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DOI: http://dx.doi.org/10.1016/j.saa.2014.10.061
Reference: SAA 12876
Please cite this article as: P.S. Hariharan, S.P. Anthony, Substitutional group dependent colori/fluorimetric sensing
of Mn2+, Fe3+ and Zn2+ ions by simple Schiff base chemosensor, Spectrochimica Acta Part A: Molecular and
Biomolecular Spectroscopy (2014), doi: http://dx.doi.org/10.1016/j.saa.2014.10.061
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1
philip@biotech.sastra.edu
Abstract: Schiff base is one of the easiest synthesizable chemosensor and exhibit
strong coordination with metal ions; the property that has been vastly exploited for
metal ions sensing. Simple Schiff base chemosensors (1a-d and 2a-d) were
metal ions. Chemosensor without (1a, 2a) and OCH3 substitution (1b, 2b) did not
show any significant colour change for metal ions. However, a highly selective
colorimetric change (colourless to pink) for Mn2+ ions (10-6 M) was observed with
diethylamine substituted 1c, 2c. Hydroxyl substitution (1d, 2d) leads to selective
colorimetric sensing (colourless to orange) of Fe3+ ions (10-6 M). PVA thin films of
2c/2d were fabricated and demonstrated selective colorimetric sensing of Mn2+ and
Fe3+ ions. The practical applicability of the synthesized chemosensors were also
real samples such as tap, ground, pond and river water. Effect of substitution on the
Keywords: Fluorescence sensor, Colorimetric sensor, Zn2+ sensor, Mn2+ sensor, Fe3+
sensor.
2
1. Introduction
Selective detection and screening of heavy transition metal ions (HTM) is highly
process [1,2]. Among the various approaches developed, molecular chemosensors that
show optical (both colorimetric and fluorescence) responses upon selective binding
with metal ions have received great interest since these methods are cost-effective,
rapid, real time-monitoring and facile [3,4]. The ease of synthesis coupled with
metal coordination ability has made Schiff bases as one of the most widely explored
molecular chemosensors for selective sensing of metal ions [5-7]. Particularly, Salen,
a tetradentate [OˆNˆNˆO] chelating bis-Schiff base, based ligands and its metal
complexes have been exploited for various potential applications in many fields
including catalysts [8], DNA cleavage [9], optical materials [10], magnetic materials
[11] and sensors [6-7]. For example, the excellent luminescent properties and good
thermal stabilities of Zn(II) [12], B(III) [13], Al(III) [14], and Pt(II) [15] based Salen
emitting diodes (OLEDs). Salen type ligands have also been widely used as
[6a-d], Mg2+ [6g], Cu2+ [32,37,42], Al3+ [6h] and Pt2+ [7e]. However, there are only a
few reports on the selective colorimetric as well as multiple metal ions sensing by
Salen chemosensors that are known to have strong binding affinities with
metal ions often showed strong fluorescence enhancement via chelation enhanced
fluorescence mechanism for metal ions such as Zn2+, Cd2+ and Al3+ [17]. However,
the chemosensor should show strong preference with metal ions of interest to exhibit
3
the high selectivity in presence of other metal cations. The preferential coordination
of organic ligands with metal ions are strongly influenced by the structure,
substituents, solvent and temperature [18]. Hence a subtle change in the structure of
Salen chemosensor might affect the affinity of metal ions that could modify the
metal ions. Chemosensors, 1a-d and 2a-d, exhibited selective turn-on fluorescence for
colorimetric sensing for Mn2+ ions (colourless to pink) was observed with
practical utility of 2c and 2d for selective colorimetric sensing of Mn2+ and Fe3+ has
2. Experimental Sections
2.1. Materials
(PVA, M. W. 125000) was obtained from SD Fine chemicals, India. The solvents
were obtained from Merck India. All chemicals are used as received. The metal ion
solutions used for the colorimetric and fluorescence sensor experiments were prepared
by preparing 10-3 M stock solution in Mill-Q water. The chemosensors were dissolved
in dimethyl formamide (DMF). The sensing experiment was repeated three times to
confirm the reproducibility of the method. Absorption and fluorescence spectra were
4
recorded using Perking Elmer Lambda 1050 and Jasco fluorescence spectrometer-FP-
CHN analyzer.
dissolved in ethanol (30 ml) and stirred at room temperature. To this solution, either
drop-wise under stirring. The immediate appearance of yellow colour indicates the
formation of Schiff bases. The solution was allowed to stir for another 6 h at room
temperature that produced yellow to light yellow coloured precipitates. The formed
precipitate was filtered off, washed with ethanol and dried under vacuum.
1a: Yield = 85 %. m.p. 122 °C. 1H NMR (CDCl3) δ 13.25 (s, 2H (OH), 8.37 (s, 2H
(imine H)), 7.31-7.34 (d, 2H), 7.23-7.26 (d, 2H), 6.95-6.97 (d, 2H), 6.85-6.90 (t, 2H),
13
3.95 (s, 4H). C NMR (CDCl3) δ 166.51, 161.01, 132.41, 131.50, 118.70, 118.64,
116.96, 59.75. C16H16N2O2 (268.31): calcd. C 71.62, H 6.01, N 10.44; found C 71.27,
H 6.31, N 10.37.
2a: Yield = 80 %. m.p. 112 °C. 1H NMR (CDCl3) δ 13.37 (s, 2H (OH)), 8.28 (s, 2H
(imine H)), 7.23-7.28 (t, 2H), 7.15-7.18 (d, 2H), 6.89-6.92 (d, 2H), 6.81-6.84 (t, 2H),
13
3.29-3.35 (m, 2H), 1.88-1.98 (m, 4H), 1.46-1.52 (m, 4H). C NMR (CDCl3) δ
164.71, 160.96, 132.17, 131.48, 118.65, 118.60, 116.77, 72.63, 33.10, 24.18.
C20H22N2O2 (322.17): calcd. C 74.51, H 6.88, N 8.69; found C 74.46, H 6.94, N 8.31.
1b: Yield = 80 %. m.p. 154 °C. δ 13.72 (s, 2H (OH)), 8.18 (s, 2H (imine H)), 7.06-
13
7.08 (d, 2H), 6.35-6.41 (m, 4H), 3.83 (s, 4H), 3.78 (s, 6H). C NMR (CDCl3) δ
5
165.42, 164.76, 163.53, 132.74, 112.31, 106.43, 101.14, 58.75, 55.34. C18H20N2O4
2b: Yield = 80 %. m.p. 108 °C. 1H NMR (CDCl3) δ 13.83, (s, 2H (OH)), 8.08 (s, 2H),
6.97-7.00 (d, 2H), 6.28-6.35 (m, 4H), 3.75 (s, 6H), 3.20-3.23 (m, 2H), 1.84-1.92 (m,
4H), 1.40-1.46 (m, 4H). 13C NMR (CDCl3) δ 164.96, 163.73, 163.43, 132.77, 112.22,
106.22, 101.09, 71.56, 55.31, 33.07, 24.23. C22H26N2O4 (382.45): calcd. C 69.09, H
1c: Yield = 80 %. m.p. 131 °C. 1H NMR (CDCl3) δ 13.55 (s, 2H (OH)), 8.20 (s, 2H
(imine H)), 7.04-7.07 (d, 2H), 6.14-6.17 (d, 4H), 3.71 (s, 4H), 3.31-3.37 (q, 8H), 1.05-
13
1.10 (t, 12H). C NMR (CDCl3) δ 164.85, 164.79, 150.92, 133.00, 107.78, 102.78,
97.25, 57.56, 43.73, 12.53. C24H34N4O2 (410.55): calcd. C 70.21, H 8.35, N 13.65;
2c: Yield = 80 %. m.p. 195 °C. 1H NMR (CDCl3 ) δ 13.18 (s, 2H (OH)), 7.92 (s, 2H
(imine H)), 6.86-6.89 (d, 2H), 6.01-6.07 (m, 4H), 3.28-3.35 (q, 8H), 3.13-3.16 (m,
13
2H), 1.80-1.95 (m, 4H), 1.37-1.57 (m, 4H), 1.11-1.16 (t, 12H). C NMR (CDCl3) δ
166.17, 162.71, 151.43, 133.08, 108.25, 102.91, 98.14, 70.75, 44.44, 33.25, 24.35,
12.72. C28H40N4O2 (464.64): calcd. C 72.38, H 8.68, N 12.06; found C 72.41, H 8.65,
N 12.13.
1d: Yield = 80 %. m.p. 250 °C (decomp.). 1H NMR (CDCl3) δ 13.58-13.64 (b, 4H,
OH)), 8.35 (s, 2H (imine H)), 7.14-7.17 (d, 2H), 6.24-6.28 (d, 2H), 6.16-6.17 (d, 2H),
13
3.77 (s, 4H). C NMR (CDCl3) δ 165.78, 164.52, 161.87, 133.33, 111.11, 106.90,
102.53, 57.67. C16H16N2O4 (300.31): calcd. C 63.99, H 5.37, N 9.33; found C 63.59,
H 5.74, N 9.22.
(OH)), 8.17 (s, 2H (imine H)), 6.98-7.01 (d, 2H), 6.17-6.20 (d, 2H), 6.11-6.12 (d, 2H),
6
13
3.20-3.23 (m, 2H), 1.76-1.87 (m, 4H), 1.37-1.58 (m, 4H). C NMR (CDCl3) δ
163.74, 161.51, 132.90, 110.99, 106.78, 102.40, 70.71, 32.68, 23.77. C20H22N2O4
synthetic protocol as well as some of the chemosensor (1a, 2a) has already been
known [19], the optical sensing properties have never been investigated thoroughly.
Particularly, 1c,d and 2c,d are newly synthesized which showed substitutional group
dependent colorimetric sensing of Mn2+ and Fe3+ ions. 1a-d and 2a-d were
(both fluorescence as well as colorimetric sensing) of 1a-d and 2a-d were explored by
Figure 1 shows the absorption spectra of 1a-d and 2a-d in DMF. 1a-d and 2a-d
exhibited intense absorption in the range of 300-350 nm that are assigned to π-π*
transition involving molecular orbitals particularly localized on the C=N group and
benzene ring. The low intensity absorption around 380 nm is assigned to n-π*
transition involving molecular orbitals of the C=N chromophore and benzene ring
[20]. The absorption spectra of 1a and 2a with different metal ions are shown in figure
S1. The metal interaction especially transition metal ions (Cr3+, Mn2+, Fe3+, Co 2+, Ni2+
and Cu 2+) with 1a and 2a red shifts the absorption λmax (350-420 nm). Even though
Fe3+ addition to 1a and 2a produced very weak absorption at longer wavelength (475
nm), visible colour was not able to observe. 1b and 2b also exhibited a similar
7
absorption change without producing any naked eye detectable colour change for any
pink colour) upon the addition of Mn2+ ions (Fig. 2). Although Co2+, Ni2+ and Cr3+
addition exhibited colourless to light yellow colour formation, only Mn2+ produced
distinctly different colour. Mn2+ is one of the essential trace elements for several
endogenous anti-oxidant enzymes [21]. The absorption studies of 1c/2c showed the
emergence of two new peaks with Mn2+; a strong absorption at 415 nm and a clear
low intense broad peak around 520 nm. The intensity of π-π* transition band (320-
340 nm) was reduced by addition of Mn2+. The red shift of n-π* transition band from
380 nm to 415 nm is due to the coordination of Mn2+ with imine nitrogen. The metal
ability of C=N group [8a]. The broad low intense band at 520 nm could be assigned to
ligand to metal charge transfer (LMCT) [22]. The absorption titration showed clear
spectral changes for 1c and 2c (red shifted n-π* transition at 415 nm and LMCT at
520 nm) with the addition of Mn2+ ions (Fig. 3a, S3a). A clear reduction of absorption
intensity at 340 nm and emergence of new absorption at 415 and 520 nm could be
observed with the first addition of Mn2+ (0.1 equivalent) to 1c/2c. The intensity of
Mn2+ at µM concentration (Fig. 3a, S3a inset). The concentration dependent studies
further suggest the 5 µM detection limit of Mn2+ by 1c/2c. This suggests the
formation of 1:1 coordination complexes between Mn2+ and 1c/2c. The exact
coordination complex structure could not be established since the attempted single
crystal growth was not successful. However, the structure could be similar to the
famous Jacobson catalysts that are also 1:1 coordination complex of Mn2+ with bis-
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Schiff base tetradendate ligands [23]. The selectivity studies of 1c and 2c indicates
that other metal ions except Fe3+ and Co2+ had negligible interference on the
selectivity of Mn2+ (Fig. 3b, S3b). Mn2+ additions into 1c and 2c in presence Fe3+ and
Co2+ showed only slight enhancement absorption at 415 nm and suggest that both
metal ions are competitively coordinated with 1c and 2c. It is noted that addition of
nm compared with Mn2+-2c. The reason for the strong absorption is not clear right
Schiff bases upon addition of Zn2+ followed by Cd2+ and vice versa [24]. Absorption
peak at 415 nm was chosen for selectivity analysis since it was a distinct and strong
exhibited selective colorimetric sensing of Fe3+ (Fig. 4). Fe3+ is the most abundant
transition-metal ion in humans and other mammals, and it plays important roles in
various biological systems [25]. The deficiency of Fe3+ leads to anemia, liver and
kidney damages, diabetes, and heart diseases [26]. Addition of Fe3+ ions into 1d and
2d selectively produced orange colour solution (Fig. 4). Mn2+, Co2+, Cr3+ and Ni2+
showed only light yellow colour with 1d and 2d. The absorption measurement of 1d
and 2d with Fe3+ showed broad low intense LMCT band at 480 nm that could be
responsible for the orange colour. Other metal ions only showed enhancement of n-π*
transition around 400 nm. The concentration dependent studies again clearly showed
the linear enhancement of n-π* and LMCT band intensity with each addition of Fe3+
at µM concentration (Fig. 5a, S4a). The titration studies further suggested the
formation of 1:1.5 coordination complexes between Fe3+ and 1d/2d (Fig. 5a, S4a
9
inset). 1d/2d chemosensor can detect Fe3+ ions up to 2 µM. The interference studies
indicate the high selectivity of Fe3+ in presence of other metal ions (Fig. 5b, S4b). In
an effort to fabricate sensor devices, PVA thin films of 2c and 2d was fabricated by
PVA (1 wt%). The solution was stirred together for 1 h then it was drop coated on the
glass plate. The air dried thin film of PVA-2c and PVA-2d was dipped (1 min) into
aqueous metal ions solution of Mn2+ and Fe3+ (10-6 M), respectively. The Mn2+ ion
dipping and Fe3+ dipping clearly showed naked eye detectable pink colour and orange
colour change, respectively (Fig. 6). The reproducibility of the approach was
prepared one week before also showed similar results and suggest the good stability
of the thin film. The practical applicability of the 2c and 2d chemosensor for sensing
Mn2+ and Fe3+ ions in different water samples (tap, ground, pond and river water)
have also been demonstrated (Fig. S5). Several chemosensors have been reported for
selective colorimetric sensing of Fe3+ (Table 1, 27), however, 1d/2d offered the
Mn2+ colorimetric sensors were mostly developed based on noble metal nanoparticles
such as silver (Ag) and gold nanoparticles (AuNPs) and molecular chemosensor for
for Zn2+ compared to other metal ions including Cd 2+ [6b,c,d,15b]. The coordination
of Zn2+ with imine nitrogen of Schiff bases that restricts the free rotation of C=N bond
and rigidify the fluorophore that is responsible for the strong fluorescence
enhancement [29]. However, transition metal ions such as Fe3+, Cu2+, Co 2+, Ni2+ and
Mn2+ usually forms strong and preferential coordination with Schiff bases and
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quenches the fluorescence due to the paramagnetic nature of metal ions. Hence these
metal ions might strongly affect the selectivity of Schiff base chemosensor. 1a-d and
1a-d and 2a-d showed selective turn-on fluorescence for Zn2+ ions (Fig. 7a,
The fluorescence λmax of 1a-d and 2a-d with Zn2+ ions varied from 419 to 448 nm.
Cd2+ ions also (20 fold, λmax = 418 nm) but the intensity was slightly lesser compared
with Zn2+ ion (30 fold, λmax = 418 nm). The fluorescence titration studies showed the
Fig. 7b). The fluorescence enhancement was saturated by the addition of one
equivalent of Zn2+ and suggests the formation of 1:1 coordination complexes between
they displayed different selectivity depend on the substitutional group. 1a and 2a did
not show any fluorescence turn-on with Zn2+ in presence of Co2+ (Fig. 8a, S9). Zn2+
addition showed only weak turn-on fluorescence was observed in presence of Mn2+
and Ni2+ metal ions. 1b,c and 2b,c selectivity was strongly affected by the presence
many transition metal ions such as Cr3+, Mn2+, Fe3+, Co 2+, Ni2+ and Cu2+ (Fig. 8b, 9a,
S9, S10). However, hydroxyl group substituted chemosensor 1d and 2d showed better
selectivity for Zn2+ in presence of other metal cations (Fig. 9b, S10) except Fe3+. It is
noted that 1d and 2d showed selective colorimetric changes for Fe3+ ions. Cr3+, Mn2+,
Hg2+ and Pb2+ did not show any significant influence on the fluorescence turn-on.
Although Co2+, Ni2+ and Cu 2+ metal ions presence exerted some influence, Zn2+
11
1a and 2a without any substitution on the phenyl ring was strongly influenced by
Co2+, Mn2+ and Ni2+. Electron donor group, methoxy and diethyl amino, substitution
(1b-c and 2b-c) lead to stronger and preferential coordination with many transition
metal ions (Cr3+, Mn2+, Fe3+, Co 2+, Ni2+ and Cu 2+. But a hydroxyl group substituted 1d
4. Conclusion
Fe3+ at ppm level was demonstrated by changing the substitutional group of simple
pink) was observed with 1c and 2c. Whereas hydroxyl group substituted chemosensor
The interference studies revealed the high selectivity for Mn2+ and Fe3+ by 1c/2c and
1d/2d, respectively. Thin films of PVA with chemosensor have been fabricated and
demonstrated the selective colorimetric sensing Mn2+/Fe3+ ions in water. The practical
applications of 2c/2d for selective sensing of Mn2+/Fe3+ in real samples such as tap,
ground, pond and river water have also been demonstrated. Substitutional group
dependent fluorescence selectivity for Zn2+ in presence of other metal ions has also
been demonstrated.
Acknowledgments
Financial supports from DST, New Delhi, India (DST Fast Track Scheme No.
facility under CRF facility, SASTRA University are acknowledged with gratitude.
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Figure Caption
Mn2+.
Fe3+.
Figure 6. Digital image of PVA-chemosensor colour change with Mn2+ and Fe3+.
Figure 7. (a) Fluorescence spectra of 1a with different metal ions and (b) change
Figure 8. (a) 1a and (b) 1b selectivity of Zn2+ in presence of other metal cations.
(black bar = 1a and 1b with different metal ions (10 -3 M) and red bar =
Figure 9. (a) 1c and (b) 1d selectivity of Zn2+ in presence of other metal cations
(black bar = 1a and 1b with different metal ions (10 -3 M) and red bar =
Table 1
Compound
OH
structure N
O
N
HO
HO O
N OH N
OH
N
N
N OH O O OH
N
HO
OH
S S CH3
Scheme 1
Figure 1
24
Figure 2
25
Figure 3
26
Figure 4
27
Figure 5
28
Figure 6
Figure 7
29
Figure 8
30
Figure 9
31
Schiff base based Colori/fluorimetric chemosensor for sensing Mn2+, Fe3+ and
Zn2+ ions: Effect of structural change on the selectivity of metal ions
Highlights
• Simple Schiff base colorimetric sensor for Mn2+ and Fe3+ ions.
selectivity.