Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 129 (2014) 509–518

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Spectrochimica Acta Part A: Molecular and

Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa

Synthesis, characterization, structural analysis of metal(II) complexes

of N0 -[(E)-3-Bromo-5-Chloro-2-hydroxybenzidene]-4-hydroxy
benzohydrazide—Multisubstituted Schiff base as a F and Cu2+
ions selective chemosensor
A. Sundar a, M. Prabhu d, N. Indra Gandhi b, M. Marappan d,⇑, G. Rajagopal a,c,⇑
a
Department of Chemistry, Madras Medical College, Chennai 600 003, India
b
PG & Research Department of Chemistry, Presidency College (Autonomous), Chennai 600 005, India
c
Department of Chemistry, Government Arts College, Melur, Madurai 625 106, India
d
Department of Chemistry, Government Arts College (Men), Nandanam, Chennai 600 036, India

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Synthesis of novel multisubstituted

hydrazone based Schiff bases.
 Structurally solved Schiff bases for
the first time.
 Schiff base is selective sensor for
fluoride ion.
 Also acts as chemosensor for cations.

a r t i c l e i n f o a b s t r a c t

Article history: New colorimetric chemosensor, N0 -[(E)-3-Bromo-5-Chloro-2-hydroxybenzidene]-4-hydroxybenzohyd-

Received 9 January 2014 razide, containing OH and NH groups as binding sites have been synthesized and characterized by
Received in revised form 9 March 2014 spectral UV, IR, NMR and ESR. The molecular structure of ligand is determined by X-ray crystallography
Accepted 21 March 2014
and it has the monoclinic space group P21/c with cell parameters a = 15.1058(6), b = 14.3433(6),
Available online 5 April 2014
c = 17.5800(8) Å and Z = 8. The electronic spectral measurements show that Co2+, Ni2+ and Zn2+ com-
plexes have tetrahedral geometry, while Cu2+ complex has square planar geometry. Magnetic measure-
Keywords:
ments show that Cu2+, Co2+ and Ni2+ complexes have paramagnetic behavior and Zn2+ complex has
Hydrazones
X-ray analyses
diamagnetic behavior. Anion binding studies carried out using 1H NMR and UV–visible spectrophotomet-
Colorimetric ric titrations revealed that these receptors exhibit selective recognition towards F over other halide
Chemosensor anions. The selectivity for F among the halides is attributed mainly to the hydrogen-bond interaction
Fluoride sensor of the receptor with F. Receptor (5  105 M) shows color change from colorless to yellow in the pres-
Cation sensor ence of tetrabutylammonium fluoride (TBAF, 1.5  103 M). Moreover, F-induced color changes remain
the same even in the presence of large excess of Cl, Br and I. The binding constant is found to be higher
towards F ion and this may be due to presence of OH group, which offers extra binding site. Chromo-
genic receptor undergoes distinct color changes from colorless to green on gradual addition of Cu2+

⇑ Corresponding authors. Address: Department of Chemistry, Madras Medical College, Chennai 600 003, India. Tel./fax: +91 452 2415671 (G. Rajagopal), Department of
Chemistry, Government Arts College (Men), Nandanam, Chennai 600 036, India. Tel./fax: +91 44 24310589 (M. Marappan).
E-mail addresses: mmarappan@yahoo.com (M. Marappan), rajagopal18@yahoo.com (G. Rajagopal).

http://dx.doi.org/10.1016/j.saa.2014.03.084
1386-1425/Ó 2014 Elsevier B.V. All rights reserved.
510 A. Sundar et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 129 (2014) 509–518
can be used as colorimetric probes for spectrophotometric and visual analysis of Cu2+ in the presence of
other transition metal ions such as Co2+, Ni2+ and Zn2+.
Introduction
Metal complexes of aroyl hydrazone receptors have remained an
attractive area of research for coordination chemists and structural
chemists because of their versatile coordination chemistry and
capability to generate varied molecular architecture and coordina-
tion geometry [1–5]. Aroyl hydrazone themselves are known to
have a variety of applications such as hole transporting agents [6]
in organic layer photo conductors, and as a drugs for treatment of
cancer, schizophrenia, leprosy pharmaceutical industry [7–9]. It
has also been suggested that nucleophilic substitution [10] of
hydrazone receptors may be an important route to assemble nano-
scale molecular clusters. Ni(II) and Zn(II) complexes of aroyl hydra-
zones formed by condensation of aroyl hydrazides and diacetyl
monooxime and observed that they possess interesting supramo-
lecular structure [11]. In particular, the selective sensing of fluoride
has attention due to its significance in clinical treatment for
osteoporosis and the detection of fluoride as a result of its over-
accumulation in bones [12,13]. ‘Colorimetric chemosensors’ are
molecules that allow ‘naked-eye’ detection of anions without resort
to any spectroscopic instrumentation [14]. Such sensor systems are
generally composed of two parts: one is the anion binding part
(receptor), which is typically based on various combinations of
pyrrole, urea/thiourea, amine or phenol, ACONH centers act as
binding sites for anions [15–17] and cations [18–20] the other is a
chromophore, which converts binding induced changes into an
optical signal such as the appearance of color. These two parts are
either linked directly [21] or intramolecularly associated [22]. With
reference to binding groups, only a limited number of reports are
available using OH as a binding site [23–27]. In most cases, F is
bound to the receptor through FAHAO hydrogen-bonding interac-
tions. The presence of excess F may even cause deprotonation,
resulting in a classical Bronsted acid–base type reaction [28–30].
Hence, chromogenic receptors possessing a phenolic OH and hydra-
zine NH groups, which are able to bind fluoride via H-bond interac-
tions or deprotonation with an electron withdrawing nitro group
which acts as a chromogenic signaling unit. The nature of these
simple Schiff’s base hydrazone receptor is altered by incorporation
of an additional hydroxy group in the receptor, which is able to tune
the anion recognition selectivity. All the above said facts stimulate
our interest in the study of transition metal complexes with O and N
donor ligand and in continuation of our work in the area of Schiff
base complexes [31], the synthesis, characterization, crystal struc-
ture determination and biological screening of metal (II) complexes
of morpholinoaniline Schiff bases are described here. continuous
extension of our work on hydrazones.
Experimental
Reagents
4-Hydoxybenzoichydrazide, 3-Bromo-5-Chlorosalicylaldehyde,
copper(II) chloride.dihydrate, cobalt(II) chloride.hexahydrate,
nickel(II) chloride.tetrahydrate, zinc(II) chloride (Sigma–Aldrich)
are obtained commercially and used without any purification.
HPLC grade solvents acetonitrile, chloroform, dimethylsulphoxide,
dimethylformamside and methanol purchased from Qualigens
(Mumbai, India). Tetrabutylammonium salts of halides are
purchased from Aldrich chemicals (Mumbai, India).
Ó 2014 Elsevier B.V. All rights reserved.
Physical measurements
Elemental analysis is carried out using a Vario EL III CHNS
analyzer. 1H NMR spectra are recorded on a Bruker 500 MHz
spectrometer using TMS as an internal reference at 25 °C in
DMSO-d6. The mass spectra were recorded by the EI technique at
70 eV using Shimadzu QP-2010 coupled with GC–MS spectrometer.
IR spectra are recorded in KBr disks with a Perkin Elmer FT-IR
spectrophotometer, UV–Vis spectra of compounds are recorded
on a Shimadzu 1700 PC series spectrophotometer.
Crystallography
Single crystal X-ray diffraction experiments are performed on a
‘Bruker Smart Apex CCD, Diffractometer’ using graphite monochro-
mated Mo Ka radiation (k = 0.71073 Å) (Crystallographic data is
deposited with the Cambridge Crystallographic data centre). The
structure is solved by direct and refined by full matrix least squares
on F2 with SHELXL-97 program.
Binding constant
The binding constant values for receptor towards anions and
cations were calculated from the UV–Vis titration results using
Benesi–Hildebrand (B–H) Eq. (1).
1 1 1
¼ þ ð1Þ
DA bD ƽG0 ½H0 K a bD ƽG0 
where DA is the change in absorbance, [G0] is the concentration of
the guest molecule, [H0] is the concentration of the host molecule
and Ka is binding constant. Plot can be made with 1/DA as a function
of 1/[H0]. DÆ can be derived from the intercept while Ka can be
calculated from the slope [46].
Synthesis of receptor BCHBHBH
The 4-hydroxy benzoichydrazide (1 mmol) dissolved in 10 ml of
methanol, 3-Bromo-5-Chlorosalicylaldehyde (1 mmol) dissolved in
5 ml is slowly added and stirred for 4 h at room temperature.
Completion of the reaction is monitored through TLC for the
disappearance of the starting compound (Scheme 1). A pale yellow
crystalline solid precipitate is separated out from the mixture.
Crystalline product is washed with ice cold ethanol and dried in
vacuo over anhydrous CaCl2. Single crystals suitable for the X-ray
diffraction are obtained by slow evaporation of a solution of the
title compound in DMF at room temperature. yield – 82%, melting
point – 235 °C.
Synthesis of copper(II), cobalt(II), nickel(II) and zinc(II) complexes
The general procedure for the preparation of the complexes is as
follows. To a solution of the N0 -[(E)-3-Bromo-5-Chloro-2-hydrox-
ybenzidene]-4-hydroxybenzohydrazide (BCHBHBH) (2 mmol) dis-
solved in 15 ml methanol/DMF heating at 80 °C, methanolic
solution of metal salt [CuCl22H2O, CoCl26H2O, NiCl24H2O and
ZnCl2] (1 mmol) is added dropwise. The reaction mixture is gently
refluxed for 3 h during which a solid color complex appears. After
cooling, a crystalline solid precipitate from the mixture is
 A. Sundar et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 129 (2014) 509–518 511

Scheme 1. Synthesis of receptor.

separated out. Crystalline product is washed with ice cold metha- conductivity values (5.0–18.0 X1 cm2 mol1) in DMF indicate
nol and dried in vacuo over anhydrous CaCl2. the nonconducting nature of these complexes. Elemental analyses
and other physical data are presented in Table 2. Type of complex
Results and discussion [M(L)]Cl (where M = Cu2+, Co2+, Ni2+ and Zn2+) is formed.

The molecular structure of ligand is determined by X-ray crys- Crystal structure of BCHBHBH
tallography and it has the Monoclinic space group P21/n with cell
parameters a = 15.1058(6), b = 14.3433(6), c = 17.5800(8) Å and The crystal structure of the N0 -[(E)-3-Bromo-5-Chloro-2-
Z = 8. The dimension 0.40  0.35  0.35 mm was used and the data hydroxybenzidene]-4-hydroxybenzohydrazide (BCHBHBH.DMF)
collected at 293(2) K is shown in Table 1. The IR spectrum of recep- with atom numbering scheme showing 50% displacement ellip-
tor showed a strong band at 1603 cm1 and 1H NMR showed a sin- soids is shown in Fig. 1. Selected bond length and bond angle of
glet at d 8.52 ppm indicating the formation of Schiff base. UV–Vis the compound is listed in Table 3. The molecule exists in the keto
spectrum of receptor showed two predominant bands at 392 nm tautomeric form and the configuration of C7AN1 bond is E. The
and 337 nm suggesting the charge transfer transition taking place molecule exists mainly in two planes. One plane is corresponding
within the molecule. Additionally, a strong intense band was to the phenyl ring of the hydroxy moiety and the other to the
observed at 472 nm when the anions were detected by the recep- remaining part of the molecule. This twisting may be to relieve
tor and form a hydrogen bonding complex (Scheme 2). the steric interactions between the hydrogen atoms N2AH2A and
All the complexes are colored and stable in air. Cu2+, Co2+, Ni2+ C10AH10. The three bond angles around C8 atom are not equal
and Zn2+ are insoluble in water but soluble in coordinating sol- to 120° each. It is seen that the O2AC8AN2 bond angle is consid-
vents, such as DMF and DMSO. The metal complexes shows low erably greater than N2AC8AC9 angle. This observation is similar
to the structures of hydrazones reported earlier [32,33], which is
explained in order to decrease the repulsion between the lone pairs
Table 1 present in N2 and O2 atoms. The central part of the molecule
Crystal data and structure refinement of BCHBHBH.DMF.
adopts a completely extended double bonded conformation. It
Compound BCHBHBH.DMF can be confirmed by the C8AO2 bond length (1.219(4) Å), which
Empirical formula C17H17N3O4BrCl is considerably longer than the standard C@O bond length 1.21 Å
Formula weight 442.70 and C8AN2 bond length (1.361(4) Å), which is shorter than stan-
Temperature T = 293(2) K dard NAC single bond length (1.47 Å). The C12AO3 bond length
Wavelength 0.71073 Å
of methyl atom in the hydroxy group is disordered with site occu-
Crystal system, space group Monoclinic, P21/n
a = 15.1058(6) Å a = 90° pancies is 1.357(4) Å. Hydrogen bonds are shown as dotted lines in
Unit cell dimensions b = 14.3433(6) Å b = 94.823(2)° packing diagram (Fig. 2).
c = 17.5800(8) Å c = 90°
Volume (Å3) 3795.5(3)
NMR spectra
Z, Calculated density (Mg/m3) 8, 1.549
Absorption coefficient (mm1) 2.334
1
F(0 0 0) 1792 H NMR spectra of receptor and its zinc complex are recorded in
Crystal size (mm) 0.40  0.35  0.35 DMSO-d6 solvent. The receptor shows two singlet peaks at 12.84
Theta range for data collec h = 1.71–25.00° (Phenolic OH aldehyde) and 12.32 (Phenolic OH hydrazone) ppm
17 6 h 6 17
due to two OH protons. The peak at 12.84 ppm (Phenolic OH alde-
Limiting indices 17 6 k 6 13
20 6 l 6 17 hyde) and 12.32 (Phenolic OH hydrazone) ppm appeared in the
Reflections collec/unique 35596/6669 [Rint = 0.0466] spectrum of Zn(II) complex [34,37]. The receptor shows a singlet
Completeness to D = 25.00 100% peak at 10.26 and 8.52 ppm for NH and azomethine (ACH@N) pro-
Data/restraints/parameters 6669/376/570
tons respectively. The NH and azomethine protons are shifted in
Goodness-of-fit on F2 1.005
Final R indices [I > 2r(I)] R1 = 0.0396, wR2 = 0.1117
down field in Zn(II) complex. This observation clearly supports that
Largest diff. peak and hole 0.451 and 0.390 (e Å3) the AOH, NH and azomethine proton are involvement in the coor-
dination. The aromatic ring protons are observed as multiplet in

Scheme 2. Binding mode of fluoride ion with receptor.

512 A. Sundar et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 129 (2014) 509–518

Table 2
Analytical and physical data of the BCHBHBH and its metal complexes.

Compound Empirical formula (formula weight) Found (Calc)% Color Melting point (°C) Magnetic moment (lB)
C H N
BCHBHBH C14H10N2O3BrCl 45.42 2.68 7.47 Pale yellow 235 –
(369.6) (45.50) (2.73) (7.58)
[Cu(BCHBHBH)Cl] C14H10N2O3BrCl2Cu 35.81 2.06 5.87 Dark green 335 1.76
(468.6) (35.88) (2.15) (5.98)
[Co(BCHBHBH)Cl] C14H10N2O3BrCl2Co 36.16 2.28 6.02 Brown 356 4.62
(464.0) (36.24) (2.17) (6.04)
[Ni(BCHBHBH)Cl] C14H10N2O3BrCl2Ni 36.18 2.09 6.01 Light green 378 3.64
(463.7) (36.26) (2.17) (6.04)
[Zn(BCHBHBH)2] C28H20N4O6Br2Cl2Zn 41.72 2.44 6.66 Yellow 351 Dia
(804.61) (41.80) (2.51) (6.96)

Fig. 1. Molecular structure of BCHBHBH.DMF Ellipsoids is drawn with 50% probability.

Table 3 examples. The molecular ion peaks were in good agreement with
Selected bond lengths and bond angles of BCHBHBH.DMF. their empirical formula as indicated from elemental analyses.
C(3)ACl(2) 1.738(4) O(1)AC(6)AC(1) 117.8(3)
C(1)ABr(1) 1.873(4) N(1)AC(7)AH(7) 120.6 IR spectra
C(6)AO(1) 1.347(4) O(2)AC(8)AN(2) 119.8(3)
C(7)AN(1) 1.277(4) N(2)AC(8)AC(9) 116.9(3)
IR spectral data for the receptor and their metal complexes are
C(8)AO(2) 1.219(4) O(1)AC(6)AC(5) 122.9(3)
C(8)AN(2) 1.361(4) N(1)AC(7)AC(5) 118.8(3) given in Table 5. The receptor characteristic bands in the 1603,
C(12)AO(3) 1.357(4) O(2)AC(8)AC(9) 123.3(3) 1643, 3166 and 3423 cm1 regions due to t(C@N), t(C@O),
N(1)AN(2) 1.355(4) C(6)AO(1)AH(1) 109.5 t(NAH) and t(OAH) stretches respectively [35,36]. In the IR spec-
N(2)AH(2A) 0.870(18) C(7)AN(1)AN(2) 120.5(3) tra of the complexes, we observed the disappearance of bands due
O(1)AH(1) 0.8200 N(1)AN(2)AC(8) 116.8(3)
O(3)AH(3) 0.8200 C(12)AO(3)AH(3) 109.5
to C@O and the appearance of new bands attributed to t(CAO) in
C(10)AH(10) 0.9300 the range of 1269–1236 [37], due to enolisation followed by depro-
tonation prior to coordination. Further, the stretching frequency of
C@N slightly shifted to lower frequencies in the spectrum of metal
the region 7.65–7.86 ppm. These peaks also shifted slightly in the complexes 1586–1602 cm1, which supports that azomethine
spectrum of the Zn(II) complex (Fig. 3). nitrogen atoms are coordinated to the central metal atom [38]. In
addition, the characteristic t(NAN) stretching band in the regions
Mass spectra 1016–1035 cm1 undergoes a positive shift to a higher wave num-
ber upon complexation due to diminished repulsion between the
The mass fragmentation of the Cu(II) and Zn(II) complexes were lone pairs of adjacent nitrogen atoms [37]. The new bands in the
shown in Figs. 4a and 4b. The mass spectra of BCHBHBH with cop- regions 453–488 and 517–552 cm1 assigned to t(MAN) and
per and zinc complexes were given in Table 4 as representative t(MAO) vibrations respectively.
 A. Sundar et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 129 (2014) 509–518
Fig. 2. Packing diagram of the BCHBHBH.DMF.
UV spectra
The electronic spectrum of the receptor and its metal complexes
are recorded in DMSO solution. The electronic spectrum of the
receptor in DMSO shows (n ? p) and (p ? p) transition bands
at 392 and 337 nm respectively. On complexation, this band is
shifted to lower wavelength region, suggesting the coordination
of azomethine nitrogen with the metal ions. Cu2+ complex shows
an absorption band at 708 nm, which may be assigned to
2
B1g ? 2B2g and 2B1g ? 2Eg transitions, in a square planar
Fig. 3. 1H NMR spectra (a) BCHBHBH and (b) [Zn(BCHBHBH)2] of in DMSO-d6.
513
geometry [39,40]. The Co2+ complex shows absorption band at
687 nm. This is due to the tetrahedral environment of the receptor
around the metal ion may be assigned to 4A2(F) ? 4T1(P) transition.
The Ni2+ complex shows an absorption band at 648 nm. This peak
corresponds to the transition 3T1(F) ? 3T1(P), 3T1(F) ? 3A1(P),
which indicates the tetrahedral environment of the receptor sur-
rounding Ni2+ in the complex [41]. The Zn2+ complex shows an
absorption band at 656 nm. This peak corresponds to the transition
2
B2 ? 3E(t1), which indicates the tetrahedral environment of the
receptor surrounding Zn2+ in the complex.
Magnetic susceptibility studies
The magnetic moments of the complexes determined at room
temperature are given in Table 2. The magnetic moment of Cu2+
complex is 1.76 lB and which indicates the presence of one
unpaired electron. This is the characteristic of square planar geom-
etry [42,43]. The magnetic moment of Co2+ and Ni2+ complexes are
4.62 lB and 3.64 lB, respectively. This is the characteristic of tetra-
hedral geometry [44]. Zn2+ complex is diamagnetic which is indic-
ative of its ideal tetrahedral structure.
Sensor studies – anion sensing
Colorimetric analysis
The anion sensing ability of the receptor with halide anions (F,
Cl, Br and I) are carried out in different solvents namely CH3CN
and DMSO. The change in optical and optoelectronic properties is
monitored by visual (naked-eye). First, the halide anions (F, Cl,
Br and I) are added as tetrabutylammonium salts to
5  105 M solutions of the receptors in acetonitrile. In the naked
eye experiments, the receptor (5  105 M) showed color change
from colorless to yellow (CH3CN) and brown color (DMSO),
514 A. Sundar et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 129 (2014) 509–518

Fig. 4a. Mass spectra of [Cu(BCHBHBH)Cl].

Fig. 4b. Mass spectra of [Zn(BCHBHBH)2].

Table 4 UV–Vis spectroscopic titration

Mass spectra data of BCHBHBH with copper and zinc complexes. The change in electronic properties of receptor in the presence
Compound m/z Relative intensity (%) Fragment
of fluoride anion is investigated by UV–Vis spectroscopic methods.
The titrations are carried out in acetonitrile medium at
[Cu(BCHBHBH)Cl] 469 79 C14H10BrCl2CuN2O3(m+)
383 82 C16H16ClCuN2O3
5.0  105 M concentrations of receptor upon the addition of
355 51 C14H12ClCuN2O3 incremental amounts of 0.02 ml (1.5  103 M) of TBAF, the spec-
320 38 C14H12CuN2O3 tra of the receptor is shown in Fig. 6. From the electronic absorp-
233 100 C8H6BrClO tion spectra of the receptor in the absence of anion, it is found
139 45 C7H5O
that the maximum wavelength of (n ? p) and (p ? p) transitions
105 49 C7H5O
77 40 C6H5 for the compound within 392 and 337 nm, there is no absorption
band in the visible region. The band at 392 nm for receptor is
[Zn(BCHBHBH)2] 805 89 C28H20Br2Cl2N4O6Zn(m+)
772 42 C28H20Br2Cl2N4O4Zn due to the transition between the p orbital localized on the azome-
740 21 C28H20Br2Cl2N4O2Zn thine group [47]. However, upon addition of fluoride anion to
513 37 C28H24N4O6Zn receptor immediate color change is noticed through naked eye,
435 41 C14H10BrClN2O3Zn which on electronic (UV–Vis) spectroscopic analysis we find a
403 62 C14H10BrClN2OZn
369 100 C14H10BrClN2O3
new peak in the visible region with noticeable peak intensity
289 43 C14H12N2OZn changes in the UV region. The peak arises 472 nm for the receptor
223 39 C14H12N2O is mainly attributed to the formation of keto form of the receptors
147 48 C9H12N2 resulting from hydrogen bonding interaction with fluoride anion
[45–47]. In case of receptor the color of the solution become more
intense upon increasing the concentration of the fluoride anion.
respectively in the presence of 1.2 equivalent of tetrabutyl ammo- However, the receptor increase in the intensity of the peak in
nium fluoride (Fig. 5). The reason for this color change is probably visible region reaches a limit after the addition of 1.2 equiv. of
due to the formation of hydrogen bond interactions between the F. Upon successive addition of fluoride anion (from 0.2 to
AOH groups of the phenyl ring of salicylaldimine and fluoride ions. 1.2 equiv.) to receptor, the intensity of the peaks at 337 and
This is because of fluoride ions have higher electro negativity and 392 nm gradually decreases, a peak (472 nm) in the visible region
small size [45–47] interacts with hydroxyl group through is noticed addition of 0.2 equiv. of the fluoride anion for receptor
intermolecular hydrogen bond (OAHAF) which will affect the there is a peak in the visible region. This suggests that, the pres-
optical properties of the receptors. No color change (CH3CN and ence of hydroxy group in the receptor acts as an excellent signaling
DMSO medium) is observed in the presence of chloride, bromide unit compared to other receptors [45]. Exposure of receptors with
and iodide ions. The receptor is found to be insensitive even on other anions (chloride, bromide and iodide) did not result in any
addition of large excess of Cl, Br and I (up to 10 equiv.). spectral changes in the absorption spectrum.
 A. Sundar et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 129 (2014) 509–518 515

Table 5
IR spectral data of BCHBHBH and its metal complexes (cm1).

Compound t(OH) t(NH) t(C@O) t(C@N) t(NAN) t(MAO) t(MAN)

BCHBHBH 3423 3166 1643 1603 990 – –
[Cu(BCHBHBH)Cl] 3411 3188 – 1597 1020 543 453
[Co(BCHBHBH)Cl] 3444 3198 – 1602 1035 530 488
[Ni(BCHBHBH)Cl] 3447 3194 – 1586 1018 552 470
[Zn(BCHBHBH)2] 3448 3220 1591 1016 517 473

Fig. 5. Color changes of receptor in (a) DMSO, (b) CH3CN (5.0  105 M) before and after the addition of 1.2 equiv. of representative anions (R + F, R + Cl, R + Br, R + I). (For
interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

the absence and in the presence of 2 equiv. TBAF. In the case of

neat receptor in the absence of TBAF, AOH protons appear two sin-
1.2 0.8
glet at 12.84 (Phenolic OH aldehyde) and 12.32 (Phenolic OH
Absorbance (mAu)

0.6 hydrazone) ppm respectively, ANH proton appears as a singlet at

1.0 0.4 10.24 ppm and the imine proton (CH@N) appears at 8.52 ppm as
0.2
a sharp singlet, whereas in the presence of 2 equiv. of TBAF, the
singlet at 12.84 and 12.32 ppm disappeared immediately indicat-
0.0
0.8
Absorbance (mAu)

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4

Conc (M)
ing the hydrogen bond interaction between fluoride anion and
AOH group, consequently an up field shift from 10.26 to
0.6 8.76 ppm in the ANH proton and 8.52–7.80 ppm in the CH@NA
proton is also observed [27,46]. The disappearance of the phenolic
OH upon the addition of 2 equiv. of fluoride anion may be due to
0.4 the simultaneous formation of the alkoxide and its hydrogen bond-
ing with the F ion.
0.2
Cation sensing

0.0 Colorimetric analysis

300 350 400
Wave length (nm)
Fig. 6. UV spectra of the receptor recorded in CH3CN (5.0  105 M) after addition
of 0–1.2 equiv. of TBAF. Inset: UV–Vis change at 472 nm of receptor in an
acetonitrile solution.
From the UV–Vis absorption measurements the binding con-
stant (Ka) of the fluoride complex of the receptor is calculated from
the variation in the absorbance at 472 nm, respectively and is
found to be 3.742  104 M. This suggests that the receptor forms
strong binding with fluoride anion [46].
We investigated sensing ability of receptor (5  105 M)
450 500
towards cations, such as Cu2+, Co2+, Ni2+ and Zn2+ (as its perchlorate
salts) are tested by colorimetric analysis in CH3CN solution (Fig. 8).
The color change in receptor upon addition of Cu2+, Zn2+ ions
(5.0  103 M) shows a green color and pale yellow color solution
are visible to naked eye. Co2+ and Ni2+ ions are not shows any vis-
ible color changes even with a large excess of metals ions (0.2 ml of
1  102 M). The ionic size of Cu(II) was 0.73 Å, while that of Zn (II)
was 0.74 Å. whereas Co2+ and Ni2+ ionic size is 0.79 and 0.83 Å,
which was larger than those ions. So, it could not accommodate
into the defined coordination sphere of the ligand. Interaction
between the electrons of ligand and orbital’s on the metal cause
the color appearance.

1
H NMR spectroscopic studies
To understand the molecular interactions between the receptor
recognition site and fluoride anion, 1H NMR titration experiments
are done with receptor in the presence and in the absence of TBAF
in DMSO-d6. Fig. 7 shows the 1H NMR spectrum of the receptor in
UV–Vis spectroscopic titration
The sensing behavior of receptor towards Cu2+ is monitored by
UV–Vis spectroscopic method. A CH3CN solution 5  105 M of
receptor is taken in the cuvette and titrated with increasing vol-
ume of concentrated solution (5  103 M) of Cu2+ ion. Receptor
516 A. Sundar et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 129 (2014) 509–518

Fig. 7. 1H NMR spectra of receptor in DMSO-d6 in the (a) absence, (b) presence of 2 equiv. of TBAF and (c) presence of 2 equivalents of TBAF expanded.

2.0 0
0.1
1.8
0.2
1.6 0.3
0.4
1.4 0.5
Absorbance (mAu)

0.6
1.2

1.0

0.8

0.6

0.4

0.2

0.0

-0.2
300 400 500 600 700
Fig. 8. Color changes of receptor in (a) Cu2+, (b) Co2+, (c) Ni2+ and (d) Zn2+ Wavelength (nm)
(5.0  103 M) after the addition of 1.0 equiv. (For interpretation of the references
to color in this figure legend, the reader is referred to the web version of this Fig. 9. UV spectra of receptor recorded in CH3CN (5.0  105 M) after addition of 0–
article.) 0.6 equiv. of Cu2+ ions.

(5  105 M) showed a gradual decrease in absorbance at
kmax = 268 nm with concomitant appearance of a new absorption
band at kmax = 474 nm on gradual addition of 0.01 ml of
5  103 M Cu2+ ion (Fig. 9). These new peaks and intensity of
the color for the receptor reached their limiting value after addi-
tion of 2 equiv. of Cu2+ ion. The utility of receptor as a Cu2+ selec-
tive chromo ionophore, the titrations of receptor in the presence
of other probable interfering metal ions have been performed. In
order to evaluate the interference from other metal ions, absor-
bance is recorded for the solutions receptor (5  105 M) contain-
ing different concentrations of Cu2+ (0.01–0.06 ml of 5  103 M)
and 0.01–0.3 ml of 5  103 M of Ni2+, Co2+, Zn2+ both at
kmax = 345 nm. The addition of receptor and Cu2+ complex peak
rises at kmax = 345 and 474 nm remains unaffected by the presence
of these metal ions. These observations indicated that the receptor
has higher selectivity towards Cu2+ ions and may be used for both
its quantitative and qualitative estimation. The binding constants
for Cu2+ complexation for the receptor are estimated as
6.43  104, 1.72  104 M. Receptor forms more stable complex
with Cu2+ ions due to the presence of OH group, which offers extra
binding site (Scheme 3).
The addition of Cu2+ ion to receptor in acetonitrile shows two
stepwise changes in the absorption spectrum, as shown in Fig. 9.
At lower concentrations of Cu2+ red-shifted absorption maximum
 A. Sundar et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 129 (2014) 509–518
Scheme 3. The coordination form of receptor with Cu2+.
(345 nm) with isosbestic points at 325 and 345 nm are observed,
whereas at higher concentration, a new absorption peak at
474 nm upon addition of Cu2+ which confirms that this peak is
formed due to the deprotonation of the amino hydrogen and phe-
nolic OH, the presence of both phenolic OH and amino NH groups
are responsible for the observed hydrogen-bonding complexation.
Conclusions
In conclusion, a novel fluorescent chemosensor based on a
Schiff-base receptor derived from 4-Hydoxybenzoichydrazide,
and 3-Bromo-5-chlorosalicylaldehyde is developed. Compared
with other metal ions, the chemosensor BCHBHBH exhibits high
selectivity and sensitivity for the detection of Cu2+ and F. The
chemosensors can be utilized for the detection of Cu2+ in the pres-
ence of other competing metal ions and for the detection of F in
the presence of other halide ions in organic solvent by both selec-
tive coloration and change in the absorption spectra. The binding
constant of receptor with F is higher due to presence of OH group,
which offers extra binding site. The spectral data’s are demonstrate
that BCHBHBH is tridentate, the Cu(II) complex has square planar
geometry, Co(II), Ni(II) and Zn(II) complexes have tetrahedral
geometry. The remarkable photophysical properties of the chemo-
sensor will be helpful for the development of fluorescent sensor
based on hydrazone derivates.
Acknowledgments
Financial assistance received from Council of Scientific and
Industrial Research (CSIR), New Delhi [No. 01(2511)/11/EMR-II
dated 12-12-2011], and Department of Science and Technology,
New Delhi, India [Grant No. SR/FTP/CS-40/2007] are gratefully
acknowledged.
Appendix A. Supplementary material
Crystallographic data for the structural analysis have been
deposited with the Cambridge Crystallographic Data Centre, CCDC
Nos. 947609 for C17H17N3O4BrCl. Copy of this information may be
obtained free of charge from The Director, 12 Union Road, Cam-
bridge CB2 1EZ, UK (fax: +44 1223 336 033; e-mail: deposit@ccdc.
cam.ac.uk or www: http://www.ccdc.cam.ac.uk). Supplementary
data associated with this article can be found, in the online version,
at http://dx.doi.org/10.1016/j.saa.2014.03.084.
References
[1] M. Ruben, J.M. Lehn, G. Vaughan, Chem. Commun. (2003) 1338–1339.
[2] L.H. Uppadine, J.P. Gisselbrecht, J.M. Lehn, Chem. Commun. (2004) 718–719.
[3] L.H. Uppadine, J.M. Lehn, Angew. Chem. Int. Ed. 43 (2004) 240–243.
[4] P.B. Sreeja, A. Sreekanth, C.R. Nayar, M.R.P. Kurup, A. Usman, I.A. Razak, S.
Chantrapromma, H.K. Fun, J. Mol. Struct. 645 (2003) 221–226.
[5] S. Naskar, M. Corbella, A.J. Blake, S.K. Chattopadhyay, Dalton Trans. (2007)
1150–1159.
[6] P.J. Melz, R.B. Champ, L.S. Chang, C. Chiou, G.S. Keller, L.C. Liclican, R.R. Neiman,
M.D. Shattuck, W. Weiche, J. Photogr. Sci. Eng. 21 (1977) 73.
517
[7] M. Carcelli, P. Mazza, C. Pelizzi, G. Pelizzi, F. Zani, J. Inorg. Biochem. 57 (1995)
43–62.
[8] A. Bacchi, A. Bonardi, M. Carcelli, P. Mazza, P. Pelagatti, C. Pelizzi, G. Pelizzi, C.
Solinas, F. Zani, J. Inorg. Biochem. 69 (1998) 101–112.
[9] A.R. Todeschini, A.L.P. de Miranda, K.C.M. da Silva, S.C. Parrini, E.J. Barreiro, Eur.
J. Med. Chem. 33 (1998) 189–199.
[10] A. Wood, W. Aris, D.J.R. Brook, Inorg. Chem. 43 (2004) 8355–8360.
[11] C.D. Geddes, Meas. Sci. Technol. 12 (2001) 53–88.
[12] S. Naskar, R.J. Butcher, S.K. Chattopadhyay, Inorg. Chim. Acta 363 (2010) 3641–
3646.
[13] K.L. Kirk, Biochemistry of Halogens and Inorganic Halides, Plenum Press, New
York, 1991.
[14] J. Xu, K. Liu, D. Di, S. Shao, Y. Guo, Inorg. Chem. Commun. 10 (2007) 681–684.
[15] R.M. Duke, T. Gunnlaugsson, Tetrahedron Lett. 48 (2007) 8043–8047.
[16] H.J. Kim, J.H. Lee, T.H. Kim, W.S. Lyoo, D.W. Kim, C. Lee, T.S. Lee, J. Polym. Sci.,
Part A: Polym. Chem. 45 (2007) 1456–1556.
[17] F. Sancenon, R.M. Manez, M.A. Miranda, M.J. Segui, Angew. Chem. Int. Ed. 42
(2003) 647–650.
[18] T.L. Kao, C.C. Wang, Y.T. Pan, Y.J. Shiao, J.Y. Yen, C.M. Shu, G.H. Lee, S.M. Peng,
W.S. Chung, J. Org. Chem. 70 (2005) 2912–2920.
[19] P. Kar, M. Suresh, D.K. Kumar, D.A. Jose, B. Ganguly, A. Das, Polyhedron 26
(2007) 1317–1322.
[20] D.A. Jose, P. Kar, D. Koley, B. Ganguly, W. Thiel, H.N. Ghosh, A. Das, Inorg. Chem.
46 (2007) 5576–5584.
[21] C. Lee, D.H. Lee, J.I. Hong, Tetrahedron Lett. 42 (2007) 8665–8668.
[22] K. Niikura, A.P. Bisson, E.V. Anslyn, J. Chem. Soc. Perkin Trans. 2 (1999) 1111–
1114.
[23] E.R. Libra, M. Scott, J. Chem. Commun. (2006) 1485–1487.
[24] T. Ghosh, B.G. Maiya, M.W. Wong, J. Phys. Chem. A 108 (2004) 11249–11259.
[25] D.E. Gomez, L. Fabbrizzi, M. Lichelli, E. Monazani, Org. Biomol. Chem. 3 (2005)
1495–1507.
[26] S. Devaraj, D. Saravanakumar, M. Kandaswamy, Tetrahedron Lett. 48 (2007)
3077–3081.
[27] D. Saravanakumar, S. Devaraj, S. Iyyampillai, K. Mohandoss, M. Kandaswamy,
Tetrahedron Lett. 49 (2008) 127–132.
[28] X. Peng, Y. Wu, J. Fan, M. Tian, K. Han, J. Org. Chem. 70 (2005) 10524–10531.
[29] V. Amendola, D. Boiocchi, B. Colasson, L. Fabbrizzi, Inorg. Chem. 45 (2006)
6138–6147.
[30] A.M. Shallaby, N.M. Hosny, Trans. Met. Chem. 32 (2007) 1085–1090.
[31] (a) S. Mathan Kumar, K. Dhahagani, J. Rajesh, K. Nehru, J. Annaraj, G.
Chakkaravarthi, G. Rajagopal, Polyhedron 59 (2013) 58–68;
(b) J. Rajesh, A. Gubendran, G. Rajagopal, P.R. Athappan, J. Mol. Struct. 1010
(2012) 169–178;
(c) J. Rajesh, M. Rajasekaran, G. Rajagopal, PR. Athappan, Spectrochim. Acta
Part A 97 (2012) 223–230;
(d) K. Kanmani Raja, D. Easwaramoorthy, S. Kutti Rani, J. Rajesh, Y. Jorapur, S.
Thambidurai, P.R. Athappan, G. Rajagopal, J. Mol. Catal. A: Chem. 303 (2009)
52–59;
e G. Puthilibai, S. Vasudhevan, S. Kutti Rani, G. Rajagopal, Spectrochim. Acta
Part A 72 (2009) 796–800.
[32] B.N. Bessy Raj, M.R.P. Kurup, E. Suresh, Spectrochim. Acta Part A 71 (2008)
1253–1260.
[33] M. Prabhu, K. Parthiban, A. Ramu, G. Chakkaravarthi, G. Rajagopal, Acta Cryst.
E67 (2011) 2716–2717.
[34] P.B. Sreeja, M.R.P. Kurup, A. Kishore, C. Jasmin, Polyhedron 23 (2004) 575–581.
[35] L.L. Koh, O.L. Kon, K.W. Loh, Y.C. Long, J.D. Ranford, A.L.C. Tan, Y.Y. Tjan, J. Inorg.
Biochem. 72 (1998) 155–162.
[36] P. Sathyadevi, P. Krishnamoorthy, M. Alagesan, K. Thanigaimani, P. Thomas
Muthiah, N. Dharmaraj, Polyhedron 31 (2012) 294–306.
[37] E.B. Seena, M.R.P. Kurup, Spectrochim. Acta Part A 69 (2008) 726–732.
[38] K. Dhahagani, S. Mathan Kumar, G. Chakkaravarthi, K. Anitha, J. Rajesh, A.
Ramu, G. Rajagopal, Spectrochim. Acta Part A 117 (2014) 87–94.
[39] V.P. Singh, S. Singh, D.P. Singh, P. Singh, K. Tiwari, M. Mishra, R.J. Butcher,
Polyhedron 56 (2013) 71–81.
[40] R.M. Silverstein, F.X. Webster, D. Kiemle, Spectrometric Identification of
Organic Compounds, seventh ed., Wiley, New York, 2005.
[41] A.B.P. Lever, Inorganic Electronic Spectroscopy, second ed., Elsevier, New York,
1968.
[42] I.M. Procter, B.J. Hathaway, P. Nicholls, J. Chem. Soc. A (1968) 1678–1684.
[43] B.N. Figgis, J. Lewis, Prog. Inorg. Chem. 6 (1964) 37–239.
[44] B.D. Cullity, Introduction to Magnetic Materials, Addison-Wesley Publisher,
London, 1972.
518 A. Sundar et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 129 (2014) 509–518

[45] (a) R. Sivakumar, V. Reena, N. Ananthi, M. Babu, S. Anandan, S. Velmathi,
Spectrochim. Acta Part A 75 (2010) 1146–1151;
(b) S. Suganya, S. Velmathi, R. Sivakumar, S. Anandan, Sens. Lett. 9 (2011) 570–576;
(c) D. Udhayakumari, S. Saravanamoorthy, M. Ashok, S. Velmathi, Tetrahedron Lett.
52 (2011) 4631–4635;
(d) D. Udhayakumari, S. Saravanamoorthy, S. Velmathi, Mater. Sci. Eng. C 7 (2012)
1878–1882.
[46] S. Prabhu, S. Saravanamoorthy, M. Ashok, S. Velmathi, J. Lumin. 132 (2012)
979–986.
[47] V. Luxami, S. Kumar, Tetrahedron Lett. 48 (2007) 3083–3087.