Chinese Journal

CJC of Chemistry
中 国 化 学 - An International Journal

Accepted Article

Title: Monodentate AIEgen Anchored on Metal-Organic Framework for Fast

Fluorescence Sensing of Phosphate

Authors: Xinli Gao, Lei Pei, Wenjuan Xue, Hongliang Huang,* Zhuqing Gao, and
Xudong Zhao*

This manuscript has been accepted and appears as an Accepted Article online.

This work may now be cited as: Chin. J. Chem. 2020, 38, 10.1002/cjoc.202000364.

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published online in Early View: http://dx.doi.org/10.1002/cjoc.202000364.

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 Metal-organic framework, Fluorescence sensing, Phosphate, Chinese Journal
Report Monodentate ligand, AIEgen
CJC of Chemistry
中 国 化 学 - An International Journal

Monodentate AIEgen Anchored on Metal-Organic Framework for Fast

Fluorescence Sensing of Phosphate
Xinli Gao,a Lei Pei,b Wenjuan Xue,c Hongliang Huang,*,c Zhuqing Gao,b and Xudong Zhao*,b
a
Instrumental analysis center, Taiyuan University of Science and Technology, Taiyuan 030024, China
b
College of Chemical and Biological Engineering, Taiyuan University of Science and Technology, Taiyuan 030024, China
c
State Key Laboratory of Separation Membranes and Membrane Processes, School of Chemistry and Chemical Engineering, Tiangong University, Tianjin
300387, China

Cite this paper: Chin. J. Chem. 2020, XX, XXX—XXX. DOI: 10.1002/cjoc. XXX

Summary of main observation and conclusion Herein, a novel sensor (TPE-UiO-66) was designed via anchoring monodentate tetraphenylethylene (TPE)
onto UiO-66 framework. The combination of the distinct aggregation-induced emission (AIE) of TPE and the easy replacement of monodentate linker by
guest phosphate, makes TPE-UiO-66 an ideal platform for sensing HPO42-. Experimental results indicate that TPE-UiO-66 can selectively sense HPO42- from
other common anions. The limit of detection (LOD) can reach to 5.56 μM and more importantly, TPE-UiO-66 also exhibits an ultra-fast equilibrium
response of 2 min, far faster than those other sensors especially for UiO-66-NH2. The combination of experimental analysis and density functional theory
(DFT) calculations demonstrate that the high selectivity, high sensitivity and fast response of HPO42- detection in TPE-UiO-66 can be attributed into the
stronger coordination interactions of HPO42- with Zr-O cluster of UiO-66 than that of TPE molecule. This study not only provides a potential probe for
phosphate, but also represents a novel strategy to design stimuli-responsive fluorescent MOF-based sensors via using monodentate AIEgens.

Background and Originality Content
Phosphate ion is involved in several important biological
processes including cell signaling, energy exchange, DNA synthesis,
and transport across membranes, etc.1 However, excessive uptake
of phosphates may cause the diseases such as
hyperphosphatemia and cardiovascular complications.2 Therefore,
selective, sensitive, and fast detection of phosphates in
liquid-phase systems is of significance but challenging to date.
Among the developed detection methods, fluorescence sensing
exhibits distinct characteristics including fast response, high
selectivity and sensitivity.3 To achieve highly effective sensing of
the targets, intense ongoing researches are in progress to exploit
new sensor species.
Since 2000s, metal-organic frameworks (MOFs), a class of
porous material consisting of inorganic metal clusters and organic
ligands, have attracted interests in applications of chemical
engineering, environmental engineering, and biological medicine,
etc.4-7 Particularly, thanks to abundant conjugated systems,
designable binding sites, and regular frameworks structures,
MOFs as sensory materials were widely used to detect guest ions
or molecules.8-10 Recently, exploiting MOF sensors by taking
advantage of the reversibility and instability in certain conditions
of coordination bonds has become a research hotpot.11-14 For
phosphate sensing, one of the current strategies is to utilize the
coordination effect between phosphate and inorganic clusters to
control the luminescence of MOFs, and the distinct binding of
central metals towards phosphate is the dominant reason for the
high selectivity. Up to date, such MOF-based sensors have been
reported, for example, UiO-66-NH2 and other Eu/Tb-based
MOFs.15-17 However, those MOFs are commonly composed by
bidentate ligands or polydentate ligands. Accordingly, the
interaction of clusters and organic ligands is reasonably strong,
which restricts the fast and easy coordination of phosphate
towards central metals and thereby limits fast and sensitive
sensing of phosphate. Unlike that, in monodentate
ligand-containing frameworks, the binding of phosphate and MOF
clusters and even the complete replacement of the ligand by
phosphate are more feasible. Thus, based on the superiority of
monodentate ligand, effective sensing of targeted ions may be
achieved.
To construct this species of sensors, proper selection of
inorganic cluster and monodentate ligand is greatly crucial. The
former plays a dominant effect on sensing selectivity based on the
coordination interaction between clusters and phosphate. In this
respect, Zr-O clusters have demonstrated to be capable of
interacting strongly to phosphate,15,16,18,19 and thereby can serve
as the binding sites of the sensors. On the other hand,
monodentate ligand should exhibit switchable luminescence with
and without the excitation of the targets. In this respect,
tetraphenylethylene (TPE), with distinct aggregation-induced
emission (AIE), can exhibit luminescence “turn-on” and “turn-off”
in the anchored and free (or dissolved) states, respectively.20,21 Up
to date, various TPE-based compounds have been exploited and
further applied in fluorescence biosensing based on the AIE
function.22-24 Thus, this AIEgen may be used as an ideal optical
conversion unit.

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Scheme 1 Schematic diagram of TPE-UiO-66 preparation and phosphate
sensing.
Non-emissive
Non-emissive
Emissive
ZrCl4 +
DMF
Anchored AIEgen Free AIEgen
H2BDC Zr-O cluster HPO4 2- Other anions
Herein, as a proof-of-concept experiment, a novel sensory
material, TPE-UiO-66, was prepared via in-situ anchoring
monodentate TPE-COOH molecule into UiO-66 framework, as
illustrated in Scheme 1. In virtue of the distinct AIE effect, the TPE
molecule can exhibit emissive fluorescence in anchored state
while non-emissive fluorescence in free state after being replaced
by phosphates for the intramolecular rotation. Although some
TPE-based MOFs have been exploited as fluorescence sensors,25-31
to the best of our knowledge, the prepared TPE-UiO-66 is the first
example to construct MOF-based sensors via monodentate TPE
molecule, and also the first MOF-based sensor for phosphate
detection based on AIE effect of AIEgens. As expected, this
material was demonstrated to serve as a selective and sensitive
probe for HPO42- with a fast response time. The selective sensing
mechanism was systematically studied via combination of
experiment methods and theoretical thermodynamics calculation.
Results and Discussion
Characterization of TPE-UiO-66
(a) (b)
(c) (d)
Figure 1 Characterization results of TPE-UiO-66: (a) PXRD patterns; (b) N2
adsorption-desorption isotherms at 77 K; (c,d) 1H NMR spectra.
In previously reported MOFs, Zr-O cluster has been
demonstrated to coordinate with small monodentate
carboxylated molecules (such as formic acid,32,33 acetic acid34 and
benzoic acid35) via in-situ synthesis methods. Therefore, in this
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First author et al.
work, with UiO-66(Zr) as the platform, we used monodentate
TPE-COOH molecule to construct the fluorescence sensor,
TPE-UiO-66. Compared with other MOFs, UiO-66 exhibited
excellent chemical stability and its framework topology will not be
changed even with addition of various small molecules in the
synthesis process. More importantly, the window of UiO-66 cages
is smaller than the molecular size of TPE-COOH, indicating that
the encapsulated TPE in the internal space of UiO-66 via in-situ
method will not be leached out. Thus, UiO-66 can serve as an
ideal platform for TPE loading.
The crystal structure of the synthesized material was verified
based on PXRD pattern measurement as shown in Figure 1a.
Clearly, the characteristic diffraction peaks in the PXRD pattern of
TPE-UiO-66 can match with that in the simulated pattern of
UiO-66 crystal, indicating the topology of TPE-UiO-66 is similar to
that of UiO-66. The permanent porosity of the sample was
evaluated using N2 adsorption-desorption isotherms at 77 K.
According to the curves in Figure 1b, the BET specific surface area
of TPE-UiO-66 was calculated to be 817.3 m2 g-1, slightly lower
than that of UiO-66 (917.5 m2 g-1). This decrease is mainly
attributed to the introduction of TPE molecules that leads to the
blockage of the micropores. At last, the morphology of the sample
was observed through TEM images. As seen from Figure S1,
TPE-UiO-66 is composed of the octahedral particles with the
uniform size of ~70 nm.
The composition of TPE-UiO-66 was investigated according to
1H NMR spectra. As illustrated in Figure 1c, the characteristic sign
of H2BDC at 7.8 ppm appears in the spectrum of TPE-UiO-66,
indicating the existence of BDC ligand. From Figure 1d, most of
the characteristic peaks attributed to TPE-COOH molecule can be
also found in the NMR spectrum of TPE-UiO-66, demonstrating
the successful introduction of TPE into UiO-66. Further, the
content of TPE in the synthesized material was measured via the
integration of NMR peaks (Figure S2). The molar ratio of TPE and
BDC was found to ~1:110, and the content of TPE was estimated
to ~1.24 wt%. FTIR spectra were utilized to study the
immobilization form of TPE molecule in the synthesized sample.
As shown in Figure S3, the peak at 1688 cm-1 in the spectrum of
TPE-COOH is assigned to the vibration of free carboxyl groups.
After the synthesis reaction, it is clear that this typical peak
disappeared completely, indicating the free carboxyl groups of
TPE-COOH coordinated to the Zr-O clusters of UiO-66. Thus,
concluded above, we suggest that TPE molecule was anchored
into UiO-66 framework through coordination interaction rather
than the simple encapsulation.
At last, the existence position of TPE-COOH in TPE-UiO-66 was
studied via two simple experiments. On the one hand, TPE-UiO-66
was immersed in HPO42- solution for 12 h and then the
supernatant was collected for UV-vis spectra measurement. As
shown in Figure S4, an obvious peak assigned to TPE can be found
in UV region clearly. To further prove that, concentrated
hydrochloric acid was added in the supernatant and some white
solid with the characteristic fluorescence of TPE was precipitated
out (Figure S5), confirming the leaching out of TPE-COO- (rather
than TPE-COOH) from TPE-UiO-66. Considering the undamaged
framework (Figure S6) and the larger size of TPE than the window
of UiO-66 cages, the leached TPE was just from the outer surface
Chin. J. Chem. 2019, 37, XXX－XXX
Running title
of TPE-UiO-66. On the other hand, after being treated by HPO42-,
the residual sample was collected and further dried. As expected,
this solid can still emit obvious fluorescence (inset of Figure S4),
indicating the existence of TPE in the internal defects of the
framework. Concluded above, we suggest TPE molecule
coordinated to not only the surface but also the internal defects,
as illustrated in Figure S7.
Luminescence property
(a) (b)
UV 365nm
Figure 2 (a) Solid-state excitation and emission spectra of TPE-UiO-66 at
room temperature; the inset image shows the practical images of
TPE-UiO-66 under natural light and UV light of 365 nm; (b) the ratio of the
fluorescence intensity at different immersion time (I) and the initial
intensity (I0) of TPE-UiO-66.
Tetraphenylethylene and its derivatives, as a typical class of
AIE-activated luminophore, have attracted significant interests in
constructing fluorescent sensors. The nonplanar TPE molecule is
non-emissive in the free state for intramolecular rotation
mechanism, while can emit strong fluorescence in anchored
states.36,37 To verify the emissive fluorescence of TPE-UiO-66, the
room-temperature solid-state luminescence excitation and
emission spectra of the sample were measured. As shown in
Figure 2a, upon the excitation wavelength of 330 nm, the
emission spectrum of the sample exhibits a broad peak centered
at 475 nm. Meanwhile, under the UV light of 365 nm, TPE-UiO-66
can glow a bright blue-green fluorescence, which can be easily
seized by naked eyes. This strong emission is attributed to the
anchored state of TPE: the intramolecular rotation of the four
phenyl rings are limited by the solid framework of UiO-66, further
preventing the nonradiative relaxtion.36 Besides, we tried to boost
the luminescence property of the sample via controlling the
addition amount of TPE-COOH amount. However, the small
addition (3 mg) will lead to weak solid-state fluorescence and bad
sensing performance; while the large amount of TPE (25 mg) will
restrict the growth of UiO-66 crystal and the yield of the resulting
sample is only 20% that of optimal TPE-UiO-66 (10 mg TPE used ).
Also, as a comparison, TPE molecule without carboxyl was also
used to prepare the fluorescent material. However, the
synthesized sample cannot exhibit obvious fluorescence
compared to TPE-UiO-66 (Figure S8), suggesting the key role of
free carboxyl in the anchoring of TPE molecule and constructing
the fluorescent sensors.
Furthermore, the stability of the material and its fluorescence
in the blank solution (HEPES solution) was investigated. First, as
shown in Figure S9, the PXRD patterns of TPE-UiO-66 before and
after being immersed in HEPES solution are almost consistent with
each other, indicating the framework of TPE-UiO-66 can keep
Chin. J. Chem. 2019, 37, XXX－XXX © 2019 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Chin. J. Chem.
stable in the aqueous solution. Further, Figure 2b shows that the
luminescence intensity at 475 nm keeps almost unchanged even
with a long immersion time of 2880 min. Thus, TPE-UiO-66 can
serve as a potential luminescent material used in water-phase
sensing.
Sensing performance
To investigate the anions recognition performance of
TPE-UiO-66, the sample was added into the HEPES solutions of 0.1
mol L-1 anions (including Cl-, Br-, I-, NO3-, OAc-, SO42-, HPO42- and
H2PO4-) and the resulting suspensions were used for fluorescence
spectra measurement. As shown in the inset of Figure 3a, upon
the contact with HPO42-, the blue light of the suspension was
quenched clearly; while the fluorescence kept almost unchanged
upon the addition of other common anions. Further, this
quenching phenomenon was evaluated via fluorescence spectra
measurement. From Figure 3a, the emission intensity of the
suspension at 475 nm decreased sharply while contacting with
only HPO42-. Thus, from the results above, we suggest that
TPE-UiO-66 can selectively sense HPO42- over other anions at the
fluorescence “turn-off” mode.
(a) (b)
(c) (d)
Figure 3 Sensing performance for anions of TPE-UiO-66: (a) fluorescence
spectra of samples in HEPES solutions containing various anions; (b)
intensity (at 475 nm) at different reaction time; (c) fluorescence spectra of
samples in HPO42- solutions with different concentrations; (d) intensity (at
475 nm) of samples in the anions solutions with and without the addtion
of HPO42-.
Response time is one of important factors to evaluate the
performance of sensors. Herein, the fluorescence emission
intensity of TPE-UiO-66 at the time range of 30 s-40 min and the
initial concentration of 0.1 mol L-1 was measured. From Figure 3b,
it is clear that the intensity decreases quickly in tens of seconds
and reaches equilibrium at ~2 min for HPO42-, superior to other
reported sensors such as pyrene-tagged MOF (> 20 min),1
UiO-66-NH2 (~60 min),15 and spinel cobalt ferrite nanoparticle
(120 min),38 etc.
The sensitivity as well as the detection limit was further
investigated via adding TPE-UiO-66 sample into the HPO42-
solutions with various concentrations. From Figure 3c, the
emission intensity decreases gradually with the increasing
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concentrations of the ions. To obtain the limit of detection (LOD)
of the sensor, the linear fitting between the emission intensity
and the concentration at 1.0×10-5-5.0×10-5 mol L-1 was carried out.
As illustrated in Figure S10, the good fitting relationship
(R2=0.9932) can be achieved. The LOD for HPO42- was calculated to
5.56 μM according to the equation: LOD = 3Sb/S, where S is the
slope of the fitting curve and Sb is the standard deviation for
replicating detections of blank solutions. To evaluate the
sensitivity, a comparison with other reported sensors especially
for bidentate and tridentate ligands-MOFs was carried out. The
LOD of TPE-UiO-66 is found to be superior to those of the
materials such as Tb(H2O)BTB (35 μM), Eu(bcpt)(HCOO) (274 μM),
Eu(ppda)2(npdc)(H2O) (14.2 μM), Eu-triazole MOF (6.62 μM),
Eu3(TTA)9trisphen (67.2 μM), and Eu-BTB (10 μM).16,39-43
Furthermore, the LOD value of TPE-UiO-66 is comparable with
that of UiO-66-NH2 (1.25 μM), while the response equilibrium (2
min) is far faster than that of UiO-66-NH2 (~60 min). Thus,
monodentate ligand may have superiority in constructing
MOF-based sensors with substantial performance.
At last, from the view of practical use, the detection of HPO42-
in binary system was carried out. As shown in Figure 3d, upon the
addition of HPO42-, the fluorescence of the solutions of the anions
(Cl-, Br-, I-, NO3-, OAc-, SO42-, and H2PO4-) were quenched and the
final intensities are almost consistent. This result indicates that
the detection of HPO42- in binary system can be also achieved and
the type of co-existing anion has not obvious effect. The slight
interference from other anions is attributed to their much weaker
interactions towards Zr-O clusters than HPO42- (discussed below).
Thus, TPE-UiO-66 may have practical potentials in the application
of HPO42- sensing.
Sensing mechanism
The selective sensing mechanism for HPO42- was studied via
the combination of experimental analysis and theoretical
calculation. Firstly, since TPE molecule is anchored in TPE-UiO-66
via just the monodentate coordination, the substitution by the
phosphate cannot induce the collapse of the framework of
TPE-UiO-66, demonstrated by PXRD pattern measurement as
shown in Figure S6. Secondly, the FTIR of the sample before and
after contacting with the various ions were measured. As shown
in Figure 4a, the anions including Cl-, Br-, I-, NO3-, OAc-, and SO42-
cannot induce obvious changes while HPO42- and H2PO4- can lead
to a new broad peak at ~900-1100 cm-1, assigned to the vibration
of P-O bonds. The interaction between the phosphates and
TPE-UiO-66 was further investigated via XPS measurement. From
Figure 4b, similarly, only HPO42- and H2PO4- led to that the peaks
for Zr 3d shifted to higher binding energies, indicating the
formation of P-O-Zr bonds. These evidences indicate both HPO42-
and H2PO4- may coordinate the Zr sites of UiO-66.
However, based on the fluorescence experiments previously,
HPO42- rather than H2PO4- can quench the fluorescence of
TPE-UiO-66. For explaining that, a DFT calculation for the
substitution process of TPE molecule by the phosphates was
carried out. Herein, a classical thermodynamics criterion of Gibbs
free energy (ΔG), commonly used to study the probability of a
reaction, was introduced. As illustrated in Figure 4c and d, the ΔG
value for the substitution process of TPE-COO- ligand by HPO42-
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First author et al.
was calculated to be -75 kJ mol-1, indicating that the substitution
reaction of TPE-COO- by HPO42- is spontaneous. On the contrary,
the ΔG value for that of H2PO4- was found to be +0.3 kJ mol-1,
suggesting that the substitution of TPE-COO- by H2PO4- may be
rather difficult. The P-O-Zr for H2PO4- may be attributed to the
coordination towards the Zr-H2O or Zr-DMF in the defects.44-46
(a)
P-O
(b)
(c)
+
HPO42-
ΔG= -75 kJ/mol (TPE-COO-)
(d)
H2PO4-
+
ΔG= +0.3 kJ/mol
(TPE-COO-)
Figure 4 (a) Zr 3d high-resolution XPS patterns and (b) PXRD patterns of
TPE-UiO-66 before and after being immersed in the HPO42- solution; (c)
DFT calculation result for the replacement of TPE-COOH by HPO42-; (d) DFT
calculation result for the replacement of TPE-COOH by H2PO4-.
Concluded above, HPO42- has stronger affinity towards the
Zr-O cluster than TPE-COOH, and accordingly, the anchored
TPE-COOH ligand can be easily replaced by the anion. On the one
hand, the TPE molecules on the outer surface were leached out
by HPO42- and dissolved in HEPES solution. Accordingly, their
fluorescence was quenched for the unlimited intramolecular
rotation, as shown in Figure S5. On the other hand, the TPE in the
internal defects was also substituted by HPO42- but still remained
in the defects for its larger size than the window of UiO-66 cages.
Due to the free intramolecular rotation in the large-size defects
under the liquid-phase system, the fluorescence of the TPE in the
defects was also quenched. Concluded above, the TPE molecules
on the outer surface and in the internal defects both contribute
to the selective sensing of HPO42- at the fluorescence “turn-off”
mode. The sensing mechanism was illustrated in Figure S11.
Conclusions
In summary, a novel fluorescent material, TPE-UiO-66, was
successfully constructed based on UiO-66 framework and the
monodentate TPE molecule and further employed as a probe to
detect HPO42-. Due to the distinct host-guest coordination effect
and the AIE function of TPE molecule, TPE-UiO-66 can selectively
and sensitively detect HPO42- over other common anions. Besides,
the sensor also exhibits a fast sensing response and excellent
anti-interference ability from co-existing ions. This work not only
demonstrates the synthesized TPE-UiO-66 is a potential probe for
Chin. J. Chem. 2019, 37, XXX－XXX
Running title
HPO42-, but also provides some guidelines for the design of
MOF-based sensors based on monodentate AIEgens.
Experimental
Materials and synthesis. All reagents used in this work were
commercially available and used as supplied without further
purification. UiO-66 was prepared according to the literature.47
TPE-UiO-66 was synthesized as the following procedure. In a 100
mL beaker, zirconium tetrachloride (53 mg) and terephthalic acid
(34 mg) were dissolved in DMF (26 mL). After that,
4-(1,2,2-triphenylvinyl)benzoic acid (TPE-COOH, 10 mg) was
added and the resulting mixture was stirred for 20 min. Then, the
solution was transferred into a 100 mL Teflon-lined stainless steel
autoclave and heated at 393 K for 24 h. After being cooled down
to room temperature, the white solid was collected and washed
with DMF and methanol several times. At last, the solid was dried
at 373 K for 24 h.
Characterization of MOFs. Powder X-ray diffraction (PXRD)
data of the synthesized materials was collected on a D8 ADVANCE
XRD-6000 X-ray diffractometer using Cu Kα radiation (λ = 1.54056
Å). The 2θ range from 5° to 50° was scanned with the step size of
0.02°. The morphology of the sample was characterized using an
F-200 transmission electron microscope (TEM). Infrared spectra
analysis was carried out on a Nicolet iS50 FTIR spectrophotometer.
X-ray photoelectron spectroscopy (XPS) data was collected on an
Thermo escalab 250Xi X-ray photoelectron spectroscope with the
excitation source of Al Kα radiation. 1H nuclear magnetic resource
(NMR) spectra were measured on a Bruker AVANCE III 600 mHz
spectrometer at 298 K. The sample was prepared via dissolving 10
mg of the materials into the mixed solution of H2SO4-d6/DMSO-d6
(0.3 mL/1.0 mL). N2 adsorption-desorption isotherms at 77 K of
the samples were measured on an ASAP 2020 surface area
analyzer.
Fluorescence sensing experiments. In a 4 mL vial, 3 mg of
TPE-UiO-66 was added into the HEPES solutions (pH=7.4, 20 mmol
L-1, 3 mL) containing various anions. After ultrasound treatment
for ~10 s, the resulting suspension was aged for a certain time
and further used for the fluorescence spectra measurement with
the excitation wavelength of 360 nm. In detail, in the experiment
on type of anions and concentration of phosphate, the
concentration of anions and the aging time were set as 0.1 mol L-1
and 2 h, respectively; in the experiment on response time, the
concentration of phosphate was set as 0.1 mol L-1; in the
experiment about the effect of co-existing anions, the
concentrations of phosphate and other anions were both 0.1 mol
L-1 and the aging time was 2 h.
Computational method. The UiO-66 cluster model was
truncated from an optimized periodic structure of UiO-66. To
minimize the boundary effects in the cluster model calculations,
the unsaturated carbon atoms in the cluster model was saturated
with hydrogen atoms. The Gaussian 09 suite of quantum
mechanical program was used for all density functional
calculations.48 Geometry optimizations and the single-point
energy calculations were performed at the Becke three
parameters hybrid exchange-correlation functional (B3LYP) level
of theory.49 The def2-SVP basis set was employed for C, H, and O
atoms, the def2-TZVP basis set was employed for P atoms, and
Chin. J. Chem. 2019, 37, XXX－XXX © 2019 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Chin. J. Chem.
the def2-TZVPP basis set was employed for Zr atoms with the SDD
effective core potential.50,51 In all cases, the positions of all atoms
were optimized in the gas phase, except for the C atoms of the
capping benzoate groups, which were fixed at their positions in an
optimized structure of UiO-66. Zero-point energies and thermal
contributions to enthalpies and Gibbs free energies were derived
from vibrational frequency calculations performed at the same
level of theory at 298.15 K and 1 atm. We verify that none of the
stationary points have imaginary frequencies. It is noted that in
the calculation process, HPO42- and H2PO4- were used at the
protonated mode and deprotonated TPE-COO- was used
(demonstrated in Figure S5). Besides, because it is difficult to
obtain the exact structure of TPE-UiO-66 with defects and the
structure of the possible defective cavity contains too much
atoms, the corresponding DFT calculation is difficult. Thus, the
Van der Waals interaction between TPE and MOF cavity was not
considered in the MOF-TPE relative DFT calculations.
Supporting Information
The supporting information for this article is available on the
WWW under https://doi.org/10.1002/cjoc.2020xxxxx.
Acknowledgement
This work is supported by Ph.D. Scientific Research
Foundation of Taiyuan University of Science and Technology (No.
20182020, 20182058), National Natural Science Foundation of
China (No. 21978212), Science and Technology Plans of Tianjin
(No. 18PTSYJC00180), Scientific and Technological Innovation
Project of University in Shanxi Province (No. 2019L0657,
2019L0628), and Doctoral Award Fund of Shanxi Province (No.
20192045)
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Manuscript received: XXXX, 2019
Manuscript revised: XXXX, 2019
Manuscript accepted: XXXX, 2019
Accepted manuscript online: XXXX, 2019
Version of record online: XXXX, 2019
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Entry for the Table of Contents

Page No.
Monodentate AIEgen Anchored on Non-emissive
Metal-Organic Framework for Fast
Fluorescence Sensing of phosphate Non-emissive
Emissive

ZrCl4 +
DMF

Anchored AIEgen Free AIEgen

H2BDC Zr-O cluster HPO42- Other anions

Xinli Gao, Lei Pei, Wenjuan Xue, Hongliang Present here is the selective sensing of HPO42- by using a novel sensor constructed by MOF and
Huang,* Zhuqing Gao, and Xudong Zhao* monodentate AIEgen molecule.

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