Journal of Fluorine Chemistry 175 (2015) 180184

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Journal of Fluorine Chemistry

journal homepage: www.elsevier.com/locate/fluor

Novel chemosensor for multiple target anions: The detection of F and

CN ion via different approach
Duraisamy Udhayakumari a, Sivan Velmathi a,*, Maria Susai Boobalan b
a
Department of Chemistry, National Institute of Technology, Organic and Polymer Synthesis Laboratory, Tiruchirappalli 620 015, India
b
Department of Chemistry, St. Josephs College (Autonomous), Tiruchirappalli 620002, India

A R T I C L E I N F O A B S T R A C T

Article history: A novel chemosensor based on azo linked Schiff base (receptor 1) was synthesized by simple
Received 10 February 2015 condensation method. The sensor studies of receptor 1 disclose the selectivity toward uoride and
Received in revised form 30 March 2015 cyanide ion with a color change among the other common anions in aqueous medium. The binding
Accepted 18 April 2015
afnity of receptor 1 was also enlightened by 1H NMR titration and DFT calculation.
Available online 12 May 2015
2015 Elsevier B.V. All rights reserved.

Keywords:
Azo dye
Nucleophilic addition
Cyanide detection
Aqueous solution
Colorimetric

1. Introduction
Selective sensing of anions has received considerable attention
over recent years due to their important role in the biological
process, medicinal chemistry, environmental chemistry and
catalysis. In addition, colorimetric chemosensors have many
advantages like low cost, suitability for biological concern, easy
detection and high selectivity [15]. During the last few years, a
number of colorimetric anion sensors have been developed using
urea, thiourea, amide and pyrrole based binding units. Most of the
receptors sense different anions such as uoride, acetate, nitrate,
dihydrogen phosphate and hydroxyl group [612]. Cyanide is one
of the most toxic anion, harmful to the environment. It plays an
important role in various industrial processes, for example gold
mining, synthetic bers and resins [1317]. On the other hand,
uoride is a biologically important anion due to its wide role in
dental care and treatment of osteoporosis [1820]. Novel
colorimetric cyanide ion sensors, which allow naked eye detection
of the color change without resorting to the use of expensive
instruments is most attractive approach. However, nding a
simple receptor selectively sensing cyanide anion in aqueous
medium is still a challenge. To the best of our knowledge, a simple
* Corresponding author. Tel.: +91 431 2503640/9486067404;
fax: +91 431 2500133.
E-mail address: velmathis@nitt.edu (S. Velmathi).
sensor that can sense differentially F and CN ion has rarely been
reported [2123]. Recently we reported azo Schiff base [24,25] to
act as a colorimetric, uorescent chemosensors for F /AcO ions in
organic and semi-aqueous medium. In continuation of our
research interest in the chemosensors, we herein report the
application of receptor 1 toward sensing of CN in pure aqueous
medium.
In this paper, we report a simple receptor which can selectively
detect cyanide in aqueous medium via colorimetric and UVvis
spectroscopic method. With appropriate analysis, it is possible to
detect uoride and cyanide ions separately in the same sample by
tuning the solvent medium. The absorption spectra indicated the
formation of complex between receptor and anions in 1:1
stoichiometric ratio with micromolar detection limit. The interac-
tion mechanism between the receptor 1 with uoride and cyanide
was investigated using 1H NMR titration experiment.
2. Materials and methods
All reagents used were obtained commercially and used
without further purication. In the titration experiments, all the
anions were added in the form of tetrabutylammonium (TBA) salts
and analytical grade solvents such as acetonitrile (CH3CN) and
ethanol (EtOH) were purchased commercially. Shimadzu UV-2600
UV-vis spectrophotometer was used to record UVvisible spectra
using quartz cell with 1 cm path length. 5  10 5 M solution of
receptor 1 in CH3CN and 1.5  10 3 M solutions of the anions in

http://dx.doi.org/10.1016/j.juchem.2015.04.014
0022-1139/ 2015 Elsevier B.V. All rights reserved.
 D. Udhayakumari et al. / Journal of Fluorine Chemistry 175 (2015) 180184
CH3CN, H2O were prepared. 0.2 equiv. (20 mL)2 equiv. (200 mL) of
guest solution was added to 3 mL of R1 taken in the UV cuvette.
3. Results and discussion
The synthesis of chemosensor (receptor 1) is outlined in
Scheme 1. 1 mmol of 4-amino azobenzene (0.200 g) and 1 mmol of
2-hydroxy-5-(phenyldiazenyl) benzaldehyde (0.229 g) in ethanol
(10 mL) was reux for 23 h at 85 8C. After cooling, the precipitate
formed was ltered, washed, recrystallized from EtOH and dried in
vacuum oven. Yield: 85%, mp: 160 8C. 1H NMR (300 MHz, DMSO-d6
d ppm): 9.25 (s, 1H, OH), 8.37 (s, 1H, CH5 5N), 8.028.07 (d, 3H, Ar,
J = 15 Hz), 7.877.94 (m, 4H, Ar, J = 5.7 Hz), 7.557.71 (m, 9H, Ar,
J = 8.4 Hz), 7.187.21(d, 1H, Ar, J = 9 Hz). HRMS: Calcd: 406.1600,
Found: 406.1660 (Figs. S1 and S2).
The sensing behavior of receptor 1 with anions was observed by
naked-eye and detection was further conrmed by UVvis
spectrophotometer. In the presence of different counter anions,
receptor 1 showed selective sensing of CN in aqueous environ-
ment. To investigate the anion recognition property of receptor 1,
four different types of colorimetric and UVvis titrations were
carried out. The binding afnity of receptor 1 (5  10 5 M in
CH3CN) in the presence of various anions such as F , Cl , Br , AcO ,
H2PO4 , HSO4 , HO and CN (1.5  10 3 M in CH3CN) was carried
out. Fig. 1a and b shows the color changes and the absorption
spectrum of receptor 1 with different anions in CH3CN. The solution
of receptor 1 resulted in an immediate color change from colorless to
orange for F , yellow color for AcO and green color for CN ions. The
other ions like Cl , Br , H2PO4 , HSO4 and HO did not induce any
color changes and absorption changes even in large excess. The
incremental addition of F and CN shows a band at 450 nm
increased, at the same time the band at 350 nm decreased with the
clear and single isosbestic point at 385 nm (Figs. S3 and S4).
In second titration, the effect of water on the binding afnity for
uoride was carried out in different wateracetonitrile mixtures
Scheme 1. Synthetic route of receptor 1.
Fig. 1. (a) The corresponding color changes and (b) absorption spectra of receptor 1 when treated with 2 equiv. of various anions (F , Cl , Br , AcO , H2PO4 , HSO4 , HO and
CN ) in CH3CN.
181
(0%, 20%, 40%, 60%, 80% and 90% water, respectively) with receptor
1 (CH3CN). 20% aq solution of F resulted in a marginal color
change, but did not show any optical changes (Fig. S5). So the
outcome of the second titration indicates, receptor can sense
uoride, only in organic medium and not in aqueous medium. In
the third titration, in order to gain systematic knowledge on the
effect of water on the binding afnity and selectivity for cyanide
(100% H2O), we took receptor 1 in wateracetonitrile mixtures (0%,
20%, 40%, 60%, 80% and 90% water) and CN ion in 100% H2O. When
receptor 1 was taken in 20:80 wateracetonitrile mixtures as
solvent, CN showed obvious interaction with the receptor 1. The
color changed to green upon addition of CN , correspondingly in
optical spectrum the band at 350 nm shifted (red shift) to 390 nm.
When increase the percentage of water from 40% to 90%, same
result was observed in color change and UVvis change (Fig. 2a and
b). From these results, it is conrmed that cyanide can be
selectively sensed in 90% aqueous medium.
In general, hydration will terminate the anion sensing behavior,
water the strong competitive solvent in the hydrogen bonding
and lead to the leaching of anions and regenerate the receptor
molecule. We chose receptor 1 in 90% H2O (5  10 5 M) and
anions in 100% H2O (1.5  10 3 M), only CN ion showed obvious
interaction with the receptor 1 (Fig. 3a). The color changed to
green and the band shifted to 350390 nm (40 nm) only for CN
ion (Fig. 3b). Increasing the amount of water content is avoiding
completely the interference of F and ACO ions. The anions such
as F , AcO , H2PO4 and HSO4 should interact with water
through hydrogen-bonding leading to a large decrease in their
nucleophilicity. While cyanide has weaker hydrogen-bonding
ability and stronger nucleophilicity toward the carbonyl group.
Cyanide has much weaker hydrogen bonding ability in
comparison with other anions like F and AcO and stronger
nucleophilicity toward the imine group [2628], which results
in the addition of CN ions to the carbon atom of an electron
decient imine group and, subsequently, fast proton transfer of
182 D. Udhayakumari et al. / Journal of Fluorine Chemistry 175 (2015) 180184

Fig. 2. (a) The corresponding color changes and (b) absorption spectra of receptor 1 in wateracetonitrile mixtures (0%, 20%, 40%, 60%, 80% and 90% water, respectively) when
treated with 2 equiv. of CN ion in 100% H2O.

Fig. 3. (a) The corresponding color changes and (b) absorption spectra of receptor 1 in water (90%)acetonitrile (10%) mixtures when treated with 2 equiv. of various anions
(F , Cl , Br , AcO , H2PO4 , HSO4 , HO and CN ) in 100% H2O.

the phenol hydrogen to the neighboring nitrogen anion through
an intramolecular hydrogen bond.
The detection of anions by receptor 1 is further supported by 1H
NMR titration. 1H NMR titrations were carried out in DMSO-d6.
Tetra butyl ammonium salt of uoride and cyanide were used as
anions sources. Without the addition of anions, receptor 1 showed
signals at d 8.37 ppm due to HC5 5N proton and 9.25 ppm
corresponds to OH proton. After the addition of 2 equiv. of F
ions, the resonance signal of OH proton becomes disappeared
(Fig. 4). This might be due to the formation of hydrogen bonds
between the anions and the OH group of receptor 1. This indicates
that deprotonation of the receptor 1 can possibly occur. In addition,
the signals correspond to imine and aromatic protons were shifted
to upeld with the addition of F ions. The 1H NMR titration studies
sustain the proposed sensing mechanism of receptor 1 with F ions
(Scheme 2). But in the case of CN ions to receptor 1, the OH signal
of receptor 1 disappeared and a new peak at 6.36 ppm started
appearing. All the aromatic protons were shifted to upeld. This
result strongly supports the nucleophilic attack of CN ions toward
the carbon atom of an electron decient imine group of receptor 1
(Scheme 3).
Binding constant (Ka) for all anion complexes of the receptor 1
were calculated using BenesiHildebrand plot and stoichiometry
of the complex was calculated using Jobs plot. The detection limit
(LOD) of F and CN ions by receptor 1 was calculated using the
formula, LOD = 3s/m. Where s the standard deviation and m is
the slope obtained in the plot of absorbance vs. concentration of
anions. The detection limit value implies that the receptor 1 can
easily detect F and CN at micro molar level in both organic and
aqueous medium. Binding constants and detection limit are
calculated with repeated titrations and the values are given in
Table 1. The receptor 1 was compared with some reported
chemosensors for CN (Table 2). While each chemosensor showed
some advantages such as easy synthesis, high sensitivity, no
interference and naked eye detection. Our receptor 1 exhibited
quite appealing analytical features such as easy synthesis, high
selectivity and naked-eye sensing (R15 5CN ) [2934].
Density Functional Theory (DFT) calculations have been used to
understand the behavior of receptor 1 with the F and CN ions.
Highest occupied molecular orbital (HOMO) and lowest unoccu-
pied molecular orbital (LUMO) for receptor 1 and their complexes
have been generated from the optimized structures of the receptor

Fig. 4. 1H NMR spectrum of receptor 1 recorded in DMSO-d6 in the absence and presence of F and CN ions.
 D. Udhayakumari et al. / Journal of Fluorine Chemistry 175 (2015) 180184 183

Scheme 2. The proposed sensing mechanism for receptor 1 with uoride.

Scheme 3. The proposed sensing mechanism for receptor 1 with cyanide.

1 and their respective anion complexes (Fig. 5). The structural
optimization and the computational calculations were carried
out using Gaussian09 quantum chemistry package and results
were viewed with GaussView5 GUI. The appropriate choice of
model chemistry for the computation of electronic structure
property is indispensable. In the present scenario, Density
Functional Theory (DFT) supported B3LYP/6-31G (d, p) model
chemistry was implemented particularly for Schiff base ligands
under gas phase condition. DFT calculations were carried out to
investigate the change of the absorption spectra upon the
addition of F and CN . From the energy level diagram (Fig. 6), it
can be seen that the addition of the anions lead to the
stabilization of the HOMO and LUMO of the sensor molecule.
From the calculated results, the energy levels of HOMO and
LUMO of receptor 1 increased after the addition of F and CN
ions when compared to that of the free receptor 1 (Table 3). For
F and CN complexes of receptor 1, the absorption bands
predicted by the theoretical methods is red shifted compared
with those of the independent probes, which is in good
agreement with the experimental observations.

Table 1
Binding constant, stoichiometry, detection limit value of the complex formed for receptor 1 with CN and F ion.
1 1
S. no Receptor + ions Solvent system Binding constant (M ) Stoichiometry LOD (M )
4 6
1 R1 + F 100% CH3CN 4.6  10 1:1 1.5  10
2 R1 + CN 100% CH3CN 3.3  105 1:1 1.9  10 6

3 R1 + CN 90% H2O (R1) 100% H2O (CN ) 5.5  104 1:1 5.2  10 6

Table 2
Comparison of some of the reported chemosensors for CN with the present work.

Sensors Solvent system Sensing ions LOD Binding constant Linear range Reference
(M 1) (R2)

Thiazole based sensor DMSO/bis-tris buffer (8:2) CN 60 mM 3.2  102 0.994 [29]
AcO 140 mM 1.0  102
Azo based sensor H2O CN 0.010.07 mM [30]
Azo coupled tripodal based sensor CH3CN:DMSO:HEPES (93:1:6) CN 01.9 mM 2.3  103 0.990 [31]
Azo coupled NBD unit based sensor EtOH:H2O (3:7) CN 1.5 mM 0.990 [32]
Bis-pyrene derivative based sensor CH3CN:DMSO (99:1) CN 1.79 mM (R1) 5.89  104 (R1) 0.990 [33]
2.43 mM (R2) 3.98  108 (R2)
Imidazo-anthraquinones based sensor CH3CN:H2O (97:3) CN 3.31 mM 6.808.96 [34]
F 4.97 mM 6.318.50
Azo linked Schiff base sensor CH3CN F 1.5 mM 4.6  104 0.993 This work
CH3CN:H2O (1:9, v/v) CN 1.95.2 mM 5.5  104

Table 3
Energies of HOMO and LUMO of the R1 and complexes.

R1 and complexes HOMO (eV) LUMO (eV) DE (eV) Theoretical wavelength (nm) Observed wavelength (nm)

R1 5.774 2.361 3.413 363 354

R1 + F 3.434 0.807 2.627 471 450
R1 + CN 3.282 0.633 2.649 350 385
184 D. Udhayakumari et al. / Journal of Fluorine Chemistry 175 (2015) 180184
Fig. 5. Optimized structures of (a) receptor 1, (b) receptor 1 + F and (c) receptor 1 + CN .
Fig. 6. Energy levels of various HOMO and LUMOs of receptor 1 in the absence and presence of F and CN .
4. Conclusion
In summary, we have developed a novel and highly sensitive
receptor 1 that can detect both F and CN ion selectively with the
distinct color changes, where F ion shows colorless to orange and
CN ion shows colorless to green. Further, receptor 1 showed
selective detection of cyanide ion in 90% aqueous medium based
on a nucleophilic addition followed by a intra molecular proton
exchange process. Receptor 1 was found to provide sensitive and
good selective recognition of CN conrmed through its absorption
spectrum.
Acknowledgment
Authors express their thanks to DRDO (ERIP/ER/1006004/M/01/
1333 dated 23-05-2011) for nancial assistance in the form of a
major sponsored project.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the
online version, at http://dx.doi.org/10.1016/j.juchem.2015.04.014.
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