A Hexanuclear Cadmium Metal–Organic Framework Exhibiting Dual Mechanisms to Trigger a Fluorescence-Quenching Response toward Iron(III) Ions

Article abstract of DOI:10.1002/ejic.201701290

A hexanuclear Cd^II metal–organic framework (1) based on 4-(1H-pyrazole-4-carboxamido)benzoic acid (H₂L) and featuring a three-dimensional microporous framework was synthesized. Notably, 1 shows a unique fluorescence-quenching response toward Fe³⁺ ions with high selectivity and sensitivity (Stern–Volmer constant K_SV = 2.07 × 10⁴ m^–1). The response is attributable to the coaction of absorption competition and energy-transfer (ET) mechanism. Furthermore, spectral analysis indicates that the energy-transfer mechanism makes the dominant contribution to the fluorescence quenching of 1.

Full text of DOI:10.1002/ejic.201701290

A Journal of
Accepted Article
Title: A Novel Hexanuclear Cd-MOF Exhibiting Dual Mechanisms-
triggering Fluorescence Quenching Response toward Fe3+ Ions
in DMF
Authors: Ying-Hui Zhang, Long-Sheng Li, Xi Wang, Yan-Yuan Jia, Shi-
Xian Xu, and Mei-Hui Yu
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Eur. J. Inorg. Chem. 10.1002/ejic.201701290
Link to VoR: http://dx.doi.org/10.1002/ejic.201701290

European Journal of Inorganic Chemistry
10.1002/ejic.201701290
FULL PAPER
A Novel Hexanuclear Cd-MOF Exhibiting Dual
Mechanisms-triggering Fluorescence Quenching Response
3+
toward Fe Ions in DMF
[
a]
[b]
[a]
[b]
[b]
[b]
Long-Sheng Li, Xi Wang, Yan-Yuan Jia, Shi-Xian Xu, Mei-Hui Yu, Ying-Hui Zhang,*
3
+
Abstract: A novel hexanuclear Cd(II) metal-organic framework (1)
based on 4-(1H-Pyrazole-4-carboxamido) benzonic acid (H L) has
been synthesized, featuring three dimensional microporous
framework. Notably, 1 shows a unique fluorescence quenching
constructed some MOFs for selective detection of Fe based on
10e,10f
2
ET mechanism or absorption competition mechanism.
a
However the MOFs exhibit fluorescent response toward iron ion
triggered by multi-mechanism were less reported, and
particularly, the strategy to quantitatively distinguish the
contribution of different factors co-acting is scarcely investigated.
3+
response toward Fe
with high selectivity and sensitivity
4
-1
(Stern-Volmer constant KSV = 2.07 × 10 M ), attributable to the
coaction of absorption competition and energy transfer (ET)
mechanism. Further spectral analysis indicates that energy transfer
mechanism contribute dominantly to the fluorescent quenching of 1.
In
{[Cd
this
(L )
work,
we
reported Cd-MOF,
a
namely
2
-
3
3
(H
2
O)]·(DMF)·(H
2
O)} (1) (H L: 4-(1H-Pyrazole-4-
n
2
carboxamido) benzonic acid ligand, see Scheme 1), featuring
highly selective and sensitive fluorescent quenching response
toward Fe
3
+
in DMF solution (Stern-Volmer constant KSV = 2.07
4
-1
×
10 M ), which was ascribed to the coaction of absorption
Introduction
competition and ET mechanism based on spectral analyses.
Furthermore, we develop a convenient and reliable method to
assess the contribution from these two mechanisms.
Metal Organic Frameworks (MOFs) are constructed through
1
ordered assembly of organic ligands and metal ions or clusters.
As a new class of inorganic-organic hybrid crystalline materials
with tailorable topologies, MOFs have promising applications in
2
3
many fields, including gas storage and separation, catalysis,
4
5
6
drug delivery, proton conduction, chemical sensing, and so on.
Recently, increasing attention has been paid on the fluorescent
response behaviors of MOFs toward guest species such as
2
Scheme 1 4-(1H-Pyrazole-4-carboxamido) benzonic acid (H L)
7
,8,9
organic molecules and metal ions,
which favors the
development of new kinds of fluorescent materials as well as Results and Discussion
new spectral analysis method. In general, the fluorescnet
response of MOFs may be triggered by many factors, including
the collapse of the framework, ion-exchange process, absorption
Crystal Structure of 1
Single-crystal X-ray diffraction analysis reveals that compound
1 crystallizes in the triclinic system with P-1 space group. The
asymmetric unit consists of three crystallographically
independent Cd (II) ions, three crystallographically independent
1
0
competition and energy transfer. It’s reasonable to hypothesis
that the coaction of several factors would results in much
sensitive fluorescence response, which, however, are confused
due to difficult quantitative identification of the contribution from
different effects.
2
-
L
ligands, one coordinated water molecules, one lattice water
and one lattice DMF guest. As illustrated in Fig. S1, Cd1 is
five-coordinated by three N donors from three pyrazole rings of
As an essential transition metal involved in some biological
1
1,12
2-
2-
processes,
It has been clearly demonstrated that the
different L and two O atoms from other two L , forming a distort
coordination configuration between tetragonal pyramid and
deficiency or overloading of iron will bring about various
biological disorders, including hepatic cirrhosis, endotoxemia,
14
trigonal bipyramid with a τ value of 0.58; Cd2 ion is coordinated
by four chelating O atoms from two carboxylate groups of two L
ligands, one water oxygen atom and one pyrazole N atoms,
leading to a distorted octahedral geometry; Cd3 centers inside a
distorted tetragonal pyramid geometry (τ = 0.07) surrounded by
1
3
2-
hereditary hemochromatosis, and so on. Therefore, various
3
+
MOFs featuring fluorescent response toward Fe
were
developed and investigated in their response mechanis. Yan and
3
+
14
coworkers reported an excellent fluorescent probe for Fe based
1
1b
on cation exchange mechanism.
Our group has also
two chelating carboxylate oxygen atoms, two pyrazole N atoms
2
-
of different L ligands, and one water molecule. These three
kinds of Cd ions are bridged by carboxylate and pyrazole ring to
form a linear trinuclear cluster. Meanwhile, two neighboring
trinuclear clusters are double interlinked by two pyrazole ring to
[
[
a]
b]
Department of Chemistry, Nankai University, Tianjin 300071, China
E-mail: zhangyhi@nankai.edu.cn.
School of Materials Science and Engineering, National Institute
for Advanced Materials, Tianjin Key Laboratory of Metal and
Molecule-Based Material Chemistry, Nankai University, Tianjin
2
-
generate a hexanuclear Cd (II) cluster. For three kinds of L ,
there are two kinds of coordination modes observed for
3
00350, China.
carboxylate group, one is 
 -O :O :O mode (L2 and L3), while pyrazole group adopts only
3 1 1 2
2
-O
1 2
:O mode (L1) and the other is
Supporting information for this article is given via a link at the end of
the document.
′
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European Journal of Inorganic Chemistry
10.1002/ejic.201701290
FULL PAPER
one 
2
-N
1
:N
2
mode. In addition, a hydrogen bonding interaction
Fluorescence properties
2
The emission spectra of 1 and free ligand H L were both
was observed between L2 and one lattice DMF molecule (Fig.
S2).
measured (Fig. S6 and S7). As shown in Fig. S8, the
fluorescence spectrum of 1 in DMF has the strongest emission at
347 nm (λex=310 nm), which is somewhat close to the 390 nm
emission of free ligand in DMF solution (λex=337 nm), and thus is
supposed to be ligand-dominated. Similar case is also observed
for the solid sample (Fig. S7). The blue shifted emission
In the ac plane, adjacent hexanuclear Cd (II) clusters are
linked by L3 ligands through Cd1 and Cd2 atoms, to form one
dimensional (1D) chain (Fig. 1a). Each chain interacts with two
neighboring ones through hydrogen bonding between the
acrylamide group of L3 and the carboxylate group of L1, leading
to a two-dimensional (2D) sheet (Fig. 1b). Furthermore, the 2D
layers are pillared by L2, giving a three dimensional (3D)
non-interpenetrated framework. Meanwhile, L1 acts as lateral
pillar to strengthen the 3D framework (Fig. 1c). Careful inspection
of the 3D framework reveals a channel with a section area of 7.5
Å ×9.0 Å (Fig. S3), which results in a total accessible volume of
2
observed for 1 relative to H L can be rationally interpreted in
terms of coordination interaction.
49.5% for 1 by using PLATON software after removing lattice
DMF molecules. To better understand the structure of 1, the
topological structure was analyzed by simplifying the ligands as
three-connected nodes (L1) and four-connected nodes (L2 and
L3), and Cd(II) ions as 3-connected nodes (Cd2 and Cd3) and
5
-connected nodes (Cd1), which gives a (3,3,,4,5)-connected
2
2
4
2
8
4-nodal net for 1 with a Schläfli symbol of {4·8 }
2
{4 ·8 }
2
{4 .8 }
2
{
8 .12} (Fig. 1d).
Fig 2 The maximum emission intensities (at 347 nm) comparison among 1
Powder X-ray Diffraction Analyses (PXRD) and
Thermogravimetric Analyses (TGA)
−4
suspension (in DMF, 5×10 M) and that upon the addition of various metal ions,
λ
ex = 310 nm.
Before the measurement of fluorescence properties, the phase
purity and stability of compound 1 were investigated by PXRD
and TGA, respectively. The experimental diffraction pattern of
the as-synthesized 1 matches very well with the simulated one
based on single crystal data (Fig. S4), testifying the high phase
purity of the sample. Thermogravimetric analyses were
performed at air atmosphere after immersing 1 in ethanol for 2
days. As shown in Fig. S5, the mass loss (~20%) occurring
before 150 °C corresponds to the escape of free solvent
molecules as well as coordinated water, and no further mass loss
was observed before the decomposition of 1 starting from 350 °C,
manifesting the good thermal stability of 1.
Fluorescence response toward metal ions
To explore the fluorescent respond of 1 toward various metal
ions,
4 mg 1 was ground and dispersed in 3.8 mL
dimethylformamide (DMF) to form suspension system after
ultrasonication for 30 min. And then to the suspension system
was added 0.2 mL DMF solution of M(NO ) (1×10 mol/L, M =
3 x
−2
3+
+
+
+
+
2+
2+
2+
2+
+
3+
2+
2+
Al , Li , Na , K , Cs , Mg Ca , Sr , Ba , Ag , Cr , Co , Ni ,
2+
2+
2+
3+
Zn , Cd , Cu , or Fe ). The emission spectra of 1 suspension
upon addition of different metal ions were collected in Fig. S8,
and the emission intensities at 347 nm were compared in Fig 2. It
3+
is clearly revealed that Fe drastically quenches the emission
intensity of 1, while other metal ions exert relatively negligible
influence. This suggests the selective fluorescent response of 1
3
+
toward Fe .
In addition, the interference of other metal ions on the
3
+
fluorescence response of 1 toward Fe was also explored. In a
3
+
-2
typical procedure, 0.2 mL DMF solution of Fe (1×10 M) and
-2
0
.2 mL DMF solutions of another metal ions (1×10 M) were
added, sequentially and dropwise, into a 3.6 mL 1 suspension.
The maximum emission intensity were recorded and compared
with that of 1 as shown in Fig 3, in which the great quenching
3
+
effects of Fe on the fluorescence emission of 1 suspension was
protruded even in the presence of other metal ions.
Above spectral analyses testified the selective fluorescence
3
+
response of 1 toward Fe , which encouraged us to further
evaluate the response sensitivity by spectral titration of 1
suspension with Fe . As shown in Fig. S9, the emission intensity
Fig. 1 Single-crystal structure of 1: (a) 1D chain formed by connecting
2-
hexanuclear Cd(II) cluster with L in ac plane (color scheme: Cd, cyan; N, blue;
O, red; C, 1/4 gray. H atoms are omitted for clarity); (b) 2D layer in space-filling
mode formed by hydrogen bonding interaction between neighboring 1D chains;
3+
of 1 suspension decreases gradually along with increasing
3+
-7
addition of Fe with a total concentration growing from 1×10 to
(c) The 3D framework of 1. (d) The topological net of 1 with a Schäfli symbol of
-4
2
.5×10 M. The Stern-Volmer equation, I
to evaluate the quenching effect, where I
0
/I=1+ Ksv [M], was used
and I stand for the
2
2
4
2
8
2
{
2 2
4·8 } {4 ·8 } {4 .8 } {8 .12}.
0
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European Journal of Inorganic Chemistry
10.1002/ejic.201701290
FULL PAPER
fluorescence intensity before and after the addition of metal ions,
respectively, Ksv is the Stern-Volmer constant, and [M] is the
framework, cation exchange, absorption competition or energy
transfer. In the following section, we tried to clarify the
mechanism of the selective fluorescence response of 1 toward
Fe .
The influence of possible decomposition of framework can
firstly be excluded as supposed by the similar PXRD pattern of
the recovered 1 to that of as-synthesized one illustrated in Fig.
S10. Moreover, inductive coupled plasma spectroscopy (ICP)
experiment of recovered 1 reveals much higher content of Cd
element relative to Fe (Table S4), suggesting negligible degree of
cation exchange. Moreover, the good recyclability also strongly
suggests the fluorescence quenching should be ascribed to other
factors.
3
+
concentration of Fe . According to spectral titration data, the
linear relationship between I /I and [M] was simulated in Fig 4,
3
+
0
4
-1
with a Ksv of about 2.07 × 10 M . This Ksv value is comparable to
3
+ 15
that of some organic sensors for Fe , which manifests the high
3
+
response sensitivity of 1 toward Fe .
3+
Fig 3 The quenching effects of Fe on the emission intensity of 1 suspension
Considering the spectral properties of 1, the action of
absorption competition or energy transfer mechanism is of great
possibility. To verify this assumption, the UV-Vis absorption
spectra of metal ions solution were measured and compared with
the fluorescence spectra of 1 suspension. As shown in Fig. 5,
3
+
Fe exhibits strong absorption in a wide range from 285 to 500
nm, originating from the d-d electron transition. This overlaps
greatly both with the excitation (285-325 nm) and emission
(
340-500 nm) regions of 1, and consequently may result in great
in the presence of other metal ions, λex = 310
quenching of the fluorescent emission of 1. On contrary, no
obvious absorption was observed in these two regions for other
metal ions studied here, which is consistent with the little or
negligible fluorescence response of 1 toward other metal cations.
Based on above analyses, it is deduced convincingly that the
coaction of absorption competition and energy transfer may
account for the highly sensitive fluorescence response of 1
The recyclability of fluorescence materials is crucial for their
practical application and thus was also investigated for 1 here.
The recovery of 1 after fluorescence response is carried out by
centrifuging the suspension and then washing the collected
precipitate with DMF for three times. Similar PXRD pattern
verifies the same crystal structure of the recovered 1 with that of
as-synthesized one (Fig. S10). After repeating the
response/recovery procedure for three times, 1 still exhibits
3+
towards Fe .
3
+
highly sensitive response toward Fe (Fig. S11), which unveils
3
+
the good repeatability of 1 in fluorescence response toward Fe .
-
4
Fig 5 The absorption spectra of the DMF solutions of 5×10 M M(NO
3
)
x
(solid
3+
+
+
+
+
2+
2+
2+
+
3+
2+
2+
2+
2+
line, M = Al , Li , Na , K , Cs , Ca , Sr , Ba , Ag , Cr , Co , Ni , Zn , Cd
,
2+
2+
3+
Mg , Cu , Fe ) and the excitation (dashed line) and emission profile (dotted
line) of 1 dispersed in DMF (4 mg in 4 mL).
It’s necessary to evaluate the contribution from these two
mechanisms to the fluorescence quenching, respectively.
Fig 4 The Stern-Volmer plot predicted based on fluorescence spectral titration
3+
0
of 1 suspension with Fe , where I and I stand for the emission intensity of 1
Accordingly,
a
convenient and reliable experiment was
3+
suspension before and after the addition of Fe ion, respectively.
performed to assess the contribution only from absorption
3
+
competition as shown in Figure S12, where the Fe ion was
increasingly added into 4 mL DMF solution in the cuvette placed
in the incident path before sample cell. This setting would
Fluorescence response mechanism analyses
In general, fluorescence emission quenching of MOFs may be
triggered by many factors, including the decomposition of the
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European Journal of Inorganic Chemistry
10.1002/ejic.201701290
FULL PAPER
exclude the possible contribution from energy transfer to the
fluorescence quenching and thus give a convincible assessment
of the role of absorption competition. The simulation based on
this experimental data with Stern-Volmer equation gives a slope
of ca. 4800 (abbreviated as K′SV). By comparing K′SV and Ksv, it is
reliably concluded that the contribution from energy transfer
mechanism is dominant.
NMR (300 MHZ, DMSO-d
6
, δppm): 10.5 (s, 1H, CONH), 8.23 (s, 2H, CH
(pyrazole)), 7.91, 7.89, 7.84 and 7.81 (q, 4H, ArH) (see Fig. S13).
2-
3 3 2 2 n
Synthesis of {[Cd (L ) (H O)]·(DMF)·(H O)} (1).
To a mixture of 3 ml N,N-dimethylformamide (DMF) and 0.5 ml ethanol
(
(
C
2
H
5
OH) in 20 ml Teflon-lined stainless steel autoclave, CdCl2 ·2.5H
2
O
56 mg, 0.2 mmol) and H L (23.1 mg, 0.1 mmol) were dissolved. The
2
autoclave was heated at 150 °C for 2 days under autogenous pressure
and then cooled slowly to room temperature at a rate of 5°C /h under
ambient conditions. The resulting pale yellow crystals were collected and
Conclusions
washed with DMF. The product yield was 60% estimated based on H
Elemental analysis calc. for (C36 ): C, 38.16; H, 2.82; N,
2.36; found C ， 38.32; H, 3.15; N, 13.14. FT-IR (KBr pellets,
2
L.
32 10 3
H N O12Cd
In summary, a novel hexanuclear Cd-MOF (1) was constructed
with 4-(1H-Pyrazole-4-carboxamido) benzonic acid ligand. The
1
-
1
cm ) :1659.14(s); 1600.83(s); 1543.35(s); 1504.05(s); 1389.40(s);
311.81(m); 1175.89(m); 783.71(m); 660.17(m) (Fig. S14).
good selectivity, high sensitivity (Stern-Volmer constant KSV
=
1
4
-1
2
.07 × 10 M ) and repeatability of 1 in fluorescence response
3
+
toward Fe , based on absorption and fluorescence spectral
analyses, were ascribed to the coaction of absorption
competition and ET mechanism, Further spectral analysis
indicates that ET contributes mainly to the fluorescence
quenching of 1.
Determination of Crystal Structure
The X-ray diffraction data was collected on
a Rigaku SCX-mini
diffractometer at 293 K with a Mo-Kα radiation (λ= 0.71073 Å) at scan
mode. The structure was solved by direct methods and all non-hydrogen
atoms were located from the trial structures and then refined
2
anisotropically on F refined by full-matrix least-squares procedures using
SHELXTL. All H atoms were refined isotropically with the isotropic
vibration parameters related to the non-hydrogen atoms to which they are
bonded. The guest molecules in 1 are disordered and could not be
Experimental Section
Materials and methods
17
modeled properly, and so were removed by SQUEEZE in PLATON (the
results were appended in the CIF files). Detailed crystallographic data are
summarized in Table S1 and some selected bond lengths and angles are
listed in Tables S2 and S3. The crystallographic data of 1 has been
deposited in CCDC (1549978) and can be obtained free of charge from
All reagents and solvents used for synthesis were AR grade and used as
received without further purification. 4-(1H-Pyrazole-4-carboxamido) benzonic
16 1
2
acid (H L) was synthesized according to the method reported earlier.
H
NMR spectra were recorded on a Varian Mercury Vx-300 spectrometer.
Powder X-ray diffraction (PXRD) data were collected over a 2θ range
from 3° to 50° on a Rigaku D/Max-2500 diffractometer using Cu radiation
and a graphite monochromator at room temperature. Thermogravimetric
the
Cambridge
Crystallographic
Data
Centre
via
www.ccdc.cam.ac.uk/data_request/cif.
(
TG) analyses were carried out on a Rigaku PTC-10A TG-DTA analyzer
−
1
Acknowledgements
with a heating rate of 10 °C min from ambient temperature to 800°C in
air using an Al crucible as reference. IR spectra were recorded on a
TENSOR 37 (Bruker) FT-IR spectrometer with KBr pellets. UV/Vis
absorption spectra were measured with Hitachi U-3010 UV-Vis
spectrophotometer (Hitachi, Japan). Fluorescence spectra were recorded
at room temperature on a Hitachi F-4500 fluorescence spectrometer.
Elemental analyses (C, H and N) were performed on a Perkin-Elmer
analyzer. Inductively coupled plasma (ICP) analyses were carried out on
a Perkin-Elmer Optima 3300 DV spectrometer.
2 3
O
This work was financially supported by the NSFC (21371102,
1531005, and 21673120) and the NSF of Tianjin
15JCZDJC38800 and 16JCZDJC36900).
a
2
(
Keywords: Cd-MOF • Absorption competition • Energy transfer •
Dual quenching mechanism • High sensitivity
2
Synthesis of 4-(1H-Pyrazole-4-carboxamido) benzonic acid (H L).
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A mixture of 1H-pyrazole-4-carboxylic acid (30 mmol), freshly distilled
thionyl chloride (60 mL) and two drops of dry DMF was heated to reflux for
1
2h at nitrogen atmosphere. Then excess thionyl chloride was removed
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a
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European Journal of Inorganic Chemistry
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This article is protected by copyright. All rights reserved.

European Journal of Inorganic Chemistry
10.1002/ejic.201701290
FULL PAPER
FULL PAPER
A novel
Key Topic*
Long-Sheng Li, Xi Wang
Yan-Yuan Jia, Shi-Xian Xu,
Mei-Hui Yu, Ying-Hui Zhang
hexanuclear
Cd-MOF was
constructed with
highly selective and
sensitive
,
*
fluorescent
quenching
Page No. – Page No.
response toward
A Novel Hexanuclear
3
+
Fe , attributable to
the coaction of
absorption
competition and
energy transfer
mechanism.
Cd-MOF Exhibiting Dual
Mechanism-Triggering
Fluorescence Quenching
3
+
Response toward Fe Ions
in DMF
This article is protected by copyright. All rights reserved.