
1
o
c
o
2
o
c
o
B
DOI: 10.1021/acs.cgd.5b01026
Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design
Article
Figure 1. (a) View of the coordination environment of the Eu(III) ions in 1; symmetry codes: (i) −x, y, 0.5 − z. (b) View of the framework of 1. (c)
Schematic representation of six-connected topology, with the trinuclear europium cluster as the six-connected node.
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
Three Eu(III) ions in Eu −SBU are triply bridged by six
3
carboxylate groups from six bcbp ligands with an Eu···Eu
distance of 5.217(2) Å. Other coordination sites of Eu(III) ions
are completed by O atoms from the nitrate ions or hydroxyl
ions. All Eu−O bond distances fall in the normal range of
RESULTS AND DISCUSSION
■
Crystal Structure of 1. Single-crystal X-ray analysis reveals
that 1 crystallizes in space group C2/c. There are one and a half
2.374(5)−2.850(5) Å. Eu −SBU further connects to six
3
neighboring ones through six bcbp ligands, forming a 3D
framework. From the viewpoints of topology, 1 features a
1
2 3
̈
uninodal six-connected network with a Schlafli symbol of 4 .6
(
Figure 1c), where the Eu −SBU units are considered to be six-
3
connected nodes and the bcbp ligands act as linkers. Such a
network had been identified as pcu-net according to the RCSR
51
symbol. Significantly, some methanol molecules can be
detected, but most of them are disordered and could not be
well-located during the refining of the crystal structure, which
is, indeed, supported by thermogravimetric analysis (Figure S6,
Supporting Information). Accordingly, the contribution of all of
the methanol molecules is subtracted from the data using
SQUEEZE during the refinement. After subtracting the
methanol contribution, PLATON calculations indicate that
3
the effective pore volume is 2310.7 Å per unit cell, which is
2
4.6% of the crystal volume. However, the small diameter of
this pore implies that it is inaccessible for bulky guest
molecules.
Figure 2. Photoluminescence spectra (λ = 395 nm) of 1 in the solid
state.
ex
Photoluminescence. The photoluminescent properties of
1
(
in the solid state at room temperature were investigated
Figure 2). As expected, 1 shows characteristic emission bands
of the Eu(III) ion centered at 594, 616, 651, and 694 nm, which
Eu(III) ions, one and a half bcbp ligands, three and a half
nitrate ions, and one hydroxyl ion in the asymmetric unit. As
shown in Figure 1a, all of the deprotonated bcbp ligands exhibit
5
7
can be attributed to the f−f D → F (j = 1−4) transitions,
0
j
respectively. The spectrum is dominated by the intense band of
1
1
1
1
5
7
μ -η -η -η -η coordination modes. One prominent structural
the D → F electron dipole transition, which is the so-called
4
0 2
feature of 1 is the presence of an unusual trinuclear Eu(III) unit
hypersensitive transition and is responsible for the brilliant red
emission of the complex.
The photoluminescence properties of 1 were also inves-
tigated after dispersing it in different solvents. Excitingly, the
(
Eu (CO ) (NO ) (OH), Eu −SBU). Two Eu(III) ions at the
3
2 6
3 7
3
ends of Eu −SBU have a common ten-coordinate geometry,
3
and the central Eu(III) ion is in eight-coordinate geometry.
C
DOI: 10.1021/acs.cgd.5b01026
Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design
Article
Figure 5. Percentage of luminescence quenching obtained in solutions
5
7
of 0.03 mM organic amines in methanol. The D → F transition
0
2
intensities (616 nm) were selected.
Figure 3. (a) Photoluminescence spectra of 1 dispersed in various
5
7
pure solvents. (b) D → F transition intensities (616 nm) of 1 in
0
2
various pure solvents.
Figure 6. Photoluminescence spectra of 1 dispersed in MeOH with
incremental addition of ethylamine. Inset: Photograph showing the
changes in fluorescence under UV light (365 nm) upon incremental
addition of ethylamine (left: 1 in methanol; right: 1 in methanol
containing ethylamine).
3
) when a finely ground sample of 1 (2 mg) was suspended in 3
mL of various solvents (CH Cl , MeCN, H O, THF, DMF,
2
2
2
EtOH, and MeOH) and sonicated for 1 h. The PXRD patterns
of the samples after immersion in various organic solvents are
consistent with that of the original sample (Figure S7,
Supporting Information), which suggests that the frameworks
of 1 is stable in organic solvents. In addition, due to 1 having
the strongest emission in methanol, we selected methanol as
the solvent in the following measurements.
Sensing of Organic Amines in Solution. Because of the
possible electron transfer between the bipyridinium moieties of
and aromatic molecules, we first investigated its luminescent
responses to aromatic molecules, including benzene (Ph),
Figure 4. Photoluminescence spectra of 1 obtained after introducing
different guest molecules into the MeOH emulsion of 1. Inset:
Photograph of samples immersed in solutions containing different
guest molecules.
1
toluene (PhCH ), chlorobenzene (PhCl), bromobenzene
3
(
PhBr), phenol (PhOH), 4-nitrophenol, nitrobenzene
photoluminescence intensities of 1 were observed to be
(PhNO ), and aniline (PhNH ). After the samples had been
2
2
independent of the solvent, exhibiting limited changes (Figure
suspended in MeOH solution (0.1 M) containing various
D
DOI: 10.1021/acs.cgd.5b01026
Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design
Article
Figure 7. (a) Photograph showing the color changes of 1 treated in different organic amines; (b) Solid state UV−vis spectra of amine@1.
propanediamine, diethylamine, and cyclohexylamine, were
selected as the investigated reagents. The results show that all
organic amines can weaken the fluorescence intensities of 1
gradually by increasing the concentration of organic amines
(
Figures S12 and S13, Supporting Information), but the
percent of quenching that results differs (Figure 5). At a
concentration of 0.3 mM, the aniline, diethylamine, and
cyclohexylamine solutions caused relatively little change in
the fluorescence intensity. However, the addition of ethylamine
and 1,3-propanediamine significantly quenched the fluores-
cence intensity. The fluorescence quenching efficiency was
5
2
calculated using the Stern−Volmer (SV) equation, (I /I) =
0
K [A] + 1, where I is the initial fluorescence intensity before
sv
0
the addition of analyte, I is the fluorescence intensity after
adding the analyte, [A] is the molar concentration of analyte,
and K is the quenching coefficient. According to the equation,
sv
the quenching efficiency for the organic amines in MeOH was
found to follow the order ethylamine > 1,3-propanediamine >
diethylamine > cyclohexylamine > aniline (Figure S8,
Supporting Information), which is consistent with the order
of their sizes and can be attributed to their diffusion abilities
toward the pores of the framework. The small size of the
ethylamine molecule leads to it having easy access to the pore
and causes a more efficient electron transfer with the
pyridinium moieties within the framework.
In addition, the detection sensitivities toward amine
compounds, especially toward ethylamine with its small size,
are very important. Hence, the dependence of the degree of
luminescence quenching on the concentration has also been
examined, which reveals that 1 is indeed very sensitive to
ethylamine even at very low concentrations (Figures 6 and S9).
At around 500 ppm, the luminescence intensity is nearly
completely quenched with a yield of 94%. This result
demonstrates that 1 has good sensitivity for detecting small
Figure 8. Recyclability of 1 dispersed in MeOH in the presence of 500
ppm ethylamine.
aromatic molecules, their photoluminescence spectra were
measured. As shown in Figure 4, except for PhNH , none of
2
these aromatic molecules shows any influence on the
luminescence intensity of 1, indicating that 1 can be considered
to be a probe to detect PhNH . The quenching mechanism is
2
likely derived from electron transfer from the electron-rich
PhNH to the electron-deficient bipyridinium moieties (Figure
2
S22, Supporting Information). More importantly, the PhNH2-
treated sample undergoes a color change from yellow to brown,
whereas the remaining samples remain yellow, which suggests
that 1 can also serve as a sensor for PhNH because of this
2
visible color change.
In order to further explore the sensing potentials of 1 toward
other organic amines, four analogues, e.g., ethylamine, 1,3-
E
DOI: 10.1021/acs.cgd.5b01026
Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design
Article
FTIR, 1H NMR, HRMS, and photoluminescence
spectra; TGA and powder XRD data; and other
photographs (PDF).
amounts of ethylamine in a MeOH solution, which is superior
to that of previously reported sensors for detecting ethyl-
amine. Meanwhile, PXRD patterns of 1 after being immersed
in organic amine solutions for 12 h confirmed that the original
framework structure is retained (Figure S11, Supporting
Information).
5
3
X-ray crystallographic data (CIF).
AUTHOR INFORMATION
Corresponding Authors
(M.-J.L.) E-mail: meijin_lin@fzu.edu.cn.
(C.-C.H.) E-mail: cchuang@fzu.edu.cn.
■
UV−vis Spectra. As mentioned above, 1 treated with
PhNH undergoes a color change from yellow to brown.
2
*
*
However, 1 treated with 0.1 M of different amines in MeOH
exhibits different colors (the treated samples are denoted
amine@1, Figure 7a), and this color change is extremely rapid
and very prominent and can be easily detected by the naked
eye. The solid-state UV−vis spectra of 1 showed a strong
absorption band at about 380 nm (Figure 7b), which
corresponds to the n−p* and π−π* transitions of the aromatic
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We thank Prof. Jun-Dong Wang and Prof. Xin Fang for useful
discussions. This work was supported by the National Natural
Science Foundation of China (21202020 and 21273037), the
Doctoral Fund of the Ministry of Education of China
5
4−56
carboxylate ligands.
(
The UV−vis spectra of amine@1
Figure 7b) displayed a gradual broadening of the absorption
band in the region 400−800 nm after exposure to the different
organic amines, which may arise from an intermolecular
electron-transfer transition from the organic amines to the
bcbp linker. These results again supported the ability of 1 to
sense organic amines through distinct color changes, a
characteristic that has been rarely observed in previous reports.
Sensing of Organic Amine Vapors. The significant ability
of 1 to sense organic amines in a MeOH suspension prompted
us to study its capabilities to detect vapor-phase organic amines
at room temperature. In a typical experiment, vacuum-dried 1
was exposed to the above organic amine vapors for a period of
time at room temperature, and we then measured their
photoluminescence properties. Due to larger vapor pressures of
ethylamine, 1,3-propanediamine, and diethylamine at room
temperature, the fluorescence of 1 was completely quenched
within a few minutes (Figures S14−S16). However, the
fluorescence quenching abilities of aniline and cyclohexylamine
toward 1 are rather low. Only when 1 was exposed to aniline or
cyclohexylamine vapors for 1 day at room temperature was its
emission remarkably quenched (Figures S17 and S18). These
results indicate that 1 is also able to sense vapors for some
organic amines. Importantly, 1 can be regenerated by
centrifuging the samples, washing with MeOH several times,
and further heating at 80 °C for 2 h. Remarkably, limited
quenching efficiency losses occur even after five cycles, which
suggests that 1 is highly recyclable and supports its use for
detection applications (Figure 8).
(
20123514120002), the Natural Science Foundation of Fujian
Province (2014J01040 and 2014J01045), and the Science &
Technical Development Foundation of Fuzhou University
(
2012-XQ-10 and 2013-XQ-14).
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CONCLUSIONS
(
■
2
In summary, a porous and luminescent 3D lanthanide
coordination polymer containing a rigid pyridinium moiety
and two electrical charges at its conjugated tectons was
synthesized, and it exhibited selective colorimetric and
fluorescent sensing toward trace amounts of organic amine
solutions and vapors. More importantly, due to the small pores
of the coordination polymer, such sensing is size-dependent.
Further studies of analogous coordination polymers in various
applications are under way.
(
(
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