Colorimetric sensing and anion recognition by Kalanchoe flower-like ligand and its transition metal complexes with polarized N-H interaction motifs

Article abstract of DOI:10.1016/j.molstruc.2020.129701

Herein we report the selective sensing of fluoride ion with kalanchoe flower-like ligand, L ( 2?chloro?3?((3?dimethylamino)propylamino)naphthalene?1,4?dione) and it's metal (K1-Cu(II), K2-Co(II), K3-Zn(II)) complexes. The morphology and anion sensing prop

Full text of DOI:10.1016/j.molstruc.2020.129701

Journal of Molecular Structure 1228 (2021) 129701
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstr
Colorimetric sensing and anion recognition by Kalanchoe flower-like
ligand and its transition metal complexes with polarized N-H
interaction motifs
a,∗
b
b
a
A. Kosiha , M. Devendiran , K. Krishna Kumar , R.A. Kalaivani
a
Department of Chemistry, School of Basic Science, Vels Institute of Science, Technology & Advanced Studies (VISTAS)(Deemed to be University), Chennai
00 117, India
6
b
Central Instrumentation Laboratory, Vels Institute of Science, Technology & Advanced Studies (VISTAS)(Deemed to be University), Chennai 600 117, India
a r t i c l e i n f o
a b s t r a c t
Article history:
Herein we report the selective sensing of fluoride ion with kalanchoe flower-like ligand, L ( 2–chloro–3–
Received 4 May 2020
((3–dimethylamino)propylamino)naphthalene–1,4–dione) and it’s metal (K1-Cu(II), K2-Co(II), K3-Zn(II))
Revised 12 November 2020
Accepted 30 November 2020
Available online 3 December 2020
complexes. The morphology and anion sensing properties of the L and K1-K3 compounds were investi-
gated with microscopic and spectroscopic techniques. 1H NMR titration was carried out to understand the
fluoride ion interaction with the N-H interacting site of the ligand and its metal complexes. Furthermore,
quantum chemical calculations were conducted to rationalize the interaction between chemosensors and
anions.
Keywords:
Anion sensing
DFT
©
2020 Elsevier B.V. All rights reserved.
Fluoride ion
kalanchoe flower-like ligand
N-H interaction motifs
1
. Introduction
areas of supramolecular chemistry, environmental ecosystem, and
diagnostic tool in medicinal fields due to its selectivity and sen-
sitivity [9]. Some of the anions like phosphate, fluoride, cyanide,
and nitrate are convicted as pollutants due to their harmful roles.
Among these, a great deal of attention is devoted to the devel-
opment of chemosensors for the basic anion of fluoride recogni-
tion and real-time monitoring because of its clinical treatments
for osteoporosis, orthodontics. The excess of fluoride entry into the
body leads to adverse effects like fluorosis and urolithiasis [10–12].
Fluoride ion sensing motifs occur in hydrogen bonding units such
as triarylboranes, desilylation, pyrroles, amides, ureas, thioureas or
sulphonamides [9] and are available in the literature. Sensing mo-
tifs are developed based on NH deprotonation or hydrogen bond
Quinone derivatives signify a large group of substances present
in several families of plants and microorganisms. They enact key
roles in vital processes such as cellular respiration and photosyn-
thesis due to its facile electron transfer property. Quinones are
classified as benzoquinones, naphthoquinones, and anthraquinones
based on aromatic systems [1,2]. Though quinones imprinted their
promising anticancer activities, tailoring with naphthaquinone
derivatives exhibit diverse pharmacological properties and po-
tential anticancer activities [3]. In particular 1,4-naphthoquinone
demonstrates important anticancer activity in several drugs, such
as streptonigrin, mitomycin, and actinomycin, [4]. It is worth to
note that 2,3-dichloronaphthoquinone is key synthetic intermedi-
ate in organic, medicinal, and industrial chemistry. In this study,
the synthesized ligand was used to make CT (charge transfer) com-
plexes by external electron donors. In this phenomenon, the amine
group is formed between a weak nucleophile, the ligand precur-
sor 2,3-dichloronaphthoquinone, and dimethyl propylene diamine
−
formation with F ion which has been reported for the selectiv-
−
ity of F ions over the other competitive anions [12,13]. Synthesis,
spectral characterization, and their biological activity of L and K1-
K3 compounds were reported earlier [14]. In the present study, the
selective colorimetric sensing of fluoride anion with the naphtho-
quinone L and K1-K3 compounds was reported.
[
5–7]. The biological activity of quinone enhances when it is coor-
dinated to transition metal ions [8]. The design and development
of anion recognizing motifs gain much attention in the research
2. Experimental methods
2
.1. Chemicals
∗
All the anions as their tetrabutylammonium salts, solvents,
Corresponding author.
E-mail address: kosiha@gmail.com (A. Kosiha).
and other chemicals were purchased from Sigma-Aldrich and
https://doi.org/10.1016/j.molstruc.2020.129701
0
022-2860/© 2020 Elsevier B.V. All rights reserved.

A. Kosiha, M. Devendiran, K.K. Kumar et al.
Journal of Molecular Structure 1228 (2021) 129701
Fig. 1. Optimized Structures of L (A), K1 (B), K2 (C) and K3 (D).
Fig. 2. FESEM images for L (A) (Inset: Magnified image), K1 (B), K2 (C) and K3 (D).
2

A. Kosiha, M. Devendiran, K.K. Kumar et al.
Journal of Molecular Structure 1228 (2021) 129701
Merck (India). The precursor, chemosensor ligand (L) (2–chloro–3-
(
(3–dimethylamino)propylamino)naphthalene–1,4–dione) and K1-
K3 complexes, were prepared as reported in our previous paper
14].
[
2
.2. Instrumentation
The absorption spectra were carried out on JASCO (V630, Japan)
double beam spectrophotometer, while fluorescence spectra were
on the Caryeclipse fluorescence spectrophotometer (Agilent tech-
nologies). Nuclear magnetic resonance spectra were recorded on
Bruker, 300 MHz spectrometer in presence of DMSO-d6 solvent
using tetramethylsilane (TMS) as internal reference. The chemical
shift were expressed in units of ppm (normalized integration, mul-
tiplicity, and the value of J in Hz) with respect to the DMSO-d6 . 1H
NMR titration studies were carried out with incremental addition
−
of (0.5 and 1eq.) F to the DMSO-d6 solution of L and K3. Sur-
face morphology investigation was done using the Thermo Scien-
tific QuattroS field emission scanning electron microscope (FESEM).
The geometrical optimization of the complexes was performed us-
ing Density Functional Theory with the B3LYP hybrid functional,
by using a basis set of 6-31G. Computations have been performed
using the Gaussian 03 Revision D.01 program package.
2
.3. Synthesis of the L and K1-K3
The and K1-K3 were synthesized and characterized
L
by using various analytical methods as mentioned in our
previous work [14]. In brief, an ethanolic solution of 2,3-
dichloro-1,4-naphthoquinone (DCNQ) (5g, 0.0220 mol) and
N,N’-dimethylpropylenediamine (6.15g, 0.0220 mol) was stirred
at RT for 4 h, resulting in the precipitation of solid product. It
was washed with 50% ethyl acetate and pet ether. Then it was
dissolved in water, neutralized with potassium carbonate and
obtained as pure product after dried.
Fig. 3. Color changes of L, K1, K2 and K3 with anions.
Ligand (1.7 mmol) was dissolved in 10 mL of dichloromethane
structure. The micrograph of K1 shows the formation of loosely ag-
gregated rods (Fig. 2B). FESEM image of K2 has looping stick with
fine-sized particles (Fig. 2C) like morphology. Finally, K3 exhibits
a large quantity of flower-shaped nanoflakes aggregation(Fig. 2D).
Hence, FESEM micrographs indicated the L and K1-K3 compounds
were microns in size [15].
(
DCM) and then metal chloride salts (1.7 mmol) dissolved in 10 mL
of ethanol was added drop-wise, stirred and heated at 50°C for 5
h [14]. After the evaporation of all the solvents, the solid product
collected was washed with DCM and ethyl acetate. The optimized
structures of L, K1, K2, and K3 have been depicted in Fig. 1.
3. Results and Discussion
3
.3. Anion Sensing
3
.1. Structure Characterization
The anion sensing properties of compounds (L, K1-K3) were in-
vestigated using various techniques such as UV-vis, fluorescence,
1H NMR, and DFT computations to substantiate the spectral con-
The chemical structure of L was confirmed by elemental and
spectral analyses. The IR spectrum of L exhibits the characteris-
clusions.
−1
tic peaks at 3433 ʋ(NH), 1595 and 1679cm pro to ʋ(C=O) which
confirms the structure of the ligand. The molecular structure of L
was also determined by X-ray crystallography. The compounds K1-
K3 were prepared in high yields in single step reaction. The struc-
tural identities of K1-K3 were also characterized by FT-IR, UV–vis,
ESR spectroscopy, HR-MS technique, thermal analysis (TGA), and
magnetic moment measurements(Figure S1-S8 and Table S1,S2)
3
.3.1. Naked-eye detection
The colorimetric sensitivity of L and K1-K3 compounds towards
−
−
−
−
−
−
−
various anions such as F , Br , I , AcO , H PO , CN and NO3
2
4
in their tetra butyl ammonium form, was monitored visually con-
comitantly. As shown in the figure (Fig. 3), a color change from
yellow to blue was observed upon the addition of fluoride ion to
the solution of L and K1 (in 20% aq. DMF), K2 and K3 compounds.
At the same time, their color remains unchanged after the addi-
[
14].
− − − − − −
tion of Br , I , AcO , H PO , CN and NO3 this is probably due
2 4
3
.2. Morphological study
−
to high negative charge density on F which brings out the strong
The surface morphology of the
L
and K1-K3 compounds
hydrogen bonding with NH in L and K1-K3 compounds [16,17].
was studied by using a Field emission scanning electron micro-
scope (FESEM) under Environmental Scanning Electron Microscopy
3.3.2. UV-vis spectroscopic studies
(ESEM) mode. Fig. 2 shows the FESEM surface morphology of all
The interaction of the L and K1-K3 compounds with F- was in-
vestigated in detail through UV-vis spectroscopy in DMF solutions
containing 2.5 × 10−4M of the test compounds. The titration was
the compounds. The L was distributed uniformly as shown in
Fig. 2A and resembles a kalanchoe flower (four-leaf flower) like
3

A. Kosiha, M. Devendiran, K.K. Kumar et al.
Journal of Molecular Structure 1228 (2021) 129701
Fig. 4. UV-vis absorbance changes of L, K1, K2, and K3 upon addition of fluoride ions in DMF.
Fig. 5. Other anions with L (A) and K3 (B).
−
carried out with L, K1-K3 and their corresponding UV-vis spectral
changes are depicted in Fig. 4. With the addition of incremental
amounts of fluoride ion to the solution of L and K1-K3, the absorp-
tion spectral peak at λmax474 nm (log ε=2.95), which corresponds
to the ICT transition between the receptor (amine N-H—F ) and
quinone signaling units. Thus, the metal complex is passably a bet-
ter electron donor than free ligand. The UV-vis spectra of L and
K1 compounds were showed no perceptible color change during
∗
−
to the intramolecular charge transfer (ICT) transition (n-π ) from
the addition of other anions except F (Fig. 5) and confirmed that
N-atoms to the quinone moiety [18] disappears gradually and ac-
companying the formation of the new band centered at 585 nm
the compounds were highly selective towards fluoride ion [19,20].
The stoichiometry of L and metal complexes (K1- K3) with an-
ions, were studied by continuous variation method (jobs pot) [19].
The proposed complex of compounds with anion stoichiometries
(
bathochromic shift). The K1 also exhibited similar spectral behav-
ior on adding fluoride ions (Fig. 5) to the solution of DMF: H O
2
−
(
80:20%). This is accompanied by the instantaneous formation of
is shown in Fig. 6. The L, K1, and K2 with F ion seemed to have
blue color (ꢀ λICT=111nm) with a occurrence of new band due
the binding mole fraction of compounds of 0.5, which means L and
4

A. Kosiha, M. Devendiran, K.K. Kumar et al.
Journal of Molecular Structure 1228 (2021) 129701
ally increased. These results indicate that the fluoride ions interact
with the L and K1-K3 compounds through H-bonding [22,23].
From the fluorescence enhancement data the binding constant
−
of the Ligand-F complex can be determined using the Bensi-
Hildebrand equation [24].
Fα − F0)/(Fx − F0) = 1/k[F−]
(
Where F , Fα, and Fx are the fluorescence response observed in
0
−
the absence, presence of F ion, and at a specific concentration
−
of F to complete the interaction, respectively. Fig. 8 shows linear
−
plots of (Fα-F )/(Fx-F ) versus 1/[F ] for the L and K1-K3. From the
0
0
observed enhancement of emission intensity, the binding constant
−
of the compounds -F was calculated using the following equation
[
23]
log (Fo − F)/F = log Ka + n log [Q]
Fig. 6. Job’s plot for L, K1, K2, and K3.
Where F0, F fluorescence responses observed in the absence and
presence of fluoride ion, at the quencher concentration [Q] and Ka
is the binding constant and n is the stoichiometry ratio between
K1-K3 compounds form a complex with anions at a stoichiometry
of 1:1 ratio. The mole fraction of K3 is 0.3, which means the stoi-
chiometry of K3 and anion complex is 1:2 ratio [21].
−
the F and L, K1-K3. The plot of log (F0 – F) versus log [Q] is lin-
−
ear for F with L, K1, K2, and K3 as shown in Fig. 9. The binding
4
5
5
constants were calculated to be 4.67 × 10 , 2.81 × 10 , 1.41 × 10 ,
4
and 4.81 × 10 for the L, K1-K3, respectively. The result of emis-
3
.3.3. Emission spectral studies
sion study was manifested that the alliance of the L and K1-K3
with fluoride ions are in the sequence of K1 >K2 >K3> L. These
results anticipated that the complexation process would make the
amine hydrogen atom more acidic and inevitably a better H-bond
donor towards fluoride ions [25]. The detection limit of L, K1-K3
The fluorescence spectroscopy measurements that respond to
the ability of L and K1-K3 with fluoride ions were recorded with
excitation at 475,472, 472, and 473nm, respectively. As shown in
Fig. 7 it is evident that the addition of an incremental amount of
−
−
F
to the L and K1-K3 in all cases, the emission intensities of these
for F was calculated and showed in Table 1. From that, the low-
−
compounds at 587, 620, 620, and 403 nm respectively were gradu-
est detection limit of F with K1 is 2.04 μM.
Fig. 7. Fluorescence titration curves of L, K1, K2, and K3 upon addition of fluoride ion in DMF.
5

A. Kosiha, M. Devendiran, K.K. Kumar et al.
Journal of Molecular Structure 1228 (2021) 129701
Fig. 8. Benesi-Hildebrand plot used to determine the association constant of the ICT complex formed by and F¯ at different fluoride concentrations.
Fig. 9. 1H NMR spectra of (a)L with (b) 0.5, (c) 1 eqv. of F- ion in DMSO-d6.
Table 1
−
Detection Limit, Association and Binding constants (KA) of ligand and its complex with F ions.
−1
−1
Binding Constant (K)/mol L
Receptor
λ
ICT (nm)
ꢀλICT (nm)
Association Constant (KA)/ M
λex (nm)
λ
em (nm)
Detection Limit (μM)
−
−
Without F
With F
3
4
L
475
472
472
473
585
590
591
587
110
118
119
114
2.43 × 10
475
472
472
473
416
620
620
411
4.67 × 10
68
3
5
Cu(II)
Co(II)
Zn(II)
5.30 × 10
2.81 × 10
2.04
3.81
27
3
5
3.45 × 10
1.41 × 10
3
4
3.22 × 10
4.81 × 10
−
3
.3.4. 1H NMR titration
of NH in both the L and K1-K3 compounds with F was down-
−
1
−
The interaction of L and K3 with F ion was deliberated with H
field broadening, because F causes deshielding of NH proton due
NMR titration in DMSO-d6 solvent, which results a significant
chemical shift changes on the N-H proton with the addition of
to H-bonding that resulted into downfield shifting [23].
−
F ion [26,27]. This was emblematic of strong hydrogen bonding in-
3
.3.5. Theoretical studies
teraction between the N-H group and the anion. Before the addi-
DFT study calculations were used to monitor and support the
−
tion of F , NMR chemical shift, for NH proton was observed at δ
−
photophysical changes of F with L and K1-K3 and the ener-
8
.08 ppm (in case of L) and δ 8.07 ppm (in case of K3). Upon the
gies were compared with experimental observation. The geome-
−
addition of 0.5 and 1equiv. of F to the L and K3, the characteristic
sharp NH peak of sensing motifs were moved to broadening and
disappeared finally without disturbing other organic protons as il-
lustrated in Figs. 9 and 10. Surprisingly, we observed broadening
tries were optimized at DFT based B3LYP/6-31G level of theory
−
[
28]. The interaction of F with L and K1-K3 was analyzed com-
putationally by predicting frontier molecular orbitals (HOMO and
LUMO) along with the difference in energy between them and is
6

A. Kosiha, M. Devendiran, K.K. Kumar et al.
Journal of Molecular Structure 1228 (2021) 129701
Fig. 10. 1H NMR spectra of (a) K3 with (b) 0.5, (c) 1 eqv. of F ion in DMSO-d6.
−
Fig. 11. Frontier MO’s of L, K1, K2, and K3.
7

A. Kosiha, M. Devendiran, K.K. Kumar et al.
Journal of Molecular Structure 1228 (2021) 129701
Table 2
Acknowledgement
Theoretical data of the L, K1, K2, and K3.
Compound/Complex
L
HOMO (eV)
LUMO (eV)
࢞E (eV)
The authors are thankful to Dr. T. Sathiya Kamatchi, Dr. D S
Kothari Post Doctoral Fellow for her timely help to improve the
quality of the manuscript.
5.4564
3.6937
6.6268
6.3769
6.0715
6.4918
5.8292
5.6899
4.5024
3.0983
3.7108
4.1764
3.4943
3.9146
3.4422
3.9356
0.9540
0.5953
2.9159
2.2005
3.2356
2.5772
2.3870
1.7543
−
L + F
Cu(II)
Cu(II)+ F−
Co(II)
Co(II) + F−
Supplementary materials
Zn(II)
Zn(II) + F−
Supplementary material associated with this article can be
found, in the online version, at doi:10.1016/j.molstruc.2020.129701.
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Declaration of Competing Interest
3
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CRediT authorship contribution statement
A. Kosiha: Conceptualization, Methodology, Investigation, Writ-
ing - original draft. M. Devendiran: Formal analysis, Writing -
review & editing. K. Krishna Kumar: Resources. R.A. Kalaivani:
Project administration.
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