Journal of Fluorescence

https://doi.org/10.1007/s10895-021-02765-6

ORIGINAL ARTICLE

Pyrene‑Hydrazone‑π···Hole Coupled Turn‑on Fluorescent and Naked‑

Eye Colorimetric Sensor for Cyanide: Role of Homogeneous π‑Hole
Dispersion in Anion Selectivity
Vanthana Jeyasingh1 · Kumaresan Murugesan1 · Sudha Lakshminarayanan1 · Narayanan Selvapalam1 ·
Geetha Das1 · Lakshminarayanan Piramuthu1 

Received: 10 April 2020 / Accepted: 1 June 2021

© The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature 2021

Abstract
A pyrene based probe associated with π···hole – hydrazone as one of the recognizing elements is synthesized and its turn in
to a selective colorimetric and turn-on fluorescent sensor, (L3) for cyanide anion. This chemo sensor show high selectivity
towards cyanide anion through photo electron transfer (PET) mechanism. The binding strength and sensitivity of the chemo
sensor L3 towards cyanide are found to be 2.0 X ­104, and 4.44 x ­10-4 respectively. We have compared this high selectivity of
the receptor towards cyanide, with our previously reported receptors L1 and L2. The detailed UV-Vis, Emission, 1H-NMR,
IR spectroscopic and Molecular Electrostatic Potential (MEP) studies reveals that the homogeneous π···hole dispersion in
the aromatic ring governing the selectivity of the receptor towards cyanide anion. Such a positive π···hole homogeneous
dispersion is missing in the case of sensor L2, instead we have polarized π···hole dispersion towards ­2nd and ­4th position of
di-nitrophenyl chromophoric unit in L2.

Keywords  Anion receptors · Anion – π interaction · Colorimetric anion sensor · Cyanide Sensors

Constructing a synthetic chemo sensor is demanding area
of sensory research. Designing and synthesis of selective
and naked eye colorimetric sensor for any particular anion
is even difficult task for chemists [1–5]. Very recently we
have reported a molecular phototropic system L2 for ani-
ons and the prepared molecular phototropic system is acts
as a molecular sunflower where the conformation of this
molecular sunflower was altered in response to the sunlight.
Further this molecular sunflower colorimetrically senses the
anions viz. cyanide, acetate, bifluoride and fluoride through
its transition state [6]. A reference compound L1 is also pre-
pared, and the spectroscopic investigation shows that this
reference compound is almost intact with any anionic inputs,
Scheme 1 [6].
We would like to dedicate this manuscript to Mr. R. Jeyasingh,
F/O J. Vanthana Jeyasingh.
* Lakshminarayanan Piramuthu
lakshmi16narayanan@gmail.com;
p.lakshminarayanan@klu.ac.in
1 of the ring), di-nitro phenyl (polarized electron deficient aro-
Department of Chemistry, International Research Centre,
Centre for Supramolecular Chemistry, Kalasalingam
Academy of Research and Education (KARE), Anand Nagar,
Srivilliputtur Tamil Nadu 626126 Krishnankoil, India
Benjamin P Hay et. al has theoretically proved that the
substitution of electron withdrawing moiety on the aromatic
ring of a chemo sensor will improve the selectivity and sen-
sitivity [7, 8]. In recent years, we have applied and supported
this hypothesis in our various reported chemo sensor sys-
tems though our crystallographic and spectroscopic findings.
Meanwhile, we are unable to control the selectivity of the
receptor L2 [9–15].
In order to make a selective chemo sensor for a particular
anion, requires a careful designing strategy and hence we
have decided to play with phenyl, nitro- phenyl and perfluoro
phenyl moieties as π···hole entity in our designing towards
preparation of a selective anion sensor [16]. With this back-
ground, we have designed a pyrene-hydrazone based recep-
tor L3, which is coupled with 2,3,4,5,6 pentafluorophenyl
moiety as π···hole entity, hydrazone moiety as binding unit,
and pyrene as fluorescence signaling element.
At this juncture, first we have performed the molecular
electrostatic potential (MEP) analysis [17] for L1, L2 and L3
consisting of phenyl (electron rich aromatic moiety in middle
matic moieties at 2nd and 4th position) and perfluoro phenyl
(electron deficient aromatic moiety in middle of the ring)

13
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Scheme 1  Structures of chemo sensors L1, L2 and L3
moieties respectively. As we can see in the Fig. 1a, since the
receptor ­L1 has the electron rich phenyl moiety, the clouds
of negative charge is uniformly dispersed in the middle of
the ring. On the other hand, since the receptor ­L2 having two
electron withdrawing moieties at 2nd and 4th position in the
phenyl moiety, the positive clouds is dispersed in polarized
manner towards 2­ nd and ­4th position. Unlike in the receptors
L1 and L2, in receptor L3 we have five electrons withdrawing
natured fluorine substitution are present directly on the rim of
the phenyl ring, Fig. 1 (Supplementary S1)[18].
It has been already observed that the receptor L1 almost
intact with anions and does not shows any color changes upon
addition of any anions. On the other hand, receptor L2 showed
colorimetric responses towards cyanide, fluoride, bifluoride
and acetate anions. Similar way, the naked-eye colorimetric
sensing capability of L3 is also studied by addition of tetra
butyl ammonium salts of various anions into acetonitrile
­(CH3CN) solution contains L3. Very interestingly, the color
of the receptor L3 in acetonitrile is changed from pale yellow
to dark pink color and there is no color changes observed
with addition of other anions in to L3 consequently we have
also recorded UV-Vis spectra for the respective samples and it
supports the colorimetric response of L3 with anions, Fig. 2.
The UV-Vis spectrum of chemo sensor L3 is composed
with a characteristic absorption band of pyrene moiety of
Fig. 1  Molecular Electrostatic Potential (MEP) surfaces for receptor
(a) L1, (b) L2 and (c) L3
13
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Journal of Fluorescence
Fig. 2  Colorimetric responses and UV-Vis Spectroscopic investiga-
tion of receptor L3 with respective anions in acetonitrile solution.
Insert picture: The observed color change upon addition of cyanide
(a) only L3 (b) L3 + ­CN-
L3 which is centered at λmax = 387 nm and upon addition
of ­CN- anion into the acetonitrile solution of L3 shows a
very distinguishable change in the UV-Vis absorption spec-
tra with formation of a new absorption band in the visible
region which is centered at 535 nm; which causes a sharp
color change from faint yellow to dark pink in color. There
is no spectral change observed upon addition of any other
anions into to the acetonitrile solution of L3, Fig. 2.
In order to find out the strength of the receptor L3 towards
cyanide, we have performed a UV-Vis spectrometric titration
experiments. Aliquots amount of cyanide is added into L3,
subsequently the binding constant and limits of detection
(LoD) are found to be 2.0 x ­104 and 4.44 x ­10-4 respectively,
Fig. 3 [19]. Further the stoichiometric ratio for the host:
guest complex is also calculated with the help of job’s plot
titration by continuous variation method. UV-Vis absorption
Fig. 3  UV-Vis spectrometric titration: The observed spectral changes
upon aliquots addition of cyanide in to the acetonitrile solution of L3
Journal of Fluorescence

spectra are recorded continuous variation concentration of

L3 and tetrabutyl ammonium cyanide concentrations further
the host: guest is found to be 1:1 stoichiometric fraction of
­L3: ­CN- complex, Fig. 4.
The chemo sensor L3 displays a weak single fluorescence
band λmax at 460 nm when we excited the molecule at 410
nm in acetonitrile solution. Changes are observed in the
emission spectra upon addition of cyanide anion as tetrabu-
tyl ammonium salt; further no considerable or very marginal
spectral changes were observed upon addition of any other
anion. In general, the chemo sensor L3 displays a strong
fluorescence response with an enhancement of fluorescence
intensity, Fig. 5.
Solution state binding capacity of the chemo sensor L3
towards cyanide anion is calculated from the fluorescent
data recorded upon addition of aliquots amount cyanide ion
Fig. 5  Fluorescence emission spectroscopic investigation of receptor
on to the acetonitrile solution of L3 lead to the increase in L3 with respective anions in acetonitrile solution. Insert picture: The
fluorescence intensity at λmax = 460 nm, Fig. 6 [19]. We observed visible change under UV illumination: (a) L3 and (b) L3 +
have calculated the fluorescence quantum yield of cyanide ­CN-
complex and it is found to be ΦF = 0.0385.
We have also performed a competitive study in the excess
of cyanide and equal same excess of other respective anion disappearance of hydrazone –NH proton signal (10.595
as listed in the Fig. 7. From the figure, it is very clear that, ppm) upon addition of excess equivalent of cyanide anion.
the chemo sensor L3 has very high selectivity towards cya- The disappearances of (hydrazole) –NH peak is most prob-
nide than in presence of any tested other anions. The selec- ably due to the strong hydrogen bonding interaction of
tivity of cyanide in the presence of other anions, especially cyanide ion with the receptor L3, Fig. 8. In addition to the
in the presence of dihydrogen phosphate, fluoride and ace- disappearance of –NH peak, it is observed that the aromatic
tate are very important because presence of these anions will Ar-CH is also gets disturbed upon addition of cyanide (9.202
affect the selectivity of the any anion receptors, in general. to 9.110 ppm) suggests the Ar-CH also involved in the anion
The binding mode of L3 with cyanide anion is also inves- binding in solution state. This result supports the Benjamin
tigated with help of proton nuclear magnetic resonance P Hay’s theoretical observations. The native 1H-NMR spec-
spectroscopy (1H-NMR) in deuterated acetonitrile solu- trum of L3 is almost intact with other anionic inputs.
tion. The partial 1H-NMR spectra of receptor L ­ 3 is depicted The nature of the host: guest interactions are also ana-
in Fig. 8, which is clearly demonstrating that a complete lyzed by FT-IR spectroscopy. It has been observed that huge
disturbance of hydrazone (from 3329 to 3458 c­ m-1 shift)

Fig. 4  Evaluation of Host: Guest ratio by Job’s plot. Absorbance Fig. 6  Change in the fluorescence intensity of L3 at 460nm in the
value used to plot the job plot is λ = 535 presence of cyanide anion

13

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Fig. 7  Bar chart: Fluorescent intensity of L3, change of fluorescent
intensity of L3 with anions and Change of fluorescent intensity of L3
with cyanide in presence of other respective at 460 nm
–NH, -C=N and Ar-CH with reference to the native FT-IR
spectrum. The detailed shifts were depicted in the Fig. 9.
Based on the UV-Vis, Emission, 1H-NMR, and FT-IR spec-
troscopic analysis here in, we are proposing a possible sensing
mechanism for receptor L1, L2 and L3
Since receptor L1 has very weak binding site, it does
not sense any anions and acts as a reference compound.
In the case of receptor L2, 2,4 dinitro phenyl moiety acts
as a chromophoric unit, further the receptor is sensing the
cyanide, acetate, bifluoride and fluoride anions via Internal
Charge Transfer (ICT) mechanism. Observed ICT indicates
that, strong 2,4 dinitro substituted benzene chromophoric unit
turn out to be as an active signaling unit than fluorophoric
pyrene moiety. On the other hand, in the case of receptor L3
2,3,4,5,6 pentafluoro substituted electron deficient benzene
ring turn out to be a completely active receptor site by its
π-holed character Hence, the pyrene becomes only active
signaling unit causes the photo induced electron transport.
In this report the receptor L3 sense exclusively cyanide anion
via Photo Electron Transfer (PET) mechanism [20–23]. In
the present case, the receptor L3 show a weak fluorescence
Fig. 8  Partial 1H-NMR spectra of L3 in the presence of tetrabutyl
ammonium cyanide in deuterated acetonitrile
13
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Journal of Fluorescence
Fig. 9  Analysis of host: guest interactions interaction by FT-IR spec-
troscopy
emission spectrum which is mainly attributed due to the
transfer of electron pair from the hydrazone nitrogen (-NH)
into highly conjugated pyrene fluorophoric unit, Scheme 2.
Homogeneously distributed positive density (π···hole)
inside the pentafluorophenyl benzene brings planar π···hole
receptor site for anion where as in the case of ­L2 polarized
distribution on electron density towards 2,4 nitro substituted
benzene brings acidic aromatic C-H as additional binding site.
According to Bryans et al statement both 2,4 dinitro subsiti-
tuion and pentafluoro substitution on benzene ring enhances
acidic nature of neighbored Hydrogen bonding donor sites but
dinitro benzene act as both signaling unit and receptor site
(dinitro as signaling unit & Ar-CH as binding site) by its polar-
ized electron distribution where as pentafluoro benzene act as
complete receptor site by (π···hole ) uniformly and homogene-
ously distributed positive electron density. These differences
bring more directional or selectivity property for L3 than L2.
Scheme 2  Schematic diagram of binding mechanism of ­L3 with cya-
nide
Journal of Fluorescence

Scheme  3  Schematic representation: Preferencial binding mode of

anion(s) with ­L1, ­L2and ­L3

based chemo sensor for selective sensing of cyanide anion. The

­ 3 and
Fig. 10  Snapshot of test strips (silica plate) coated with sensor L
cyanide immersed (a), (b) under visible light; (c), (d) under UV illu-
mination
In order to use this receptor for the sensing of cyanide, we
have developed a test strip (silica coated plate) which actually
­ 3. Upon immersion of cyanide anion solu-
coated with receptors L
tion, the color was changed from its anion free strip, Fig. 10. In
conclusion, we have successfully tuned a pyrene-hydrozone
cyanide selectivity with chemo sensor L3 is achieved by attach-
ing 2,3,4,5,6 pentafluoro phenyl moiety in to a pyrene-hydrozone
compartment. The homogeneous dispersion of positive π···hole
created by the pentafluoro moiety plays a vital role in the exclu-
sive cyanide selectivity by L3. Such a positive π···hole homoge-
neous dispersion is missing in the case of sensor L3, instead we
have polarized π···hole dispersion towards ­2nd and ­4th position
of di-nitrophenyl chromophoric unit in L2, Scheme 3. A table
showing the comparison of recently reported cyanide sensors
with ­L3 is displayed below for reference (Table 1).

Table 1  Comparison table of Sl.No. Method μgL-1 References Sl.No. Method μgL-1 References
cyanide sensor
1 UV-Vis 8.7 [24] 21 Visual 26 [44]
2 Fluorescence 65 [25] 22 Visual 44.2 [45]
3 Fluorescence 3.9 [26] 23 Visual 26 [46]
4 UV-Vis 63000 [27] 24 UV-Vis 130 [47]
5 UV-Vis 2.5 [28] 25 UV-Vis 5.5 [48]
6 Fluorescence 15.6 [29] 26 Fluorescence 0.36 [49]
7 Fluorescence 49.4 [30] 27 Fluorescence 66 [50]
8 UV-Vis 50 [31] 28 Fluorescence 0.00749 [51]
9 UV-Vis 20 [32] 29 Fluorescence 0.021 [52]
10 UV-Vis 5 [33] 30 Fluorescence 0.058 [53]
11 Visual 26 [34] 31 Fluorescence 0.674 [54]
12 UV-Vis 520 [35] 32 Fluorescence 1.2 [55]
13 Visual 39 [36] 33 Fluorescence 0.1 [56]
14 Visual 130 [37] 34 UV-Vis 0.75 [57]
15 UV-Vis 39 [38] 35 UV-Vis 0.3 [58]
16 Visual 13 [39] 36 Fluorescence 0.1 [59]
17 Visual ~50 [40] 37 UV-Vis 0.7 [60]
18 UV-Vis 1.9 [41] 38 Fluorescence 5.77 [61]
19 Visual Lower than [42] 39 Fluorescence 1.05 [62]
50
20 Visual [43] 26 Fluorescence 7.2 [63]

13

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Associated Content
The Supporting Information is available free of charge on
the Publications website.
Supplementary Information  The online version contains supplemen-
tary material available at https://d​ oi.o​ rg/1​ 0.1​ 007/s​ 10895-0​ 21-0​ 2765-6.
Acknowledgment This work is financially suppor ted by
DST-SERB, India under Early Career Research Award
(ECR/2015/000318 & 09/1012(0002)/2020-EMR-I). V. J., and M. K
acknowledge Kalasalingam University (KARE) for PhD fellowship.
The authors acknowledge I.R.C, KARE for providing instrumentation
facilities. The authors thank Dr. Shasi Anand, The Vice-President of
Kalasalingam University, (KARE) for his constant support.  past least squares (PLS) regression. Talanta 71:893–899
Funding  V. J acknowledges CSIR-HRDG-INDIA for a Senior Research
Fellowship (122270/2K19/1  &  09/1012(0002)/2020-EMR-I).This
work is financially supported by DST-SERB, India under Early Career
Research Award (ECR/2015/000318).
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