A copillar[5]arene-based fluorescence “on-off-on” sensor is applied in sequential recognition of an iron cation and a fluoride anion

Article abstract of DOI:10.1039/c6nj03380f

We have synthesized a copillar[5]arene-based fluorescence “on-off-on” sensor (DBP5) and used it for sequential fluorescence sensing for Fe³⁺ and F^- in H₂O/DMSO (1:9, v/v) solution. The copillar[5]arene DBP5 can produce blu

Full text of DOI:10.1039/c6nj03380f

View Article Online
View Journal
NJC
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: J. Chen, X.
Cheng, H. Li, Q. Lin, H. Yao, Y. Zhang and T. Wei, New J. Chem., 2017, DOI: 10.1039/C6NJ03380F.
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Volume 40 Number
1 January 2016 Pages 1–846
NJC
Accepted Manuscripts are published online shortly after
New Journal of Chemistry
www.rsc.org/njc
A journal for new directions in chemistry
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 1144-0546
PAPER
Jason B. Benedict et al.
The role of atropisomers on the photo-reactivity and fatigue of
diarylethene-based metal–organic frameworks
rsc.li/njc

Page 1 of 7
New Journal of Chemistry
View Article Online
DOI: 10.1039/C6NJ03380F
A copillar[5]areneꢀbased fluorescent “onꢀoffꢀon” sensor is applied
in sequential recognition of iron cation and fluoride anion
JinꢀFa Chen, XiaoꢀBin Cheng, Hui Li, Qi Lin*, Hong Yao, YouꢀMing Zhang, TaiꢀBao Wei*
Received (in XXX, XXX) XthXXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
DOI: 10.1039/c0xx00000x
We have synthesized a copillar[5]areneꢀbased fluorescent “onꢀoffꢀon”
sensor (DBP5) and used it for sequential fluorescent sensing for Fe3+ and
F− in H2O/DMSO (1 : 9 , v/v) solution. Copillar[5]arene DBP5 can produce
blue fluorescence because it easily forms [c2]daisyꢀchain dimers by the
selfꢀassembly behavior in solution. DBP5 exhibits high selectivity and
sensitivity (1.65×10ꢀ8 M) to Fe3+. Moreover, the in situ formed DBP5−Fe3+
complex further utilized to sense the F− through complexation reaction
with high selectivity and sensitivity (6.44×10ꢀ8 M) to F−. Furthermore, we
designed the fluorescent switch of DBP5 between Fe3+ and F−. The
structure of DBP5 was proved by single crystal XRD.
simple, easy and sequential detection of Fe3+ and F− has
Introduction
attracted our attention.
Among the many metals and nonmetals in ecology
Pillararenes are a newest group of supramolecular
and the environment, both iron and fluorine are the most
macrocycles first developed in 2008.6 they have novel
plentiful necessary elements found in the human body
host–guest binding properties due to being easier to
and are critical for maintaining significant physiological
functionalize by special substituents on the benzene
processes. Iron ion (Fe3+) plays the crucial roles in
rings,7 thus functionalized pillararenes attracted a lot of
oxygen uptake, oxygen metabolism, electron transfer,
attention of scientists.8 Due to pillararenes have π
and transcriptional regulation.1 Lack of iron ions can
electronic cavities, they should have corresponding ion
lead to the permanent loss of motor skills, and its excess
responsive fluorescent properties.9 However, only a
can lead to diseases such as Parkinson’s and
handful of paper reported that pillararenes are used to
Alzheimer’s.2 A safe limit for the Fe3+ was restricted to
recognise ions,10 this may greatly impede the application
2 mg L−1 by the World Health Organization. Therefore,
of pillararenes. Therefore, it is quite necessary to design
it is very necessary to find some simple, rapid, and
and synthesize ion responsive fluorescent pillararenes.
efficient methods for the detection of Fe3+ at trace levels
In view of this, and as a part of our research interest
in biological and food specimens.3 Generally speaking,
in pillararenes chemistry and ion recognition,11 we
−
the iron complexes may be used to detect H2PO4
synthesize a fluorescent “onꢀoffꢀon” sensor DBP5 for
because H2PO4− has better binding ability with Fe3+ to
Fe3+ and F−. According to a previous report,12 the sensor
form a complex (Fe(H2PO4)3),4 several fluorescent
DBP5 was synthesized via a 2ꢀstep pathway (Scheme 1).
receptors for iron and fluoride ions have been reported,
The target compound and intermediates were
so the realization of both Fe3+ and F− for fluorescence
characterized by 1H NMR spectrum, 13C NMR spectrum
measurements is still
a challenge. Fluoride anion
and ESI−MS (Fig. S1–S4). Fortunately, by slow
evaporation of solution of DBP5 in
extremely attracting our attention because they
significantly influence our environment and health. A
high intake of fluoride can result in dental fluorosis and
skeletal fluorosis, but a low intake of fluoride can result
in caries.5 The United States Environmental Protection
Agency (EPA) obtains an executable drinking water
standard for fluoride of 4 mg L−1 to prevent skeletal
fluorosis. Therefore, the synthesis of new sensors for the
a
a
dichloromethane/ethanol mixture (1 : 1, v/v) at room
temperature, crystals suitable for Xꢀray analysis were
obtained (Fig. 1). The crystal structure gave direct proof
that
copillar[5]arene
DBP5
units
contained
one
four
1,4ꢀbis
1,4ꢀdimethoxybenzene
and
(4ꢀbromobutoxy)benzene units. The selfꢀassembly
behavior of the [c2]daisy chainꢀforming compound
DBP5 was reported.13 This report suggested that the

New Journal of Chemistry
Page 2 of 7
View Article Online
DOI: 10.1039/C6NJ03380F
aggregates of copillar[5]arene DBP5 changed from
Mercury−600BB spectrometer at 150 MHz. Chemical
selfꢀencapsulation monomers into [c2]daisy chain
dimers in solution. The 2D NOESY spectrum (Fig. S5)
also shows that there is a certain selfꢀassembly behavior.
Thus, the monomers DBP5 may forms strong
fluorescence dimers by the selfꢀassembled between the
pillar[5]arene units and Br(CH2)4− units. It is
noteworthy that the DBP5 could be a sequential
fluorescent sensor for iron ions followed by fluoride
ions with high sensitivity and selectivity in aqueous
solutions.
shifts are reported in ppm downfield from
tetramethylsilane (TMS, δ scale with solvent resonances
as internal standards). Melting points were measured on
an X−4 digital melting−point apparatus (uncorrected).
Mass spectra were performed on a Bruker Esquire 3000
plus mass spectrometer (Bruker−FranzenAnalytik
GmbH Bremen, Germany) equipped with ESI interface
and ion trap analyzer.
Synthesis
Synthesis of 1,4−bis(4−bromobutoxy)benzene 1
Hydroquinone (2.3 g, 20.0 mmol), K2CO3 (16.6 g,
120 mmol), KI (6.6 g, 40 mmol), 1,4−dibromobutane
(34.6 g, 160 mmol) and acetone (400.0 mL) were added
in a 500 mL round–bottom flask stirred at room
temperature. The reaction mixture was stirred at reflux
for 1.5 days. After the solid was filtered off, the solvent
was evaporated and the residue was dissolved in
CH2Cl2. Column chromatography (silica gel; petroleum
ether : CH2Cl2=10 : 1) afforded a white solid (6.0 g,
80%). Mp 83−85°C. 1H NMR (600 MHz, CDCl3) δ 6.83
(d, J = 0.8 Hz, 4H), 3.96 (t, J =6.0 Hz, 4H), 3.52–3.25
(m, 4H), 2.10–1.88 (m, 8H).
Synthesis of a copillar[5]arene DBP5
To a solution of 1,4−bis(4−bromobutoxy) benzene
(1.9 g, 5.0 mmol) and 1,4−dimethoxybenzene (2.76 g,
20.0 mmol) in 1, 2−dichloroethane (200 mL),
paraformaldehyde (0.75 g, 25.0 mmol) was added under
nitrogen atmosphere. Then boron trifluoride diethyl
etherate (6.75 mL, 25 mmol) was added to the solution
and the mixture was stirred at room temperature for 4 h
and concentrated by rotary evaporation. The resultant oil
was dissolved in CH2Cl2 and washed twice with H2O.
The organic layer was dried over anhydrous Na2SO4 and
evaporated to afford the crude product, which was
isolated by flash column chromatography using
petroleum ether/ethyl acetate (20 : 1,v/v) to give DBP5
(1.69 g, 34%) as a white solid. Mp 187−189 °C. 1H
NMR (600 MHz, CDCl3) δ 6.84–6.74 (m, 10H), 3.87 (t,
J= 5.9 Hz, 4H), 3.83–3.78 (m, 10H), 3.72 (t, J= 19.9 Hz,
24H), 3.33 (s, 4H), 1.94 (s, 4H), 1.84 (s, 4H). 13C NMR
(151 MHz, CDCl3) δ 150.80 (s), 150.75 (s), 150.70 (s),
150.58 (s), 149.84 (s), 128.44 (s), 128.30 (s), 128.08 (s),
114.89 (s), 114.15 (s), 113.92 (s), 113.71 (s), 67.32 (s),
55.95 (d, J= 3.6 Hz), 55.76 (s), 55.70 (s), 33.34 (s),
30.55 (s), 29.75 (s), 29.48 (d, J= 5.2 Hz), 29.19 (s),
28.32 (s). ESI−MS m/z: (M+NH4)+ Calcd for
C51H64O10Br2N 1010.2871; Found 1010.2878.
Scheme 1 Synthesis of copillar[5]arene DBP5.
Fig. 1 The crystal structure of DBP5: (a) side view and
(b) top view. Oxygen atoms are red balls, hydrogen
atoms are green balls, carbon atoms are white balls.
Experimental section
Materials and instruments
1, 4−Dimethoxybenzene, boron trifluoride ethyl ether
complex and 1,4−dibromobutane were reagent grade and
used as received. Solvents were either employed as
purchased or dried by CaCl2. 1H NMR spectra were
recorded on a Mercury−600BB spectrometer at 600
MHz and 13C NMR spectra were recorded on a
Results and discussion

Page 3 of 7
New Journal of Chemistry
View Article Online
DOI: 10.1039/C6NJ03380F
In order to investigate the influence of metal ions of
were carried out in the presence of 2.0 equiv. of Fe3+ and
the sensor DBP5 in H2O/DMSO (1 : 9 , v/v) solution, a
series of host−guest recognition experiments were
carried out. The sensor DBP5 toward various cations
(including Fe3+, Hg2+, Co2+, Ca2+, Ni2+, Pb2+, Cd2+, Zn2+,
Cr3+, Mg2+, Fe2+ and Ag+) were primarily investigated
using fluorescence spectroscopy. The free sensor DBP5
showed an absorption peak at 295 nm (Fig. S6). In the
fluorescence spectrum, the maximum emission of DBP5
appeared at 330 nm in H2O/DMSO (1 :9 , v/v) solution
while excited at λex = 295 nm. When 2.0 equiv. of Fe3+
was added to the solution of sensor DBP5, the
fluorescence emission band was quenched (Fig. S7). The
same tests were applied using Fe3+, Hg2+, Co2+, Ca2+,
Ni2+, Pb2+, Cd2+, Zn2+, Cr3+, Mg2+, Fe2+ and Ag+ cations,
and only Fe3+ have significant changes in the
fluorescence spectrum, and none of those other cations
induced any significant changes in the fluorescent
spectrum (Fig. 2).
2.0 equiv. of various cations in H2O/DMSO (1 : 9 , v/v)
solution. The fluorescence selectivity was examined at
an emission wavelength of 330 nm, all the competing
cations did not interfere in the detection of Fe3+ (Fig. 4).
This result displayed high selectivity of the sensor
DBP5 toward Fe3+ over other analytes mentioned above.
Fig. 3 Fluorescence spectra of DBP5 (2×10ꢀ4 M) in the
presence of different concentration of Fe3+ in
H2O/DMSO (1 : 9 , v/v) solution.
Fig. 2 Fluorescence spectra responses for DBP5 (2×10ꢀ4
M) and each of the various cations (4×10ꢀ4 M) as the
perchlorate, in the H2O/DMSO (1 : 9 , v/v) solution.
Inset: color changes observed for DBP5 upon the
addition of Fe3+, Hg2+, Co2+, Ca2+, Ni2+, Pb2+, Cd2+,
Zn2+, Cr3+, Mg2+, Fe2+ and Ag+ cations in H2O/DMSO (1
: 9 , v/v) solution.
Fig. 4 Fluorescence of the sensor DBP5 at 330 nm with
addition of 2.0 equiv. of Fe3+ in the presence of 2.0
equiv. of other cations in H2O/DMSO (1 : 9 , v/v)
solution.
To further investigate the efficiency of the sensor
DBP5 toward Fe3+ detection, we carried out
fluorescence emission titration experiments. In the
fluorescence spectrum, upon addition of increasing
amounts of Fe3+ ions (0~0.66 equiv.) to the solution of
DBP5, directly leading to a light purple emission almost
completely quenching (Fig. 3). The detection limit of the
fluorescent spectrum changes calculated on the basis of
3δ/S is 1.65×10ꢀ8 mol·L−1 (Fig. S8), indicating the high
sensitivity of the sensor to Fe3+. Simultaneously, this
detection limit is lower than other detection techniques
(Table S1). In addition, the fluorescence of the Job's plot
suggests that DBP5 forms a 1:1 complex with Fe3+ ion
(Fig. S9).
It is well known that anions has binding ability with
cations to form complexes, so we investigated the
fluorescence behavior of the sensor DBP5 between Fe3+
and anions. The variations of fluorescent spectrum of the
DBP5−Fe3+ complex ([DBP5]/[Fe3+]= 1 : 2, [DBP5]=
2×10ꢀ4 M) caused by the anions (1×10ꢀ3 M), namely, F−,
Cl−, Br−, I−, AcO−, H2PO4 , HSO4 , ClO4 , SCN− and
CN−, are summarized in Fig. 5. We found when a
fluoride ion was added to the DBP5−Fe3+ system, the
fluorescence intensity is completely regenerated. The
−
−
−
−
−
−
other anions (Cl−, Br−, I−, AcO−, H2PO4 , HSO4 , ClO4 ,
SCN− and CN−) show very little response. The observed
fluorescence and color regeneration can be ascribed to
the capture of Fe3+ from its chelated complexes by F−,
resulting in the formation of more stable species [FeF6]3−
and the release of free compound DBP5.
To further exploit the utility of the sensor DBP5 as
cation selective sensor for Fe3+, competitive experiments

New Journal of Chemistry
Page 4 of 7
View Article Online
DOI: 10.1039/C6NJ03380F
At the same time, fluorescence emission spectral
5.0 equiv. of various other anions in H2O/DMSO (1 : 9 ,
variation of sensor DBP5−Fe3+ in H2O/DMSO (1 : 9 ,
v/v) solution was monitored during titration with
different concentrations of F− from 0 to 7.0 equiv. The
addition of increasing concentrations of F−, the emission
peak at 330 nm gradually enhanced intensity and the
fluorescence of DBP5−Fe3+ was essentially recovered
by 5.6 equiv. of F− ion (Fig. 6). The detection limit of
the DBP5−Fe3+ for the determination of F− was
estimated to be 6.44×10ꢀ8 mol·L− (Fig. S10) pointing to
the high detection sensitivity. In addition, the changes in
the fluorescence intensity depending on the reaction
time were recorded from 0 to 150 seconds, for a 1 : 5
mixture of DBP5−Fe3+ complex and F− in H2O/DMSO
(1 : 9 , v/v) at room temperature (Fig. S11). This clearly
shows that the reaction was complete within 30 s after
the addition of F−.
v/v) solution of DBP5−Fe3+ (Fig. 7). The fluorescence
emission spectra displayed a similar pattern to that with
F− alone, suggesting that all the tested anions do not
interfere in the sensing of F−.
Due to fluoride anion has binding ability with iron
cation to form a complex [FeF6]3−, we investigated the
fluorescence “on−off−on” behavior of the sensor DBP5
between Fe3+ and F−. Fig. 8 shows the repeated
switching behavior when altering adding amounts of F−
and Fe3+ to DBP5, which evidently proved the excellent
reusability and stability of DBP5 toward Fe3+ at least for
six successive cycles.
Fig. 7 Fluorescence of the sensor DBP5−Fe3+ at 330 nm
with addition of 5.0 equiv. of F− in the presence of 5.0
equiv. of other anions in H2O/DMSO (1 : 9 , v/v)
solution.
Fig. 5 Fluorescence spectra responses for DBP5−Fe3+
and each of the various anions (1×10ꢀ3 M) as the
tetrabutylammonium salts, in the H2O/DMSO (1 : 9 ,
v/v) solution. Inset: color changes observed for
DBP5−Fe3+ upon the addition of F−, Cl−, Br−, I−, AcO−,
−
−
−
H2PO4 , HSO4 , ClO4 , SCN− and CN− anions in
H2O/DMSO (1 : 9 , v/v) solution.
Fig.
8 Emission spectra showing the reversible
complexation between DBP5 and Fe3+ (2.6 equiv.) by
introduction of F− (10.0 equiv.).
The possible mechanism was also put forward by
emission spectra. As can be seen from the emission
spectra, when adding iron ion, acyclic monomeric
analog 1 fluorescence is quenched (Fig. S12). This
shows that iron ion is coordinated with Br atom.
However, fluorescence intensity of DBP5 was
significantly higher than 1 (Fig. S13), because the
monomers DBP5 may forms strong fluorescence dimers
by the selfꢀassembled between the pillar[5]arene units
and Br(CH2)4− units. This shows that the sensor DBP5
is most likely to band with Fe3+ via Br atom on the alkyl
chain formed linear supramolecule, thereby forming a 1
: 1 complex (Scheme 2). When F− was added to the
Fig. 6 Fluorescence spectra of DBP5−Fe3+ in the
presence of different concentration of F− in H2O/DMSO
(1 : 9 , v/v) solution.
To further explore the utility of DBP5−Fe3+ as an
anion−selective sensor for F−, competitive experiments
were carried out in the presence of 5.0 equiv. of F− and

Page 5 of 7
New Journal of Chemistry
View Article Online
DOI: 10.1039/C6NJ03380F
DBP5−Fe3+ system, the capture of Fe3+ from its more
The practical utility of the probe in a daily life sample
stable complex [FeF6]3− by F− and the release of free
compound DBP5. Hereafter, the free DBP5 forming the
[c2]daisy chain by selfꢀassembly behavior.
was investigated using Fe3+ in tap water and F− in
toothpastes. The fluorescence emission spectra of DBP5
(0.2 mM in 4.5 mL DMSO) is just as line 1 shown in
Fig. 10, then, upon the titration of concentrated tap
water (0.5 mL) to obtain line 2. The fluorescence
emission spectra of the DBP5−Fe3+ complex (0.2 mM
DBP5 and 0.4mM Fe3+) is just as line 3, then, upon the
titration of soluble components of Colgate toothpaste
sample (0.5 mL DMSO) to obtain line 4. The sensor
could detect sequentially Fe3+ in tap water and F− in real
samples such as toothpastes (Fig. 10), confirming that
DBP5 is a promising Fe3+ and F− probe for practical
applications. Therefore, this copillar[5]arene DBP5 can
be used as an fluorescent sensor for the sequential
detection of Fe3+ and F− ions, which showed excellent
stability, reversibility, and repeatability.
The recognition possibilities were also investigated
by 1H NMR. Partial proton NMR spectra of DBP5,
DBP5−Fe3+ and DBP5−Hg3++F− system are shown in
Fig. S15. The addition of 2.0 equiv. of Fe3+ to DBP5
solution led to the signals of H3 of DBP5 appeared
changes. This suggested that the complexation reaction
have been taken place. When 5.0 equiv. of F− had been
added to DBP5−Fe3+ system, the signals of H3 peak
restored the original location. This implies that F−
dissociated DBP5−Fe3+ complex.
Scheme 2 The sensing mechanism of the sensor DBP5
to Fe3+ and F−.
Finally, to investigate the practical application of
DBP5, a thin film was prepared by immersing a glass
sheet into a high concentration solution of DBP5 (100
mM) and then drying it in air. The thin film was utilized
to sense Fe3+. As shown in Fig. 9, when Fe3+ were added
onto the thin film, the obvious color change was
observed under irradiation at 365 nm using a UV lamp.
Therefore, the thin film could be a convenient test kit for
Fig. 10 Fluorescence emission spectra of DBP5 (0.2
mM in DMSO) sequential detect Fe3+ in tap water and
F− in real samples such as toothpastes.
Conclusions
In summary, a fluorescent “onꢀoffꢀon” sensor (DBP5)
has been applied in sequential fluorescent sensing for
iron cation and fluoride anion in H2O/DMSO (1 : 9 ,
v/v) solution. DBP5 shows highly selective and
sensitive fluorescence “onꢀoff” behavior toward Fe3+
over other cations. The in situ prepared DBP5−Fe3+
complex exhibits high selectivity and sensitivity to F−
over other anions through a complexation reaction.
Furthermore, we designed the fluorescent switch of
DBP5 between Fe3+ and F−. This sequential recognition
behavior makes sensor DBP5 as a potential probe to
detect Fe3+ and F− in the environmental monitoring
works.
detecting Fe3+. Same manner,
a glass sheet was
immersed into a high concentration solution of DBP5 +
Fe3+ (100 mM) and then drying it in air, when F− were
added onto this thin film, the obvious fluorogenic
change was observed under irradiation at 365 nm using a
UV lamp.
Acknowledgements
Fig. 9 Photos of (A) the thin film utilized to sense Fe3+
cation and F− anion were added onto the (B) thin film
under irradiation at 365 nm using a UV lamp.
This work was supported by the National Natural
Science Foundation of China (NSFC) (no. 21574104;
21161018; 21262032) and the Program for Changjiang
Scholars and Innovative Research Team in University of
Ministry of Education of China (IRT1177).

New Journal of Chemistry
Page 6 of 7
View Article Online
DOI: 10.1039/C6NJ03380F
10 (a) Y. Fang, X. Yuan, L. Wu, Z. Peng, W. Feng, N. Liu, D.
Notes and references
Xu, S. Li, A. Sengupta, P. Mohapatra and L. Yuan, Chem.
Commun., 2015, 51, 4263; (b) P. Wei, D. Li, B. Shi, Q. Wang
and F. Huang, Chem. Commun., 2015, 51, 15169.
Key Laboratory of EcoꢀEnvironmentꢀRelated Polymer
Materials, Ministry of Education of China; Key Laboratory of
Polymer Materials of Gansu Province; College of Chemistry
and Chemical Engineering, Northwest Normal University,
Lanzhou, Gansu, 730070, P. R. China Fax: +86 9317973191;
Tel: +86 9317973191; Eꢀmail: weitaibao@126.com;
linqi2004@126.com.
† Electronic Supplementary Information (ESI) available:
[details of any supplementary information of complete
experimental procedures, CCDC: 1496652]. See DOI:
10.1039/c0xx00000x/
1 (a) E. Beutler, Science., 2004, 306, 2051; (b) S. Dai, C.
Schwendtmayer, P. Schürmann, S. Ramaswamy and H. Eklund,
Science, 2000, 287, 655; (c) A. Atkinson and D. R. Winge,
Chem. Rev., 2009, 109, 4708; (d) C. D. Kaplan and J. Kaplan,
Chem. Rev., 2009, 109, 4536; (e) E. C. Theil and D. J. Goss,
Chem. Rev., 2009, 109, 4568.
11 (a) T.ꢀB. Wei, X.ꢀB. Cheng, H. Li, F. Zheng, Q. Lin, H. Yao
and Y.ꢀM. Zhang, RSC Adv., 2016, 6, 20987; (b) Q. Lin, T.ꢀT.
Lu, X. Zhu, B. Sun, Q.ꢀP. Yang, T.ꢀB. Wei and Y.ꢀM. Zhang,
Chem. Commun., 2015, 51, 1635; (c) T.ꢀB. Wei, J.ꢀF. Chen,
X.ꢀB. Cheng, H. Li, Q. Lin, H. Yao and Y.ꢀM. Zhang, RSC
Adv., 2016, 6, 65898; (d) Q. Lin, T.ꢀT. Lu, X. Zhu, T.ꢀB. Wei,
H. Li and Y.ꢀM. Zhang, Chem. Sci., 2016, 7, 5341.
12 Z. Zhang, B. Xia, C. Han, Y. Yu and F. Huang, Org. Lett.,
2010, 12, 3285.
13 X. Wang, K. Han, J. Li, X. Jia and C. Li, Polym. Chem.,
2013, 4, 3998.
2 V. Bhalla, N. Sharma, N. Kumar and M. Kumar, Sens.
Actuators B, 2013, 178, 228.
3 (a) C. Wade, A. Broomsgrove, S. Aldridge and F. Gabbai,
Chem. Rev., 2010, 110, 3958; (b) A. Broomsgrove, D. Addy, C.
Bresner, I. Fallis, A. Thompson and S. Aldridge, Chem. Eur. J.,
2008, 14, 7525; (c) H. Zheng, X. Zhan, Q. Bian and X. Zhang,
Chem. Commun., 2013, 49, 429; (d) M. H. Lee, T. V. Giap, S.
H. Kim, Y. H. Lee, C. Kang and J. S. Kim, Chem. Commun.,
2010,46, 1407.
4 G. Gao, W. Qu, B. Shi, Q. Lin, H. Yao, Y. Zhang, J. Chang,
Y. Cai and T. Wei, Sens. Actuators, B, 2015, 213, 501.
5 (a) H. Horowitz, J. Publ. Health Dent., 2003, 63, 3; (b) J.
Farley, J. Wergedal and D. Baylink, Science, 1983, 222, 330;
(c) X. Yang, X. Gong, Y. Li, Z. Liu, B. Gao, G. Zhang, Y. Cui,
G. Sun and G. Zhang, Tetrahedron, 2015, 71, 5069; (d) Y.
Zhou, J. Zhang and J. Yoon, Chem. Rev., 2014, 114, 5511; (e)
X. Yang, L. Zheng, L. Xie, Z. Liu, Y. Li, R. Ning, G. Zhang, X.
Gong, B. Gao, C. Liu, Y. Cui, G. Sun and G. Zhang, Sens.
Actuators, B, 2015, 207, 9.
6 (a) T. Ogoshi, S. Kanai, S. Fujinami, T. Yamagishi and Y.
Nakamoto, J. Am. Chem. Soc., 2008, 130, 5022; (b) D. Cao, Y.
Kou, J. Liang, Z. Chen, L. Wang and H. Meier, Angew. Chem.,
Int. Ed., 2009, 48, 9721.
7 (a) Z. Zhang, C. Han, G. Yu and F. Huang, Chem. Sci., 2012,
3, 3026; (b) X.ꢀB. Hu, L. Chen, W. Si, Y. Yu and J.ꢀL. Hou,
Chem. Commun., 2011, 47, 4694; (c) N. L. Strutt, R. S. Forgan,
J. M. Spruell, Y. Y. Botros and J. F. Stoddart, J. Am. Chem.
Soc., 2011, 133, 5668; (d) X.ꢀY. Hu, X. Wu, Q. Duan, T. Xiao,
C. Lin and L. Wang, Org. Lett., 2012, 14, 4826; (e) B. Shi, K.
Jie, Y. Zhou, D. Xia and Y. Yao, Chem. Commun., 2015, 51,
4503; (f) S. Sun, X.ꢀY. Hu, D. Chen, J. Shi, Y. Dong, C. Lin, Y.
Pan and L. Wang, Polym. Chem., 2013, 4, 2224; (g) Y. Chen,
M. He, B. Li, L. Wang, H. Meier and D. Cao, RSC Adv., 2013,
3, 21405; (h) B. Shi, K. Jie, Y. Zhou, J. Zhou, D. Xia and F.
Huang, J. Am. Chem. Soc., 2016, 138, 80; (i) G. Yu, D. Wu, Y.
Li, Z. Zhang, L. Shao, J. Zhou, Q. Hu, G. Tang and F. Huang,
Chem. Sci., 2016, 7, 3017.
8 (a) W. Cheng, H. Tang, R. Wang, L. Wang, H. Meier and D.
Cao, Chem. Commun., 2016, 52, 8075; (b) Y. Cao, X. Hu, Y.
Li, X. Zou, S. Xiong, C. Lin, Y. Shen and L. Wang, J. Am.
Chem. Soc., 2014, 136, 10762; (c) X. Chi, X. Ji, D. Xia and F.
Huang, J. Am. Chem. Soc., 2015, 137, 1440; (d) X.ꢀY. Hu, K.
Jia, Y. Cao, Y. Li, S. Qin, F. Zhou, C. Lin, D. Zhang and L.
Wang, Chem. – Eur. J., 2015, 21, 1208; (e) G. Yu, J. Zhou, J.
Shen, G. Tang and F. Huang, Chem. Sci., 2016, 7, 4073; (f) T.
Wei, H. Li, Y. Zhu, T. Lu, B. Shi, Q. Lin, H. Yao and Y. Zhang,
RSC Adv., 2015, 5, 60273.
9 (a) F. Zhang, J. Ma, Y. Sun, I. Boussouar, D. Tian, H. Li and
L. Jiang, Chem. Sci., 2016, 7, 3227; (b) X. Cheng, H. Li, F.
Zheng, Q. Lin, Y. Zhang, H. Yao and T. Wei, Dyes and
Pigments, 2016 , 127, 59.

Page 7 of 7
New Journal of Chemistry
View Article Online
DOI: 10.1039/C6NJ03380F
A copillar[5]arene-based fluorescent “on-off-on” sensor is
applied in sequential recognition of iron cation and fluoride
anion
JinꢀFa Chen, XiaoꢀBin Cheng, Hui Li, Qi Lin*, Hong Yao, YouꢀMing Zhang, TaiꢀBao Wei*
Key Laboratory of Eco-Environment-Related Polymer Materials, Ministry of Education of China; Key Laboratory
of Polymer Materials of Gansu Province; College of Chemistry and Chemical Engineering, Northwest Normal
University, Lanzhou, Gansu, 730070, P. R. China
Text:
A copillar[5]areneꢀbased [c2]daisyꢀchain dimer is applied in sequential detection of Fe3+ and F− through
competitive complexation reaction.