Novel Isophthalohydrazide-cDB24C8 cryptand derivative for the selective recognition of fluoride ion: An experimental and DFT study

Article abstract of DOI:10.1016/j.saa.2018.06.055

A highly selective and sensitive novel Isophthalohydrazide-cDB24C8 cryptand derivative was developed for fluoride recognition at a very low concentration of 2.31 × 10^?10 M. The binding was established by UV–Vis, fluorescence and ¹H NMR titration. The receptor formed very strong H-bonded complex with fluoride, furnished a sharp new UV–Vis absorption peak at 280 nm which was also supported by the DFT-study. The fluorescence emission spectra showed large quenching up to 79.13% upon addition of fluoride.

Full text of DOI:10.1016/j.saa.2018.06.055

Accepted Manuscript
Novel Isophthalohydrazide-cDB24C8 cryptand derivative for the
selective recognition of fluoride ion: An experimental and DFT
study
Sankar Jyoti Bora, Rakesh Dutta, Dhruba Jyoti Kalita, Bolin
Chetia
PII:
DOI:
Reference:
S1386-1425(18)30595-X
doi:10.1016/j.saa.2018.06.055
SAA 16214
Spectrochimica Acta Part A: Molecular and Biomolecular
Spectroscopy
To appear in:
Received date: 22 February 2018
Revised date:
Accepted
date:
4 June 2018
14 June 2018
Please cite this article as: Sankar Jyoti Bora, Rakesh Dutta, Dhruba Jyoti Kalita, Bolin
Chetia , Novel Isophthalohydrazide-cDB24C8 cryptand derivative for the selective
recognition of fluoride ion: An experimental and DFT study. Saa (2018), doi:10.1016/
j.saa.2018.06.055
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ACCEPTED MANUSCRIPT
Novel Isophthalohydrazide-cDB24C8 Cryptand Derivative for the Selective Recognition
of Fluoride Ion: An Experimental and DFT study
Sankar Jyoti Boraa, Rakesh Duttab, Dhruba Jyoti Kalitab* and Bolin Chetiaa*
aDepartment of Chemistry, Dibrugarh University, Dibrugarh 786004, Assam, India
bDepartment of Chemistry, Gauhati University, Guwahati 781014, Assam, India
Correspodin author E-mail address: bolinchetia@dibru.ac.in (B. Chetia).
dhrubajyoti.kalita@gauhati.ac.in (D.J. Kalita)
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Abstract
A highly selective and sensitive novel Isophthalohydrazide-cDB24C8 cryptand derivative
was developed for fluoride recognition at a very low concentration of 2.31×10-10 M. The
binding was established by UV-Vis, fluorescence and 1H NMR titration. The receptor formed
very strong H-bonded complex with fluoride, furnished a sharp new UV-Vis absorption peak
at 280 nm which was also supported by the DFT-study. The fluorescence emission spectra
showed large quenching up to 79.13% upon addition of fluoride.
Keywords: Cryptand; Fluoride; DFT study; Fluorescence; Anion Sensing.
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1. Introduction
The design and synthesis of novel receptors having the capability of selectively
recognise and sense anions has become the great deal of interest in recent research fields of
supramolecular chemistry as anions play an imperative role in biological, industrial, chemical
and environmental processes like molecular probe for medicinal diagnosis, monitoring of
pollutants, enzyme-mimic etc [1-2]. Despite the numerous developments achieved in this
sensing field, selective recognition of anion continues to be a great challenge due to intrinsic
character of anions. Among the various anions, the sensing of fluoride ions has attracted
growing attention, as it plays a significant role in dental health and in treatment of
osteoporosis, but overexposure of it leads to various harmful effects like kidney failure,
incapacitating bonds etc. and recognition is most challenging because of its high hydration
enthalpy [3]. Although many scientists had reported numerous classes of hosts for anion
sensing, still it is a great problem for supramolecular chemist to design and synthesis
“substrate specific” receptors because of the large size of the anions compared to cations, the
chemical environment that determines the strength of interaction and the pH of the medium
[4]. In recent advances several receptors were synthesised such as ureas [5], thioureas [6],
pyrroles [7], amides [8], benzimidazoles [9], p-nitrophenyl [10], o-phenylenediamine [11] etc
most of them contains –NH fragment, which act as hydrogen bond donor for anion. It has
been observed that protonated amines and quaternary ammonium functions incorporated in a
suitable ligand topology make them attractive receptors for anions [12]. Cryptands have been
mostly used as host molecules for halide [13], oxo-anion [14], cation [15], paraquate [16],
molecule recognition [17] etc. Several receptors were synthesized [18] having high selectivity
and affinity for fluoride ion, but detection and intensification of fluoride ion binding is still
remain challenged. Here we have reported a novel Isophthalohydrazide-cis-dibenzo-24-
crown-8 cryptand derivative using schiff-base formation reaction and used for selective
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sensing of fluoride ion in very low concentrations. We have also performed density
functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations
to study the binding modes between the host cryptand and guest fluoride ion in DMSO
solvent environment with incorporating conductor-like polarized continuum model (C-PCM).
2. Experimental
2.1 Materials and methods
All the reagents used in this work were purchased from Sigma-Aldrich chemical co. and used
without further purification. The solvents were purchased from Merck co. and used after
distillation under desired procedure. The reagents used were analytical grade and the solvent
were of spectroscopic grade. FT-IR spectra were recorded as KBr pellets on a Shimadzu IR-
Prestige-21 FT-IR spectrophotometer operating from 400 to 4000 cm-1. The UV-visible
spectra were recorded on JASCO V-750, wave length ranging from 900-200 nm.
Fluorescence spectra were recorded on Horibajobin Yovon Fluoromax-4 spectrophotometer.
1
The compound was characterised by using FT-IR, H NMR, 13C NMR and FAB-MS
spectroscopic data. Anion-binding ability of the compound was examined by UV-Vis
absorption and fluorescence spectroscopy in DMSO. To study the binding of fluoride ion by
cryptand receptor, we recorded the gradual change in UV-Visible and fluorescence spectra of
the solution of Isophthalohydrazide-cDB24C8 cryptand in DMSO upon addition of Bu4NF
solution with the increment of 0.1 equivalent up to 1 equivalent.
2.2 Procedure for the synthesis of Isophthalohydrazide-cDB24C8 cryptand (R).
In a 250 ml round bottom flux 7 g (50.680 mmol) of 3,4-dihydroxybenzaldehyde was
dissolved in 75 ml CH3CN. To this solution excess diiodo derivative of triethylene glycol
(approx. 5 eqv) was added and refluxed for 36 hr (scheme 1). The conversion of the reaction
was monitored by TLC. After completion of the reaction, solvent was evaporated on rotary
evaporator and extracted with ethyl acetate and washed with water two to three times. The
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organic layers were separated out and dried with anhydrous sodium sulphate and filtered it
off. The filtrate was evaporated on rotary evaporator and crude product thus obtained was
purified by column chromatography using silica gel 60-120 mesh. 20.12 gm (63.8%) of 2b
was obtained. 20.12 gm (32.33 mmol) of 2b reacted with 4.46 gm of (32.33 mmol) of 2a in
CH3CN using high dilution method in presence of K2CO3 refluxed for 60 hr. The crude
product thus obtained was purified by the same way as for 2b via column chromatography
giving 39 % yield (6.36 gm) of 2c. For preparation of Isophthalohydrazide-cDB24C8-
cryptand (R), isophthalohyrdazide (2d) (2.44 gm, 12.61 mmol) was dissolved in 100 ml hot
ethanol and added drop wise into hot and stirred solution of 2c in ethanol (6.36 gm, 12.61
mmol, in 120 ml ethanol) for a period of 8 hr. This reaction was refluxed for 15 hours, where
brown colored precipitate was appeared. The precipitate was washed with ethanol for several
times, air dried and 1.6 gm (21 % yield) was obtained. Mass m/z was
Scheme 1 : (i) K2CO3, CH3CN, reflux; 36 hr, 63.8% (ii) K2CO3, CH3CN, high dilution
reflux; 60 hr, 39% (iii) Distilled Ethanol, reflux,15 hr, 21 %.
found 662.2804, calculated 662.686. IR (KBr, ʋ cm-1): The band observed at 1683 and 1734
cm-1 was assigned for C=N and C=O vibration respectively. Instance band at 3510-3608 cm-1
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was observed due to -NH- vibration of hydrazine group. Aromatic C=C vibrations came at
1506 cm-1, the band at 2922-2862 cm-1 were attributed to aliphatic C-H vibration. The band
-1
-1
1
at 3064 cm assigned to aromatic -CH- and C-O-C vibration appeared at 966-825 cm . H
NMR (400 MHz, DMSOd6, ẟ ppm): 9.82 (s, 2H, -CO-NH-), 8.90 (s, 2H, -CH=N), 8.33 (d,
2H, J=8.2 Hz), 8.20 (s, 1H), 8.03 (t, 1H, J= 10.52 Hz), 6.92 (m, 4H), 6.79 ( d, 2H, J= 8.68
Hz), 4.13 (m, 8H), 3.88 (m, 8H), 3.74 (m, 8H) 13C NMR (100 MHz, DMSOd6, ẟ ppm): 60.2,
70.0,72.3, 120.1, 125.0, 127.9,129.8, 131.9,134.8, 149.8,152.8, 153.7,170.8.
3. Result and Discussion
3.1 Synthesis:
The host Isophthalohydrazide-cDB24C8 Cryptand (R) was synthesised by adopting the
13
procedure as mentioned in the scheme 1 and characterised by 1H NMR, C NMR, mass and
FT-IR spectral data.
3.2 UV-Visible titration:
The host-guest interaction of cryptand receptor and fluoride was examined by recording the
optical changes of their solution in DMSO using UV-Vis spectroscopic titration. UV-Vis
spectroscopic titration experiment was carried out by concurrent addition of
-
-
-
-
tetrabutyamommnium salt [(Bu4N)+X-, X-=F-, Cl-, Br-, I-, CN-, N3 , NO2 , ClO4 , H2PO4 ,
-
HSO4 , CH3COO-] solutions of various anions to the 0.028 µM solution of receptor R in
DMSO. A solution of receptor R (0.028 µM) in DMSO was titrated with 0.1 equivalent
aliquots of anion solution in DMSO and the spectral changes were recorded. The addition
was done by at regular interval, at each step the optical change were noted down in UV-Vis
spectrophotometer. Fluorescence spectra were also recorded in same way as of the UV-Vis
spectra.
The host cryptand (R) in DMSO showed a characteristic sharp absorption peak at 327 nm.
when 0.1 equivalents of fluoride aliquots was added at regular interval to a quartz cuvette
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containing 2.1 ml of 0.028 µM solution of the receptor R, the absorbance at 327nm of the
receptor (R) decreased progressively and two new absorption peaks were observed at 280 nm
and 259 nm, which were increased in each addition of Fluoride [Fig.1(a)]. These sets of
spectra showed a clear isosbestic point at 295 nm, which suggest the presence of at least one
stable species at equilibrium and formation of a stable complex between receptor and
fluoride. This complex may be formed due to strong hydrogen bonding between anion and –
NH & aromatic –CH of isophthalate of cryptand. It was found that the spectral changes in
UV-Vis spectrum almost diminished when 1:1 stoichiometric ratio was reached as shown in
the figure 1 (a) and no significant spectral changes was observed after 1 : 1 eqv. which was
also confirmed by the jobs plot in figure S 6 of SI.
(a)
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(b)
Figure 1: UV-Visible titration spectra of (a) receptor R in DMSO with tetrabutylammoniun
fluoride solution and (b) with tetrabutylammonium salt solutions of various anions.
Similar investigations were carried with the tetrabutylammonium salts solution of other
-
-
-
-
-
anions (Cl-, Br-, I-, CN-, N3 , NO2 , ClO4 , H2PO4 , HSO4 , CH3COO-) and the titration were
carried out in the same procedure as of the fluoride with each anion separately. In all cases it
was observed that the absorbance of the receptor R at 327 nm was slightly decreased on
titration but no new absorption peak was observed in the recorded spectra. The slight
decreased in absorbance of the receptor was observed may be due to dilution in each addition.
From the figure 1(b), it was clear that the cryptand R selectively recognise only fluoride at
very low concentration and give spectroscopic changes either from single fluoride solution or
mixture of fluoride with other anions. The limiting value was reached on forming a 1:1
adduct between receptor and fluoride and was confirmed by the jobs plot (figure S6). Thus
gradual decrease in absorption band at 327 nm and formation two new blue-shifted higher
absorption peak at 280 nm and 259 nm with a clear isosbestic point at 295nm confirms the
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formation of hydrogen bond complex only with fluoride. This cryptand receptor gives
spectral changes at very low concentration with very high selectively, which reveals that it
could be used for recognition of fluoride from a mixer of anions solution.
3.3 Determination of association constant
The association constant Ka was calculated from UV-Vis spectroscopy at λmax of 326 nm [19].
Calculation shows that the receptor has strong binding constant of 2.7×107 M-1 with fluoride.
The selectivity test of receptor for fluoride over other halides was also studied by observing
the UV-Visible spectral change of the receptor with 0.028µM F- in presence of more
concentrated 28 µM of Cl-, Br-, I-, but the same spectra was observed as the shown in Fig .1
(b). The association constants for F-, Cl-, Br- and I- were 2.7×107 M-1, 6960 M-1, 1513 M-1 and
292 M-1 respectively. Hence the selective binding of fluoride is very high than the other
halides and 3880 folds higher than chloride. From this study it can be concluded that the
cryptand receptor could selectively recognize fluoride very strongly even in presence of high
concentration of other halides.
3.4 Limit of detection
The limit of detection was calculated from calibration curve obtained from UV-Vis titration
data according to IUPAC definition (figure S7) [20]. A plot of concentration Vs absorbance
at 326 nm was used for the determination of LOD. The receptor shows a detection limit of
2.31×10-10 M experimentally. This receptor can selectively recognize fluoride comparatively
at very low concentration compared with the other reported sensors (Table 1).
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Table 1: comparison of detection limit of cryptand receptor R with some reported receptor.
Name of receptor
Detection limit
1.38 mM for Fluoride
50 μM for Fluoride
50 μM for Fluoride
2.0 μM for Fluoride
1.0 mM for Fluoride
References
4-Chloro-2,6-bis(Hydroxymethyl)Phenol receptor
Pyrrole based receptor
21
22
23
24
25
N-Phenyl-Nʹ-(3-quinolinyl)urea receptor
Urea receptor with azobenzene group
N-imidazolyl-1,8-naphthalimide based receptor
Benzimidazolyl Based receptor
Urea and thiourea based receptor
0.1 μM for F− and CN−
0.2 μM for F- and AcO-
0.4 μM for F-
26
27
28
1,3-bis(5,6-dimethyl-1H-benzo[d]imidazol-2-
yl)benzene receptor
2,6-Bis(2-benzimidazolyl)pyridine receptor
0.96 μM for F-
29
Isophthalohydrazide-cDB24C8 Cryptand receptor
2.31×10-10 M for F-
This work
4. Fluorescence titration:
The selective detection and host–guest interaction of the cryptand R with fluoride anion in
presence of other anions was also investigated by fluorescence spectroscopic titration
experiment. Titration was done by adding tetrabutylammonium salts solution of all anions (F-
-
-
-
-
-
, Cl-, Br-, I-, CN-, N3 , NO2 , ClO4 , H2PO4 , HSO4 , CH3COO-) in DMSO to the solution of
cryptand receptor R in DMSO. The fluorescence emission spectra of 0.028 μM solution of
the receptor R in DMSO showed a broad band at 414 nm when excited at 326 nm. The
optical changes in fluorescence spectra was observed on addition of 0.1 equivalent aliquots of
fluoride solution [figure 2. (a)]. On addition 0.1 equivalent of the [Bu4N]+F- solution a large
quenching up to 79.13% of the intensity of the band at 414 nm was observed. The band was
also slightly shifted to 442 nm from 414 nm. This indicates that the formation of hydrogen
bonding between host receptor and the guest fluoride ion and the excited state was modified
considerably leading to quenching of fluorescence. Similarly tetrabutyleammonium salt
solutions of other anions were titrated with the receptor R, but no significant quenching was
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observed [figure 2. (b)], there also observed a smaller quenching of only 15 % and 12%
respectively for chloride and acetate anions.
(a)
(b)
Figure 2. Fluorescence titration spectrum of receptor R in DMSO (a) with addition of
tetrabutylammoniun fluoride and (b) with addition of tetrabutylammoniun salts solutions of
various anions.
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Therefore formation of supramolecular complex between cryptand host R and selectively
with guest fluoride was confirmed by observing the alternation of optical properties and this
sensor could be used for selective fluoride recognition even from the mixture of anions.
1
5. H NMR titration:
1
The binding and recognition of anion could be better understood by HNMR titration, as it
provides the detail information about the host-guest interaction. From the UV-Vis and
fluorescence spectra it was clear that the receptor (R) selectively recognize the Fluoride ion,
1
therefore we performed the HNMR titration of the receptor (R) with TBAF only. The
titration experiment was carried out at room temperature in DMSO-d6 solvent and the
changes in chemical shift were observed. The titration spectra of the cryptand receptor and
spectra after addition of fluoride were shown in the figure 3 .
The receptor (R) shows a characteristic peak for –NH of amide (Hb) at ẟ 9.82, which
minimized and slightly shifted to up field after addition of 1 equiv. of fluoride anion solution,
this may be due to formation of hydrogen bonding with fluoride. The Hb peak was completely
disappeared after addition of 2 eqv. of solution of TBAF. This spectral change suggests that –
amide N-H proton was deprotonated by fluoride [20b-30]. The imine proton Ha was shifted to
up field and Hc proton of isophthalate was slightly shifted to downfield. The shifting of the
Hc proton indicates that the hydrogen bond interaction was also established with inner proton
of the isophthalate aromatic ring. The other aromatic protons also become broad and formed
multipletes. When the fluoride ion binds with –NH of amide and Hc of isophthalate, large
conformational changes were occurred to accommodate fluoride in the cavity of the receptor
(R) so the changes in chemical shifts were observed. From the above discussion it was
cleared that –NH proton of amide, -CH of isophthalate and imine proton of the receptor were
actively taking part in the complexation via hydrogen bonding with fluoride and the Hb
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proton was completely abstracted by the fluoride and in order to accommodate fluoride it
undergoes sensible twist. The larger size of the other anions compared to the fluoride may not
be allowed by the receptor to enter in to the cavity due to steric hindrance.
Figure 3 : 1H NMR spectra of receptor R recorded over the course of titration with TBAF in
DMSO-d6.
6. Computational study:
To get physical information about the cryptand receptor (R) and the host-guest complex at
the molecular level, we have performed theoretical calculations employing the Density
Functional Theory (DFT) with the help of Gaussian09 program package [31]. The ground-
state geometries of the receptor R and its fluoride complex have been optimized at solvent
phase (DMSO) using the DFT incorporating B3LYP functional [32,33] and 6-311G(d,p)
basis set. From the ground state calculations, we have obtained ground-state energies of the
receptor and its fluoride complex as -2290.16 a.u. and -2389.97 a. u. respectively.
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Figure 4 : The optimized structures of (a) cryptand R and (b) cryptand-fluoride complex.
Table 2. Structural parameters of receptor-fluoride complex obtained from the optimized
geometries.
Bond parameters
Bond distance (Å)
1.98
1.61
Bond parameters
Bond distance (Å)
1.03
1.05
F-H1 (rF-H1
F-H2 (rF-H2
)
)
H1-N1 (rH1-N1
H2-N2 (rH2-N2
)
)
Foot note : Atom number in parenthesis follow the numbering pattern provided in Fig. 4 (a)
and (b).
To calculate the interaction energy we have carried out the single point energy calculation
(with counterpoise) of the receptor-F complex. We have found corrected complexation
energy (Eint(corr))= -118.19 kcal/mole and raw complexation energy (Eint(raw)) = -833.70
kcal/mole. The negative value of the interaction energy shows a strong interaction between
the receptor and the Fluoride ion.
The optimized geometries of the receptor R and its fluoride complex are shown in Fig. 4 (a)
and (b) respectively. In the fluoride complex of the receptor R, the plausible interaction
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between the receptor and the fluorine atom occurs via hydrogen-bond formation. This has
been supported by the observed bond lengths of the formed bonds between the fluoride and
the hydrogen-atoms (H1 and H2) i.e., rH-F 1.98 Å and 1.61 Å respectively. Both the hydrogen
atoms are bonded to the N1 and N2 nitrogen atoms as shown in Fig. 4. The dotted lines in
Fig 4(b) represents the hydrogen bond between the fluoride ion and the hydrogen atoms. The
reported hydrogen bonds are confirmed by comparing with the typical hydrogen bond
distance range available in literature.
Moreover, TD-DFT calculations were performed to accumulate the electronic transition
properties along with the absorption and oscillator strengths (fosc) of the receptor-fluoride
complex. Here, we have employed the CAM-B3LYP/6-311G(d,p) level of theory for the
excited state calculation. To support the experimental findings with the help of theoretical
calculation, we have computed the UV-visible spectra for the fluoride complex by using
DMSO as the solvent along with the conductor-like polarizable continuum model (C-PCM).
Figure 5: The UV-vis spectra of the receptor and receptor-fluoride complex using theoretical
calculation.
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The computed UV-visible spectra has been plotted in Fig. 5. The figure shows a principal
absorption band for the receptor at 276 nm (fosc = 0.73) . Upon binding with the fluoride ion
the absorbance gets increased i.e., fosc value changes from 0.73 to 1.02 which is in agreement
with the experimental findings. This observation can be easily understood from Table 3.
However, the receptor shows another absorption band at 302 nm (fosc = 0.74) which correlates
with the experimentally observed absorption at λmax =327 nm. After addition of the fluoride
ion the absorbance gets decreased i.e., fosc value changes from 0.74 to 0.48 which is also in
agreement with the experimental finding (Table 3). So, we can conclude that the theoretical
studies are consistent with the changes observed in the UV-vis titration experiments.
Table 3: Molecular orbitals involved in electronic transition along with the electronic
parameters.
Compounds
Receptor
Eg
Λmax (nm)
302
fosc
Transition (%)
H--->L+1 (59)
H-1--->L (56)
4.11
4.49
4.06
0.74
0.73
0.48
276
Receptor-F
305
H--->L+1 (36)
H--->L (35)
4.20
295
1.02
H-1--->L (40)
In Table 3, we have also presented the electronic transition parameters of the receptor and the
receptor-F complex. The table shows two absorption bands for the receptor at 302 nm and
276 nm. These two bands are originated from the electronic transitions H--->L+1 and
H-1--->L respectively. Here, both the absorptions observed at 302 nm and 276 nm results
into a broad absorption peak (as shown in figure 5). However, the receptor-F complex also
shows two absorption peaks at 305 nm and 295 nm (higher absorbance i.e., 1.02) due to the
electronic transitions (H—>L+1, H--->L) and H-1--->L respectively. The molecular orbitals
16

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that involved in the electronic transitions are shown in figure 6 for both the receptor and the
receptor-F complex.
Figure 6: Molecular orbital diagram of the orbitals that involved in electronic transitions.
It can be concluded from the theoretical calculation that the obtained TD-DFT absorption
maximum value at 295 nm reasonably close to the experimentally observed absorption
maximum at 280 nm. Hence, we can infer that shift of absorption band from 327 nm to 280
nm occurs due to the formation of H-bonds in the fluoride complex.
Conclusion:
In conclusion, we have designed and synthesised an efficient novel cryptand derivative as a
highly selective receptor for fluoride ion. The receptor could recognise the presence of
fluoride from its mixture with high concentrated solution of the other anions. The sensing
property of this receptor was examined very carefully at concentration as low as and the LOD
of the receptor was found to be 2.31×10-10 M. This receptor has high selectivity and
sensitivity towards fluoride ion. It can selectively detect fluoride from a mixture of other
anions. The selectivity of receptor R was established via optical changes in UV-Vis spectra
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and fluorescence emission spectra. 1H NMR titration and the theoretical study also reveal the
experimental result. This novel cryptand receptor can be used for fluoride detection at very
low concentration.
Acknowledgment
The authors acknowledge the Department of Science and Technology for financial
assistance under DST-SERB (No. SB/FT/CS-161/2012, No. SB/FT/CS-077/2013), UGC-
BSR Research start-up-grant (NO.F.30.-122/2015(BSR)) and also thankful to SAIF NEHU-
Shillong, SAIF-IITM for spectral data.
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Graphical Abstract
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Highlights
 Novel Isophthalohydrazide-cDB24C8 cryptand derivative was synthesized
 Fluoride recognition at very low concentration of 2.31×10-10
M
1
 Anion binding was studied using UV-visible and fluorescence spectroscopy and H
NMR
 TD-DFT calculation was performed to accumulate the electronic transition properties
 TD-DFT calculations qualitatively match the experimental UV-Visible spectra
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