A new luminescent metal-organic framework based on dicarboxyl-substituted tetraphenylethene for efficient detection of nitro-containing explosives and antibiotics in aqueous media

Article abstract of DOI:10.1039/c7tc05535h

In this work, we synthesized a dicarboxyl-substituted tetraphenylethene (TPE) ligand, 4,4′-(1,2-diphenylethene-1,2-diyl)dibenzoic acid (H₂BCTPE), with a prominent aggregation-induced emission (AIE) feature. A two-fold interpenetrated luminescen

Full text of DOI:10.1039/c7tc05535h

View Article Online
View Journal
Journal of
Materials Chemistry C
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: X. Liu, C. Tao, H.
Yu, B. Chen, Z. Liu, G. Zhu, Z. Zhao, L. Shen and B. Z. Tang, J. Mater. Chem. C, 2018, DOI:
10.1039/C7TC05535H.
This is an Accepted Manuscript, which has been through the
Volume
4 Number 1 7 January 2016 Pages 1–224
Royal Society of Chemistry peer review process and has been
accepted for publication.
Journal of
Materials Chemistry C
Accepted Manuscripts are published online shortly after
Materials for optical, magnetic and electronic devices
www.rsc.org/MaterialsC
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
author guidelines.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the ethical guidelines, outlined
in our author and reviewer resource centre, still apply. In no
event shall the Royal Society of Chemistry be held responsible
for any errors or omissions in this Accepted Manuscript or any
consequences arising from the use of any information it contains.
ISSN 2050-7526
PAPER
~
Nguyên T. K. Thanh, Xiaodi Su et al.
Fine-tuning of gold nanorod dimensions and plasmonic properties using
the Hofmeister effects
rsc.li/materials-c

Please do not adjust margins
Page 1 of 7
Journal of Materials Chemistry C
View Article Online
DOI: 10.1039/C7TC05535H
Journal Name
ARTICLE
A new luminescent metal-organic framework based on
dicarboxyl-substituted tetraphenylethene for efficient detection
of nitro-containing explosives and antibiotics in aqueous media
Received 00th January 20xx,
Accepted 00th January 20xx
Xun-Gao Liu,*a Chen-Lei Tao,a Huang-Qin Yu,a Bin Chen,b Zhen Liu,a Gen-Ping Zhu,a Zujin Zhao,*b
DOI: 10.1039/x0xx00000x
Liang Shen,*a and Ben Zhong Tangbc
www.rsc.org/
In this work, we synthesized a dicarboxyl-substituted tetraphenylethene (TPE) ligand, 4,4'-(1,2-diphenylethene-1,2-
diyl)dibenzoic acid (H2BCTPE) with prominent aggregation-induced emission (AIE) feature. A two-fold interpenetrated
luminescent metal−organic framework (LMOF) [Zn4O(BCTPE)3] (1) with Zn4O(CO2)6 nodes is prepared by using the trans-
isomer of H2BCTPE as a ligand, which shows a typical behavior of microporous materials and a high fluorescence quantum
yield of 64.5%. The solvent free 1 is thermal stable, water stable and highly emissive. The suspension of solvent-free 1 in
water exhibits high quenching efficiencies and low detection limits towards nitro-containing explosives (e.g. nitrobenzene,
4-nitrophenol, 2,4,6-trinitrophenol), and nitro-containing antibiotics (e.g. metronidazole and nitrofurazone). The solvent-
free 1 can be a promising alternative to efficiently detect nitro-containing explosives and antibiotics in aqueous conditions.
derivatives were relatively rare in LMOFs, and there are only
two examples: one is 4,4′-(2,2-diphenylethene-1,1-
diyl)dibenzoic acid (DPEB) and the other is dipyridine-
Introduction
Luminescent metal-organic frameworks (LMOFs), self-
assembled from metal ions and organic legends, have shown
giant potentials in chemical sensors, bioprobes, catalysis, and
other diverse research frontiers.1-3 The emissions of LMOFs
can be produced from lanthanide metals, organic
chromophores, metal-ligand charge transfer processes or
substituted
(E)-1,2-diphenyl-1,2-bis(4-(pyridin-4-yl)-
phenyl)ethane (BPyTPE).15,16 This is probably due to the
difficulty lying in isolating pure cis- and trans-isomers from the
products of McMurry coupling.17 These ligands can connect
with different metal ions to construct TPE-based LMOFs
containing of 1D chains, paddle-wheel M2(COO)4 units,
Zn4O(CO2)6 nodes or Zr6 clusters.18-21
guest molecules.4-6 Recently, tetraphenylethene (TPE),
a
simple luminogen with prominent aggregation-induced
emission (AIE) characteristic, is emerging as a popular building
block to create LMOFs.7 Immobilized in the rigid frameworks,
TPE can fluoresce intensely and make major contributions to
the emissions of LMOFs.8 The strong emissions enable TPE-
based LMOFs to serve as promising fluorescent sensors to
detect volatile organic compounds, mycotoxins and nitro
explosives in a turn-off mode.9,10 Generally, TPE derivatives
tetra-substituted with carboxyl or pyridyl groups, such as
H4TCPE, H4ETTC, H8TDPEPE, tppe and TTPE, are utilized as
ligands to construct LMOFs.11-14 However, di-substituted TPE
Nitro-containing
antibiotics,
metronidazole
and
nitrofurazone, are important medicines for mankind to
prevent and treat certain diseases, as well as for resistance to
bacterial infections in aquaculture. However, these medicines
are already in the "list of drugs prohibited in animal foods"
issued by National Bureau of Quality Inspection (AQSIQ) and
Ministry of foreign trade and economic cooperation, because
their residues in animals can be delivered to human body
through the food chain. And long-term intake of these
contaminated foods can cause a variety of diseases, like
immunity decline, allergic reactions, hereditary genetic defects
and various types of cancers.22,23 At present, various expensive
and complicated instruments, such as ion mobility
spectrometry, high-performance liquid chromatography and
other assays requiring sophisticated procedures are explored
to detect metronidazole, nitrofurazone and so forth.24-27
Therefore, as fluorescence sensors, LMOFs can provide a new
alternative to readily detect these antibiotics with high
sensitivity, short response time and high recyclability.28-32
a.College of Material, Chemistry and Chemical Engineering, Hangzhou Normal
University, Hangzhou 310036, China. *E-mail: xungaoliu@hznu.edu.cn
shenliang@hznu.edu.cn
；
b.Center for Aggregation-Induced Emission, State Key Laboratory of Luminescent
Materials and Devices, South China University of Technology, Guangzhou 510640,
China. *E-mail: mszjzhao@scut.edu.cn
c. Department of Chemistry, Hong Kong Branch of Chinese National Engineering
Research Center for Tissue Restoration and Reconstruction, The Hong Kong
University of Science & Technology, Clear Water Bay, Kowloon, Hong Kong, China
†
Electronic Supplementary Information (ESI) available: experimental details,
In principle, Zn (
and Zr6 clusters with carboxyl ligands, which are highly stable
in water.33-36 Linear organic carboxylic linkers are prone to
Ⅱ) and Zr (Ⅳ) metals can form Zn4 clusters
crystallographic data, CIF files, thermal analysis, absorption and emission spectra,
geometrical structures, PXRD patterns and fluorescence titration. See
DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
Please do not adjust margins

Please do not adjust margins
Journal of Materials Chemistry C
Page 2 of 7
ARTICLE
Journal Name
Subsequently, ethylenediamine (4 mL) and H2O V(i6ewmArtLic)lewOnelirnee
DOI: 10.1039/C7TC05535H
added into the mixture and heated to reflux for 3 h. After
cooling down to room temperature, 4,4'-(1,2-diphenylethene-
1,2-diyl) dibenzonitrile (2CN-TPE) was obtained by extracting
with dichloromethane (DCM) and drying over anhydrous
coordinate with Zn (
Ⅱ
) ions to form [Zn4(μ4-O)]6+ clusters with
a 3D structure, such as isoreticular MOF (IRMOF) series.37-40
With these considerations in mind, in this work, we use
dicarboxyl-substituted TPE (H2BCTPE) to build a 3D LMOF
[Zn4O(BCTPE)3] (
H2BCTPE are incorporated in complex
1
). Interestingly, only the trans-isomers of
, although H2BCTPE are
1
magnesium sulfate. After filtration and solvent evaporation
,
composed of cis- and trans-isomers produced from McMurry
coupling. [Zn4O(BCTPE)3] is highly emissive and stable in water,
and can function as an efficient sensor to detect nitro-
containing explosives and antibiotics in aqueous media.
crude 2CN-TPE underwent hydrolysis reaction carried out in
ethylene glycol (40 mL) containing NaOH (0.4 g, 10 mmol) at
200 °C for 3 days. Then, HCl (1 mol/L, 10 mL) solution was
added carefully to quench the reaction after cooling down to
room temperature. Pale brown solid of H2BCTPE (a mixture of
cis- and trans-isomers) was obtained in 45% overall yield after
filtering, washing with water for three times and air drying. 1H
NMR (600 MHz, DMSO-d6), δ (TMS, ppm): 12.97 (s, 2H), 7.75 (m,
4H), 7.15 (m, 8H), 7.19 (d, 2H), 6.99 (d, 4H). 13C NMR (150 MHz,
DMSO-d6), δ (TMS, ppm): 166.98, 147.37, 142.16, 140.91,
130.74, 130.55, 128.91, 128.84, 128.05, 127.96, 127.02. IR:
(KBr pellet, cm‒1): 3056 (m), 1700 (s), 1603 (s), 1563 (m), 1442
(m), 1409 (s), 1311 (m), 1273 (s), 1177 (s), 1105 (m), 1074 (w),
1017 (m), 859 (m), 761 (m), 745 (s), 699 (m). ESI (FAB): m/z=
421.136 [M + H]+.
[Zn4O(BCTPE)3] (1). Zn(NO3)2 · 6H2O (10 mg, 34 mmol), H2BCTPE (8
mg, 19 mmol) and N,N-dimethylformamide (DMF, 2 mL) were
added in a 10 mL screw-capped vial. The solids were ultrasonically
dissolved and kept at 100 °C for 2 days. After the reaction mixture
was cooled down to room temperature, the transparent pale yellow
cube crystals were harvested via filtrating and washed with DMF for
three times. Yield: 35%. IR: (KBr pellet, cm‒1): 1660 (s), 1602 (s),
1538 (s), 1408 (s), 787 (w), 755 (m), 720 (w), 701 (m).
Scheme 1. Synthetic route to TPE-based ligand H2BCTPE.
Experimental section
Synthesis
Complex 1 was soaked in DCM for 3 days, during which time
DCM was decanted and refreshed every day, and then dried under
a dynamic vacuum at room temperature for 3 h to obtain solvent-
free 1. Anal. Calcd for C28H18O4.33Zn1.33: C, 65.76; H, 3.52; O, 13.56%;
Found: C, 65.20; H, 3.36; O, 13.63%. IR: (KBr pellet, cm‒1): 1600 (s),
1548 (s), 1413 (s), 785 (m), 754 (m), 721 (w), 700 (m).
4,4'-(1,2-Diphenylethene-1,2-diyl)dibenzoic acid (H2BCTPE).
A
Sandmeyer reaction between 2Br-TPE and CuCN in
tetrahydrofuran (THF) was performed to attach the CN
moieties to TPE. To a 100 mL two-necked round-bottomed
flask, 2Br-TPE (2 g, 5 mmol), CuCN (1.1 g, 12.2 mmol) and
anhydrous THF (30 mL) were added. The mixture was heated
at 160 °C for 3 days, and then cooled down to 90 °C.
Fluorescence titration.
Solvent-free 1 was added to water, and the mixture was kept under
vortex for 30 s to form a suspension with a concentration of 0.3
Fig. 1 (A) Structure of BCTPE2- ligand in complex 1. (B) Structure of Zn4O(CO2)6 node in complex 1. (C) Cubic structure of single net of
complex 1. (D) Overall crystal structure of complex 1 (two-fold interpenetration and 1D pore). Hydrogen atoms are omitted, and
solvent molecules are removed by using the SQUEEZE routine of PLATON for clarity.
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
Page 3 of 7
Journal of Materials Chemistry C
Journal Name
ARTICLE
mg/mL. Since nitrobenzene (NB) is almost insoluble in water, we corresponding to a void of around 47.4% per unit cell V(2ie2w0A6rt6ic.l0e OÅn3linine
DOI: 10.1039/C7TC05535H
chose methanol as dispersant for detection. The fluorescence total), almost twice larger than that of classic reported MOF-5
titration was performed by adding analytes to solvent-free 1 (12860.0 Å3 in total) as calculated by using the PLATON.41
suspension and the photoluminescence (PL) spectra of the
General characterizations.
suspension were recorded on
a
Perkin-Elmer LS 55
Powder X-ray diffraction patterns (PXRD) of complex 1 and solvent-
free 1 confirmed that the bulk samples are of high purity and the
structure of solvent-free 1 is retained without collapses. Moreover,
solvent-free 1 shows good stability in H2O and methanol as proved
by PXRD patterns, which is the same as other MOFs with octahedral
oxozinc clusters (Fig. 2). Thermogravimetric analysis (TGA) of
complex 1 reveals 25% initial weight loss after heating from 30 to
180 °C in nitrogen stream, which is attributed to solvent removal. A
second sharp weight loss (~50%) occurs at 450−500 °C,
corresponding to the decomposition of the framework. However,
solvent-free 1 only starts to loose weight at 450 °C (Fig. S3),
indicative of the absence of solvent molecules.
To investigate the permanent porosity, solvent-free 1 was
activated at 333 K under vacuum for 7 h. The nitrogen sorption
isotherm for solvent-free 1 at 77 K shows a typical behavior of
microporous materials, that is a steep nitrogen uptake at low
relative pressure (P/P0 < 0.01) (Fig. 3). The Brunauer−Emmett−Teller
and Langmuir specific surface areas of solvent-free 1 estimated by
nitrogen sorption isotherms are 530.6 and 682.6 m2/g, respectively.
spectrofluorometer. By setting the excitation wavelength at 365
nm, the emission spectra from 400 to 700 nm were collected at
room temperature.
Results and discussion
Topological analysis
Single-crystal X-ray diffraction analysis revealed that complex 1
_
crystallizes in the trigonal space group R3 (Table S1). Its framework
consists of [Zn4(μ4-O)]6+ cluster cores, which are connected with six
carboxylate groups from six (trans)-H2BCTPE ligands (Fig. 1A) to
form a classic Zn4O(CO2)6 node (Fig. 1B). The bond lengths of Zn-O
are between 1.920‒1.974 Å, tallying with that of reported
octahedral oxozinc clusters compounds. The Zn4O(CO2)6 nodes are
further linked by BCTPE2‒ with co-shared carboxylate groups to
generate a cubic 3D framework, and the length of each edge is
19.47 Å (Fig. 1C). A two-fold interpenetrated framework is observed
for the entire structure (Fig. 1D). The further investigation of
geometrical conformation for BCTPE2- in complex 1 shows that the
average dihedral angles between phenyl rings and the ethene stator
are around 55° (Fig. S1). There are C−H···π interactions with a
distance of 3.24 Å formed between adjacent phenyl rings of TPE
moieties (Fig. S2). The pore volume of complex 1 is 10458.4 Å3,
Optical properties.
H2BCTPE shows a broad absorption band around 330 nm in dilute
THF solution, which mainly stems from the π−π* transition of the
Fig. 2 The PXRD patterns of simulated 1, complex 1, solvent-free
1 and solvent-free 1 after being soaked in H2O and MeOH,
respectively.
Fig. 4 (A) Photoluminescence (PL) spectra of H2BCTPE in
THF/water mixtures with various water fractions (ƒw). Inset:
photos of H2BCTPE in THF/water mixtures (fw = 99 and 0 vol%).
(B) Solid-state PL spectra of complex 1, solvent-free 1 and
H2BCTPE.
Fig. 3 Nitrogen sorption isotherms of solvent-free 1 at 77 K.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please do not adjust margins
Journal of Materials Chemistry C
Page 4 of 7
ARTICLE
Journal Name
S5). The bright emission and good water dispersion ofVsieowlvAerntictl-efOrenelin1e
DOI: 10.1039/C7TC05535H
inspired us to explore its potential applications in detection of nitro-
conjugated molecular backbone (Fig. S4). H2BCTPE, like most TPE
derivatives, exhibits prominent AIE attribute. As depicted in Fig. 4A,
it shows faint emission in THF solution or THF/water mixture with a
water fraction (fw, vol%) less than 80%. But its emission intensity is
rapidly enhanced at a higher fw. H2BCTPE emits strong fluorescence
with an emission peak at 503 nm in the aggregated state. The
fluorescence quantum yield (ΦF) of H2BCTPE is 24.5% in solid, which
is amongst those of carboxyl-substituted TPE derivatives.42 The ΦF
of H2BCTPE is much higher than that of tetracarboxyl-substituted
TPE in solid (0.8%).11c Compared with H2BCTPE, complex 1 and
solvent-free 1 show slightly blue-shifted emission peaks at 495 and
499 nm, respectively (Fig. 4B), owing to the more rigidified
molecular structure and thus reduced reorganization energy.43-45
The ΦFs of solvent-free 1 and complex 1 are 44.1% and 64.5%,
respectively, much higher than that of H2BCTPE (24.5%) in solid. The
fluorescence lifetimes (τ) of H2BCTPE solid, solvent-free 1 and
complex 1 are 4.31, 3.83 and 3.78 ns, respectively, which agree well
with the tendency of ΦFs. This is also caused by the more rigidified
molecular structure of TPE moiety when embedded into the
framework. Complex 1 has a higher ΦF solvent-free 1, probably
owing to the formation of C−H···π interaction between TPE moieties
and trapped solvent molecules. The collective forces can further
restrict molecular motions and prevent excited-state structure
distortion of TPE moieties in the framework, and thus give rise to a
higher ΦF.16, 18a, 46
containing explosives, such as nitrobenzene (NB), 4-nitrophenol (NP)
and 2,4,6-trinitrophenol (TNP) in aqueous media. The quenching
efficiency (QE) is estimated using the formula of (I0 ‒ I)/I0 (I0 is initial
fluorescence intensity and I is fluorescence intensity after adding
guest molecules).47,48 In the presence of 50 ppm analytes, the
emission intensity of solvent-free 1 declines to different extents.
The QE of NB is 7%, while those of NP and TNP are increased to 76%
and 90%, respectively (Fig. 5A to 5C). To examine the sensitivity of
solvent-free
1 dispersed in water towards nitro-containing
explosives in detail, the fluorescence titrations with gradual
additions of NB, NP and TNP were preformed and the changes in
emission intensity was monitored (Fig. S6, S8 and S10). The linear
quenching ranges of solvent-free 1 suspension upon the additions
of NB, NP and TNP are showed in Fig. S7B, S9B and S11B. From a
ratio of 3σ/k (σ: standard deviation; k: slope), the limits of detection
(LOD) are calculated to be 10, 0.13 and 0.1 ppm for NB, NP and TNP,
respectively. The detection limits are further confirmed by the
fluorescence titrations of these analytes at low concentrations (Fig.
S6 to S11). Hydrogen bonding interactions (e.g.) between the
hydroxyl of analytes and the oxygen of BCTPE2- may bring analytes
closer to solvent-free 1 and facilitate interactions between them.49
Antibiotics detection.
Nitro explosives detection.
According to Announcement No. 235 of the Ministry of Agriculture
of the People's Republic of China, nitro-containing antibiotics,
metronidazole and nitrofurazone, cannot exist in Food-Producing
Solvent-free 1 is dispersed into H2O, followed by 30 seconds vortex
to form a stable suspension, which emits strongly at 489 nm (Fig.
Fig. 5 (A) Correlation between the quenching efficiency and concentration of TNP, NP and NB within 100 ppm. (B) The quenching
efficiency of solvent-free 1 suspension by 50 ppm TNP, NP and NB (λex= 365 nm). (C) Photos of solvent-free 1 suspension and solvent-
free 1 suspension with TNP, NP and NB (50 ppm). (D) Fluorescence titration of solvent-free 1 in water suspension with varied
concentrations of nitrofurazone (λex = 365 nm). Inset: photos of solvent-free 1 in water suspension with 0 and 65.5 ppm nitrofurazone.
(E) Correlation between the quenching efficiency and concentration of nitrofurazone. Inset: the linear relationship of fitting (0‒3
ppm). (F) Reproducibility of the quenching ability of solvent-free 1 with nitrofurazone. (The blue bars represent the initial
fluorescence intensity, and the red bars represent the intensity upon the addition of 65 ppm nitrofurazone.)
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
Page 5 of 7
Journal of Materials Chemistry C
Journal Name
ARTICLE
Animals. Hence, solvent-free 1 dispersed in water is used to detect
these antibiotics. The emission intensity of solvent-free 1 is
decreased drastically by 93% of the original intensity at 50 ppm of
nitrofurazone, and 50% at the same concentration of metronidazole
(Fig. S12), which are discernible by the naked eye. As shown in Fig.
5, the emission solvent-free 1 starts to decrease upon the addition
of 0.3 ppm nitrofurazone and 2.0 ppm metronidazole. The lowest
concentrations for complete quenching (QE = 97%) are 65 ppm for
nitrofurazone and 900 ppm for metronidazole. The LODs of
nitrofurazone and metronidazole are calculated to be 0.1 and 0.6
ppm, respectively, which are confirmed by fluorescence titrations at
low concentrations (Fig. S13 to S16). Solvent-free 1 exhibits higher
sensitivities towards nitrofurazone and metronidazole than NB (10
ppm), and the LODs of antibiotics are comparable to that of TNP
(0.1 ppm). In addition, solvent-free 1 can be reused by centrifuging
the suspension and washing with water for several times.50
Obviously, solvent-free 1 can meet the requirements in detection of
antibiotics metronidazole and nitrofurazone. To understand the
sensing mechanism, the HOMO and LUMO energy levels of NB, NP,
TNP, nitrofurazone, metronidazole and H2BCTPE are investigated
theoretically.51 It is found that the excited-state electron transfer
from the higher LUMO of H2BCTPE (‒1.94 eV) to those of analyte
(<‒2.22 eV) may occur under photon excitation, resulting in severe
fluorescence quenching (Fig. S17). Therefore, the photon-induced
electron transfer (PET) could play a crucial role in the detection of
these analytes. On the othe hand, the fluorescence resonance
energy transfer (FRET) hardly contributes to the fluorescence
quenching because of less overlap between the absorption spectra
of nitro-containing analysts and emission spectrum of solvent-free 1
(Fig. S18).
Acknowledgements
View Article Online
DOI: 10.1039/C7TC05535H
We thank for financial support from the National Natural Science
Foundation of China (21788102 and 21671051), the Zhejiang
Provincial Natural Science Foundation of China (LY15B010006 and
LY16B010003) and the Innovative Research Team in Chinese
University (IRT 1231). X.-G. Liu thanks the financial support from
climb project–phase II for discipline construction project of
Hangzhou normal university. Z.Z. thanks the financial support from
Guangdong Natural Science Funds for Distinguished Young Scholar
(2014A030306035). We also thank Dr Zaichao Zhang for his
assistance in crystallographic analysis.
Notes and references
1
2
3
Y. Cui, Y. Yue, G. Qian and B. Chen, Chem. Rev., 2012, 112,
1126.
W. P. Lustig, S. Mukherjee, N. D. Rudd, A. V. Desai and J. Li,
Chem. Soc. Rev., 2017, 46, 3242.
(a) Y. Cui, B. Li, H. He, W. Zhou, B. Chen and G. Qian, Acc.
Chem. Res., 2016, 49, 483; (b) L. E. Kreno, K. Leong, O. K.
Farha, M. Allendorf, R. P. V. Duyne and J. T. Hupp, Chem.
Rev., 2012, 112, 1105.
4
5
6
7
J. Heine and K. Muller-Buschbaum, Chem. Soc. Rev., 2013, 42
9232.
,
X. Yan, T. R. Cook, P. Wang, F. Huang and P. J. Stang, Nat.
Chem., 2015, 7, 342.
J. Mei, N. L. C. Leung, R. T. K. Kwok, J. W. Y. Lam and B. Z.
Tang, Chem. Rev., 2015, 115, 11718.
(a) S. Dalapati, C. Gu and D. Jiang, Small, 2016, 47, 6513; (b)
V. W.-W. Yam, V. K.-M. Au and S. Y.-L. Leung, Chem. Rev.,
2015, 115, 7589.
8
(a) L. Ma, X. Feng, S. Wang and B. Wang, Mater. Chem. Front.,
2017, , 2474; (b) Y. Guo, X. Feng, T. Han, S. Wang, Z. Lin, Y.
Dong and B. Wang, J. Am. Chem. Soc., 2014, 136, 15485; (c) Z.
1
Zhao, J. W. Y. Lam and B. Z. Tang, J. Mater. Chem., 2012, 22
23726.
Z. Hu, B. J. Deibert and J. Li, Chem. Soc. Rev. 2014, 43, 5815.
,
Conclusions
9
In summary, a new dicarboxyl-substituted, AIE-active TPE derivative,
H2BCTPE, is designed and synthesized. Based on H2BCTPE, we have
developed a two-fold interpenetrated LMOF [Zn4O(BCTPE)3] (1)
with a classical Zn4O(CO2)6 nodes. Although H2BCTPE is a mixture of
cis- and trans-isomers obtained from McMurry coupling, only trans-
isomer of H2BCTPE is spontaneously incorporated complex 1 .
10 F.-Y. Yi, D. Chen, M.-K. Wu, L. Han and H.-L. Jiang,
ChemPlusChem, 2016, 81, 675.
11 (a) N. B. Shustova, T.-C. Ong, A. F. Cozzolino, V. K. Michaelis,
R. G. Griffin and M. Dincă, J. Am. Chem. Soc., 2012, 134
,
15061; (b) N. B. Shustova, A. F. Cozzolino and M. Dincă, J. Am.
Chem. Soc., 2012, 134, 19596; (c) N. B. Shustova, B. D.
McCarthy and M. Dincă, J. Am. Chem. Soc. 2011, 133, 20126.
Solvent-free 1 is highly emissive, thermal stable and water stable, 12 S. L. Jackson, A. Rananaware, C. Rix, S. V. Bhosale and K.
Latham, Cryst. Growth Des., 2016, 16, 3067.
and exhibits a typical behavior of microporous materials. The
emission of solvent-free 1 can be quenched efficiently by nitro-
containing explosives, and a reversible method to sensitively and
quantitatively detect trace NP and TNP in water is established. In
13 (a) B. J. Deibert, E. Velasco, W. Liu, S. J. Teat, W. P. Lustig and
J. Li, Cryst. Growth Des., 2016, 16, 4178; (b) Z. Hu, W. P.
Lustig, J. Zhang, C. Zheng, H. Wang, S. J. Teat, Q. Gong, N. D.
Rudd and J. Li, J. Am. Chem. Soc., 2015, 137, 16209.
addition, solvent-free 1 also shows good performance in the 14 (a) X. Liu, J. C. Steele and X.-Z. Meng, Environ. Pollut., 2017,
223, 161; (b) Z. Zhou, C. He, J. Xiu, L. Yang and C. Duan, J. Am.
Chem. Soc., 2015, 137, 15066.
15 M. Zhang, G. Feng, Z. Song, Y-P. Zhou, H.-Y. Chao, D. Yuan, T.
T. Y. Tan, Z. Guo, Z. Hu, B. Z. Tang, B. Liu and Dan Zhao, J. Am.
Chem. Soc., 2014, 136, 7241.
detection of antibiotics with low LODs of 0.6 ppm and 0.1 ppm for
metronidazole and nitrofurazone, respectively, in aqueous
conditions. These results demonstrate that solvent-free 1 is a
promising candidate for the detection of nitro-containing explosives
and antibiotics in aqueous environments. Further studies of 16 C.-L. Tao, B. Chen, X.-G. Liu, L.-J. Zhou, X.-L. Zhu, J. Cao, Z.-G.
Gu, Z. Zhao, L. Shen and B. Z. Tang, Chem. Commun., 2017,
53, 9975.
17 J. Shi, W. Zhao, C. Li, Z. Liu, Z. Bo, Y. Dong, T. Dong and B. Z.
Tang, Chin. Sci. Bull., 2013, 58, 2723.
detecting other drugs as well as heavy metal pollutants with TPE-
based LMOFs are in progress.
18 (a) Z. Wei, Z.-Y. Gu, R. K. Arvapally, Y.-P. Chen, J. R. N.
McDougald, F. I. Joshua, A. A. Yakovenko, D. Feng, M. A.
Omary and H.-C. Zhou, J. Am. Chem. Soc., 2014, 136, 8269; (b)
Q. Gong, Z. Hu, B. J. Deibert, T. J. Emge, S. J. Teat, D.
Conflicts of interest
There are no conflicts to declare.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Please do not adjust margins

Please do not adjust margins
Journal of Materials Chemistry C
Page 6 of 7
ARTICLE
Journal Name
Banerjee, B. Mussman, N. D. Rudd and J. Li, J. Am. Chem. Soc., 47 S.-Y. Zhang, W. Shi, P. Cheng and M. J. ZawoVrioewtkAort,iclJe.OAnlmine.
2014, 136, 16724. Chem. Soc., 2015, 137, 12203.
19 Y. Wang, B. Yuan, Y.-Y. Xu, X.-G. Wang, B. Ding and X.-J. Zhao, 48 X.-G. Hou, Y. Wu, H.-T. Cao, H.-Z. Sun, H.-B. Li, G.-G. Shan and
Chem. Eur. J., 2015, 21, 2107. Z.-M. Su, Chem. Commun., 2014, 50, 6031.
20 X.-G. Liu, H. Wang, B. Chen, Y. Zou, Z.-G. Gu, Z. Zhao and L. 49 (a) Y. Zhang, B. Li, H. Ma, L. Zhang and W. Zhang, J. Mater.
DOI: 10.1039/C7TC05535H
Shen, Chem. Commun., 2015, 51, 1677.
21 N. B. Shustova, A. F. Cozzolino and M. Dincă, J. Am. Chem.,
Soc. 2012, 134, 19596.
22 X. Wang, O. S. Wolfbeis and R. J. Meier, Chem. Soc. Rev.,
2013, 42, 7834.
23 K. Kꢀmmerer, Chemosphere, 2009, 75, 417.
Chem. C, 2017,
Dong, S. Zang and H. Hou, J. Mater. Chem. A, 2015,
(c) Q. Tan, Y. Wang, X. Guo, H. Liu and Z. Liu, RSC Adv., 2016,
6, 61725; (d) Z. Sun, Y. Li, Y. Ma and L. Li, Dyes Pigm., 2017,
146, 263; (e) R. Dalapati and S. Biswas, Sensor Actuat B:
Chem., 2017, 239, 759.
5
, 4661; (b) J. Qin, B. Ma, X. Liu, H. Lu, X.
3
, 12690;
24 Q.-Q. Zhang, G.-G. Ying, C.-G. Pan, Y.-S. Liu and J.-L. Zhao, 50 W.-M. Chen, X.-L. Meng, G.-L. Zhuang, Z. Wang, M. Kurmoo,
Environ. Sci. Technol., 2015, 49, 6772.
25 P. W. Seo, N. A. Khan and S. H. Jhung, Chem. Eng. J., 2017
315, 92.
26 N. Lu, T. Wang, P. Zhao, L. Zhang, X. Lun, X. Zhang and X.
Hou, Anal. Bioanal. Chem., 2016, 408, 8515.
27 M. Ibrahim, R. Sabouni and G. Husseini, Curr. Med. Chem.,
2017, 24, 193.
Q.-Q. Zhao, X.-P. Wang, B. Shan, C.-H. Tung and D. Sun, J.
Mater. Chem. A, 2017, , 13079.
51 (a) Y. Zhao, X. Xu, L. Qiu, X. Kang, L. Wen and B. Zhang, ACS
,
5
Appl. Mater. Interfaces, 2017, 9, 15164; (b) S. S. Nagarkar, A.
V. Desai and S. K. Ghosh, Chem. Commun., 2014, 50, 8915;
(c) M. Gao, Y. Wu, B. Chen, B. He, H. Nie, T. Li, F. Wu, W.
Zhou, J. Zhou and Z. Zhao, Polym. Chem., 2015, 6, 7641; (d) D.
28 B. Wang, X.-L. Lv, D. Feng, L.-H. Xie, J. Zhang, M. Li, Y. Xie, J.-R.
Li and H.-C. Zhou, J. Am. Chem. Soc., 2016, 138, 6204.
29 F. Zhang, H. Yao, Y. Zhao, X. Li, G. Zhang and Y. Yang, Talanta,
2017, 174, 660.
Chen, J. Tian, Z. Wang, C. Liu, M. Chen and M. Du, Chem.
Commun., 2017, 53, 10668.
30 D. Zhao, X.-H. Liu, Y. Zhao, P. Wang, Y. Liu, M. Azam, S. I. Al-
Resayes, Y. Lu and W.-Y. Sun. J. Mater. Chem. A, 2017, 5,
15797.
31 F. Zhang, H. Yao, T. Chu, G. Zhang, Y. Wang and Y. Yang, Chem.
Eur. J., 2017, 23, 10293.
32 N. S. Bobbitt, M. L. Mendonca, A. J. Howarth, T. Islamoglu, J.
T. Hupp, O. K. Farha and R. Q. Snurr, Chem. Soc. Rev., 2017,
46, 3357.
33 (a) W. Li, X. Qi, C.-Y. Zhao, X.-F. Xu, A.-N. Tang and D.-M.
Kong, ACS Appl. Mater. Interfaces, 2017, 9, 236; (b) Q. Zhang,
J. Su, D. Feng, Z. Wei, X. Zou and H.-C. Zhou, J. Am. Chem.
Soc., 2015, 137, 10064.
34 B. Wang, Q. Yang, C. Guo, Y. Sun, L.-H. Xie and J.-R. Li, ACS
Appl. Mater. Interfaces, 2017, 9, 10286.
35 B.-L. Hou, D. Tian, J. Liu, L.-Z. Dong, S.-L. Li, D.-S. Li and Y.-Q.
Lan, Inorg. Chem., 2016, 55, 10580.
36 F.-L. Yuan, Y.-Q. Yuan, M.-Y. Chao, D. J. Young, W.-H. Zhang
and J.-P. Lang, Inorg. Chem., 2017, 56, 6522.
37 R. J. Marshall, Y. Kalinovskyy, S. L. Griffin, C. Wilson, B. A.
Blight and R. S. Forgan, J. Am. Chem. Soc. 2017, 139, 6253.
38 L. Li, X. Cao and R. Huang, Chin. J. Chem., 2016, 34, 143.
39 M. Eddaoudi, J. Kim, N. Rosi, D. Vodak, J. Wachter, M.
O’Keeffe and O. M. Yaghi, Science, 2002, 98, 469.
40 C. A. Bauer, T. V. Timofeeva, T. B. Settersten, B. D. Patterson,
V. H. Liu, B. A. Simmons and M. D. Allendorf, J. Am. Chem.
Soc., 2007, 129, 7136.
41 Spek, A. L. PLATON: A Multipurpose Crystallographic Tool;
Utrecht University: Utrecht, The Netherlands, 2001.
42 J. Mei, Y. Hong, J. W. Y. Lam, A. Qin, Y. Tang and B. Z. Tang,
Adv. Mater. 2014, 26, 5429.
43 (a) S. Yuan, Y.-K. Deng and D. Sun, Chem. Eur. J., 2014, 20
,
10093; (b) Q. Wu, T. Zhang, Q. Peng, D. Wang and Z. Shuai,
Phys. Chem. Chem. Phys., 2014, 16, 5545.
44 (a) L. Zhou, Z.-G. Wang, H.-Y. Dong, K. Zhao, Y.-J. Hu, Z.-J.
Gao, S.-N. Tie and H.-G. Zheng, Inorg. Chem. Commun., 2017,
78, 1; (b) F. Bu, R. Duan, Y. Xie, Y. Yi, Q. Peng, R. Hu, A. Qin, Z.
Zhao and B. Z. Tang, Angew. Chem. Int. Ed., 2015, 54, 14492;
(c) W. Luo, H. Nie, B. He, Z. Zhao, Q. Peng and B. Z. Tang,
Chem. Eur. J., 2017, DOI: 10.1002/chem.201704182.
45 D. Jonckheere, J. A. Steele, B. Claes, B. Bueken, L. Claes, B.
Lagrain, M. B. J. Roeffaers and D. E. D. Vos, ACS Appl. Mater.
Interfaces, 2017, 9, 30064.
46 Y. Fushimi, M. Koinuma, Y. Yasuda, K. Nomura and M. S.
Asano, Macromolecules, 2017, 50, 1803.
6 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 7 of 7
Journal of Materials Chemistry C
View Article Online
DOI: 10.1039/C7TC05535H
A new luminescent metal-organic framework based on dicarboxyl-
substituted tetraphenylethene for efficient detection of nitro-containing
explosives and antibiotics in aqueous media
Xun-Gao Liu, *a Chen-Lei Tao,a Huang-Qin Yu,a Bin Chen,b Zhen Liu,a Gen-Ping Zhu,a Zujin Zhao,*b Liang Shen,*a and
Ben Zhong Tangbc
Table of contents entry
A tetraphenylethene-based luminescent metal-organic framework with high fluorescence quantum yield efficiently and quantitatively detected
trace nitro-containing antibiotics in aqueous media.
This journal © Royal Society of Chemistry