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Journal of Chemistry and Chemical Sciences, Vol.

5(1), 19-27, January 2015


www.chemistry-journal.org

ISSN 2229-760X (Print)


ISSN 2319-7625 (Online)

An Overview on Metal Complexes of selected Schiff-bases


with their Electrochemical and Sensor Aspects
Sofani Tafesse Gebreyesus and Masood Akhtar Khan
Department of Chemistry,
College of Natural Sciences, Arbaminch University, ETHIOPIA.
(Received on: December 25, 2014)
ABSTRACT
Schiff bases and their metal complexes are used for many applications
apart from the biological activities; it can be used as sensors electrodes, energy
storage devices, solar cells and environmental sensor. This review deals more about
their use in electrochemical and sensor aspects.
Keywords: Schiff base, metal complex, electrochemical, sensor.

INTRODUCTION
Schiff bases are condensation products of primary amines with carbonyl compounds
and they were first reported by Hugo Schiff in 1864. The common structural feature of these
compounds is the azomethine group with a general formula RHC=NR where R and R are
alkyl, aryl, cyclo alkyl or heterocyclic groups which may be variously substituted. These
compounds are also known as anils, imines or azomethines.1
Schiff bases have wide applications in food industry, dye industry, analytical
chemistry, catalysis, fungicidal, agrochemical and biological activities.2
In recent years, the attention of Schiff bases and their metal complexes are increasing
due to their remarkable biological and pharmacological applications.3 They are used for
many applications apart from the biological activities; it can be used as sensors4, 5 electrodes,
energy storage devices, solar cells6 and environmental sensor.7
It has high tendency to bind with the metal atom and form the complexes with
different oxidation states.8 The Schiff bases are containing different heterocyclic moieties
and they are important class of compounds in organic chemistry. In addition, Schiff base can
be used for the heavy metal sensing, and removal of pollutant in the environment. They are
good spectrophotometric and flourimetric agents.9
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Sofani Tafesse Gebreyesus, et al., J. Chem. & Cheml. Sci. Vol.5 (1), 19-27 (2015)

Application of many new analytical devices requires the presence of organic reagents
as essential compounds of the measuring system. Schiff base ligands are used in optical and
electrochemical sensors, and likewise in several chromatographic methods, to make possible
detection of enhance selectivity and sensitivity.1012
Schiff base ligands can be easily synthesized by reactions of condensation of primary
amines and carbonyl compounds in which the azomethine bond is formed and they can used
as complex formation reactions (determination of amines, carbonyl compounds and metal
ions); or utilizing the variation in their spectroscopic characteristics.
A great number of metal complexes of the Schiff bases (acyclic or cyclic) have been
prepared, and they have provided an enormously rich world of chemistry13. This paper
reviews the uses of metal complex of Schiff bases in electrochemical and sensor aspects.
1. Electrochemical sensing of N1,N1-bis((E)-2-(2-hydroxy5 bromobenzylideneamino)
ethyl)ethane-1,2-diamine to Pyrocatechol
The electrochemical sensing behavior of Schiff base towards pyrocatechol (PC) was
examined by cyclic voltammetry (CV). The Schiff base was coated on the GCE surface by
the drop coating method. There is an electrocatalytic ability of the modified electrode. This
electrocatalytic effect was enhancing due to the larger surface area available on the
modifying GCE. The study showed that the reduction peak current moved negatively, but the
oxidation peak was not showing any characteristic response. Based on that, reduction peak
was accounted for detection of PC.

Fig. 1: graphical representation of electro-catalytic reaction.


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In addition the electrode reaction was based on the hydrogen bond formation
between the Schiff base and the PC. The catalytic reaction facilitates electron transfer
between PC and the Schiff base modified electrode; as a result the electrochemical reduction
of PC becomes easier. In the electrocatalytic reaction the diffusion process was carried by the
sensing material. The reason is that the Schiff base could increase the rate of electron transfer
and lower the over potential of PC at the bare electrode.
Thus, it is clear that Schiff base modified GCE can be successfully used for the
electrochemical sensing of PC14,15 .
The Schiff base was used to sensing the pyrocatechol. From the electrochemical
sensing experiment, it can be concluded that the Schiff base has good sensing activity
towards the pyrocatechol. Hence, the GCE modified with Schiff base will be good sensor for
pyrocatechol16.
2. Electrochemical sensing of N1,N1-bis((E)-2-(2-hydroxy5 bromobenzylideneamino)
ethyl)ethane-1,2-diamine to Hydroquinone :
Electrocatalytic sensing ability of the polymerized Schiff base (P-SB) modified GCE
was investigated by using cyclic voltammetry (CV) and Differential pulse voltammetry
(DPV). It is known that the sensing occur irreversible redox process and potential shifted
positively. The modified GCE has good conduct with the analyte to form hydrogen bond,
hence it gives two fold higher current response when compare with the bare GCE. It is clear
that the Schiff base modified GCE is a good electro-catalytic sensor for sense the
hydroquinone.17
It is possible also to determine the quantity of hydroquinone in the modified GCE
using DPV, which generally has high sensitivity and selectivity. Schiff base was
electrochemically polymerized and used for the electro-catalytic sensor. The results
demonstrated that Schiff base was successfully used for the detection of hydroquinone. It is
more efficient electrode material towards the hydroquinone detection with better
electrocatalytic activity and higher sensitivity18.
3. Electrochemical properties of N,N0-bis(2-methoxy phenylidene)-1,5-diamino
naphthalene and N,N0-bis(3,4,5-trimethoxy phenylidene)-1,5-diamino naphthalene
Fig.2: Proposed structures of the synthesized Schiffbase compounds Electrochemical
properties of the Schiff base compounds (L1 and L2) were studied in NBu4BF4 as
supporting electrolyte. The compound L1 shows theirreversible and quasi reversible redox
processes at all scan rates.
In the extreme low concentration solution, the compound L1 hastwo reversible redox
processes. The compound L1 shows irreversible process at theother scan rates. The
compound L2 has only one reversible redoxcouple. In the reversible redox process, the
Schiff base compounds have been converted to the ketoamineforms19.
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Sofani Tafesse Gebreyesus, et al., J. Chem. & Cheml. Sci. Vol.5 (1), 19-27 (2015)

Fig.2: Proposed structures of the synthesized Schiffbase compounds

In this process, the oxygen atoms of the methoxy groups of the organic compounds
give the electrons to the benzenoidrings and then to the nitrogen atoms by the resonance.
This process occurs as the reversible. While the compound L1 has onlyone methoxy group
(orthoposition on the benzene rings), the othercompound L2 have three methoxy groups
(ortho, meta and parapositions on the benzene rings, respectively). Although the methoxy
groups decrease the electron density of the benzenoidrings by the inductive effect, the
electron density increase by themesomeric effect. Electron donating groups to the benzene
rings shift the potentials from the positive to negative regions. These situations were seen in
these compounds. The compound L2 shows irreversible and quasi-reversible processes at
other scan rates and concentrations. It is investigated that their sensor properties against to
the metal ions.
The compound L2 shows higher selectivity toward the softer cation Hg(II), as
compared to the harder caions K(I), Na(I), Ba(II), Cd(II), Co(II), Cu(II), Mg(II), Mn(II),
Ni(II), Zn(II) and Al(III) on day light. On the examining conditions, the Schiff base
compounds indicated higher selectivity against to the Cu(II) ion. In the electrochemical
studies, the compounds showed reversible redox processes at the some scan rates20.
4. Electrochemistry of Schiff Base Complexes Derived from Amino Acids
The electrochemical investigations of the complex in DMSO solution were
separately carried out under two different atmospheres (N2 and aerobic) between the narrow
potential windows. The electrochemical data received from the cyclic voltammogram of the
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Sofani Tafesse Gebreyesus, et al., J. Chem. & Cheml. Sci. Vol.5 (1), 19-27
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metal complexes are very much vital, sincethey can be used to study the chelate ring size,
axial ligation, degree and distribution
bution of unsaturation and substitution pattern in the
complexes21-25.

Fig. 3: Synthesis of L and [Zn(L) Cl]Cl

The cyclic voltammogram of the complex under N2 atmosphere shows a significant


electrochemical process, which is found to follow the one electron reversible mechanism.
This reversible process includes the cathodic peak which corresponds to the reduction of
Zn(II) to Zn(I) and the anodic peak which is a characteristic of the reversible oxidation of
Zn(I) to Zn(II). The reactivity of complex with the aerobic gases such as O2 and CO2 in
cyclic voltammogram of the complex in solution media can be studied under aerobic
conditions. The study proves the non-reactivity
reactivity of complex with the aerobic gases in the
solution media. Furthermore, the chemical
chemical inertness of the complex would be more in its
solid state. It is also expected that the electron with drawing groups could stabilize the
complex in Zn(II) state while the electron donating groups may favor the oxidation to next
oxidation state, Zn(III)30.
From the CV study, the electrochemical data of the complex has been calculated and
the complex involves the one electron reversible mechanism. On the other hand, the nonreactivity of the complex with the environmental gases like CO2 and O2 has been als
also tested
and proved by the CV study of the complex under aerobic conditions.
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Sofani Tafesse Gebreyesus, et al., J. Chem. & Cheml. Sci. Vol.5 (1), 19--27 (2015)

5.

Electrochemistry behavior Metal (II) Complexes Derived from Naphthofuran


Naphthofuran-2carbohydrazide and Diacetylmonoxime Schiff Base

Fig. 4: Suggested structure for [Co(C17H15O3N3)Cl2]n


[Co(

The redox property of the Cu(II) complex was investigated by electrochemical method using
cyclic voltammetry. The electrochemical behavior of Cu(II) complex exhibited the one
electron transfer quasi-reversible
reversible redox couple26.
6. PVC Based Sensor For Anion Recognition Using 1, 1212 diaaza-5,8-dioxo
dioxo-3[4],9[10]dibenzoylcyclotetradeca
dibenzoylcyclotetradeca-2,11-diene
Schiff Based Macrocyclic Receptor:
The solution for PVC membrane was prepared through mixing of the 33% PVC,
66% dibutylphthalate,1%L1(1,12-diaaza-5,8-dioxo-3[4],9[10]dibenzoylcyclotetradeca
dibutylphthalate,1%L1(1,12
3[4],9[10]dibenzoylcyclotetradeca2,11-diene)
diene) mixed and dissolved in THF. The resulting solution was poured into a glass
mould and THF was allowed to evaporate off at room temperature over 24 h. A flexible
membrane was obtained. The disc
discs were cut and pasted onto a glass-tube,
tube, which consisted of
an Ag-AgCI
AgCI wire immersed in an internal solution of anionic solution by immersion in its
respective anionic metal solution.

Fig. 5: 12- diaaza-5,8-dioxo-3[4],9[10]-dibenzoylcyclotetradeca-2,11-diene


diaaza
diene
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The conclusion can be drawn that the Schiff based macrocyclic complexes provide a
suitable matrix for the fabrication of membrane sensors for anions. These membrane
electrodes are selective to specific anions and can be successfully used as indicator
electrodes in the direct analysis of synthetic as well as real samples. These electrochemical
sensors also have enough lifetimes for estimation of samples27.
Schiff bases have been used as carriers in the preparation of mpotentiometricsensors
for determining cations and anions28-37 . Aruthenium(III) Schiff base complex was used in the
fabrication of chloride PVC-based membrane sensor38.
The sensor with a composition of 30% PVC, 62% benzyl acetate, 5% ruthenium(III)
Schiff base complex and 3% hexadecyltrimethyl ammonium bromide displays nearNernstian behavior over a wide concentration range. It shows high selectivity toward
chloride ions over several organic and inorganic anions and was successfully applied for the
determination of chloride in serum samples. It could also be used as an indicator electrode in
the potentiometric titration of chloride ions with silver nitrate solution. Recently, there is a
report on a potentiometric aluminium sensor based on the use N,N-bis(salicylidene)-1,2cyclohexanediamine as a neutral carrier in poly(vinyl chloride) matrix. It was successfully
applied for direct determination of aluminium(III) in biological, industrial and environmental
samples39.
The electrode could be used in the pH range of 2.09.0 and mixtures containing up
to 20% (v/v) non-aqueous content. It has been used as an indicator electrode in
potentiometric titration of aluminium ion with EDTA. The Schiff base, N,N,N,N1,5,8,12-tetraazadodecane-bis(salicylaldiminato), has been used as ionophore for preparing
Mn2+ selective sensor40. The sensor was found to be sufficiently selective for Mn2+ over a
number of alkali, alkaline and heavy metal ions and could therefore be used for the
determination of manganese in various samples by direct potentiometry.
ACKNOWLEDGEMENT
I would like to give thank to the digital library of College of natural sciences,
Arbaminch university. Besides, I would like to appreciate Mrs. Nitsuh Wubeshet, for her
support for the review.
REFERENCES
1. Cohen B, Biochimicaet Biophysica Acta, 391, 193 (1975).
2. (a) S.Gaur, Assian J. Chem. 15(1), 250 (2003). (b) M.J.Gemi, C.Biles, B.J.Keiser,
S.M.Poppe, S.M. Swaney, W.G.Tarapley, D.L.Romeso, Y.Yage, J.Med.Chem. 43(5),
1034 (2000).
3. R. Rao, A.K. Patra, P.R. Chetana, DNA binding and oxidative cleavage activity of
ternary (L-proline)copper(II) complexes of heterocyclic bases, Polyhedron 26, pp. 53315338, (2007).
January, 2015 | Journal of Chemistry and Chemical Sciences | www.chemistry-journal.org

26

Sofani Tafesse Gebreyesus, et al., J. Chem. & Cheml. Sci. Vol.5 (1), 19-27 (2015)

4. Y. Fu, P. Li, L. Bu, T. Wang, Q. Xie, J. Chen, S. Yao, Exploiting Metal-Organic


Coordination Polymers as Highly Efficient Immobilization Matrixes of Enzymes for
Sensitive Electrochemical Biosensing, Anal. Chem.83(17), pp.6511- 6517, (2011).
5. D.W. Kimmel, G. LeBlanc, M.E. Meschievitz, D.E. Cliffel, Electrochemical Sensors
and Biosensors, Anal. Chem. 84 (2),pp. 685-707, (2012).
6. H. Tian, Z. Yu, A. Hagfeldt, L. Kloo, L. Su, Organic Redox Couples and Organic
Counter Electrode for Efficient Organic Dye-Sensitized Solar Cells, J. Am. Chem. Soc.
133(24), pp.9413-9422, (2011).
7. M.H. Habibi, E. Shojaee, G.S. Nichol, Synthesis, spectroscopic characterization and
crystal structure of novel NNNN-donor -bis(bidentate) tetraaza acyclic Schiff base
ligands, Spectrochim. Acta A, 98, pp. 396404, (2012).
8. M. Ulusoy, O. Birel, O. Sahin, O. Buyukgungor, B. Cetinkya, Structural, spectral,
electrochemical and catalytic reactivity studies of a series of N2O2 chelated palladium(II)
complexes, Polyhedron. 38, pp.141148, (2012).
9. J.H. Billman, K.M. Tai, Reduction of Schiff bases. II. Benzhydrylamines and
structurally related compounds, J. Org. Chem. 23, pp. 535-539, (1958).
10. M. Valcarcel, M.D. Laque de Castro, Flow-Throgh Biochemical Sensors, Elsevier,
Amsterdam, (1994).
11. U. Spichiger-Kelle, Chemical Sensors and Biosensors for Medical and Biological
Applications, Wiley-VCH, Weinheim, (1998).
12. J.F. Lawrence, R.W. Frei, Chemical Derivatization in Chromatography, Elsevier,
Amsterdam, (1976).
13. R. Hernanddez-Molina, A. Mederos, in: J.A. McCleverty, T.J. Meyer (Eds.), Acyclic and
Macrocyclic Schiff Base Ligands in comprehensive Coordination Chemistry II, Vol. 2,
Pergamon Press, New York, pp. 411446 (2004).
14. R. Suresh, A. Vijayaraj, K. Giribabu, R. Manigandan, R. Prabu, A. Stephen, E. Thirumal,
V. Narayanan, Fabrication of iron oxidenanoparticles: magnetic and electrochemical
Sensing property, J Mater Sci. Mater Electron, 24, pp. 12561263, (2013).
15. K. Giribabu, R. Suresh, R. Manigandan, A. Stephen, V. Narayanan, Cadmium oxide
nanoplatelets: synthesis, characterization andtheir electrochemical sensing property of
catechol, J Iran Chem Soc., 10, pp. 771776, (2013).
16. S. Praveen Kumar, R. Suresh, K. Giribabu, R. Manigandan, S. Munusamy, S.
Muthamizh and V. Narayanan; Electrochemical sensing of Pyrocatechol by Schiff base
modified GCE; International Journal of Innovative Research in Science & Engineering;
pp. 2347-3207.
17. L.F. Fan, X.Q. Wu, M.D. Guo, Y.T. Gao, Cobalt hydroxide film deposited on glassy
carbon electrode for electrocatalytic oxidation of hydroquinone, Electrochim. Acta, 52,
pp. 3654 3659, (2007).
18. B. Yogeshwaria, S. Praveen Kumarb ,V. Narayananb and L. Leelavathya Synthesis,
Characterization of Acyclic Schiff base and its Eletrochemical Sensing property for
Hydroquinone; IJIRSE, 2347-3207.
January, 2015 | Journal of Chemistry and Chemical Sciences | www.chemistry-journal.org

Sofani Tafesse Gebreyesus, et al., J. Chem. & Cheml. Sci. Vol.5 (1), 19-27 (2015)

27

19. M. Tmer, J. Coord. Chem. 60 (19), 20512065 (2007).


20. MuhammetKose a, Gokhan Ceyhan a, Mehmet Tumer a,, _Ibrahim Demirtas_
b,_IlyasGonul c, Vickie McKee d; Monodentate Schiff base ligands: Their structural
characterization,photoluminescence, anticancer, electrochemical and sensor properties;
SpectrochimicaActa Part A: Molecular and Biomolecular Spectroscopy 137, 477485
(2015).
21. C. Kratky, R. Tschatka, C. Angst, J.E.J. Plaquevent, Helv. Chim. Acta, 68, 1312 (1985).
22. P.A. Connick, K.A. Macor, Inorg. Chem., 30, 4654 (1991).
23. A.M. Tait, F.V. Lovecchio, D.H. Busch, Inorg. Chem., 16, 2206 (1977).
24. J.A. Streeky, D.G. Pilsbury, D.H. Busch, Inorg. Chem., 19, 3148 (1980).
25. N. Raman, A. Selvan, S. Sudharsan, Spectrochim. Acta A, 79, 873 (2011).
26. R. B. SumathiandM. B. Halli; Bioinorganic Chemistry and Applications, 11, (2014).
27. Amit Nagar, Sushil Kumar Sindhu , Rahul Kumar Panwar; Study On Poly (Vinyl
Chloride) Based Sensor For Anion Recognition Using 1, 12- diaaza-5,8-dioxo3[4],9[10]-dibenzoylcyclotetradeca-2,11-diene
L1[DADODBCT]
Schiff
Based
Macrocyclic Receptor; IJPB; 4(5): 909 912.
28. T. Shamspur, I. Sheikhshoaie, M.H. Mashhadizadeh. Journal of Analytical Atomic
Spectrometry, 20, 476-478 (2005).
29. S. Sadeghi, M. Eslahi, M.A. Naseri, H. Naeimi, H. Sharghi, A. Shameli. Electroanalysis,
15, 1327-1333 (2003).
30. M. H. Mashhadizadeh, I. Sheikhshoaei, S. Saeid-Nia. Sensors and Actuators B chemical,
94, 241-246 (2003).
31. R.K. Mahajan, I. Kaur, M. Kumar. Sensors and Actuators B Chemical, 91, 26-31 (2003).
32. M.H. Mashhadizadeh, I. Sheikhshoaei. Analytical and Bioanalytical Chemistry, 375, 51
(2003).
33. L. P. Singh, J. M. Bhatnagar. Talanta, 64, 313-319 (2004).
34. A.R. Fakhari, T.A. Raji, H. Naeimi. Sensors and Actuators B Chemical, 104, 317-323
(2005).
35. T. Jeong, H.K. Lee, D.C. Jeong, S. Jeon. Talanta, 65, 543-548 (2005).
36. M. Shamsipur, M. Yousefi, M. Hosseini, M.R. Ganjali, H. Sharghi, H. Naeimi.
Analytical Chemistry, 73 (2001) 2869-2874.
37. M.R. Ganjali, T. Poursaberi, M. Hosseini, M. Salavati-Niasari, M. Yousefi, M.
Shamsipur. Analytical Sciences, 18, 289-292 (2002).
38. M.R. Ganjali, M.R. Pourjavid, M. Rezapour, T. Poursaberi, A. Daftari, M. SalavatiNiasari. Electroanalysis, 16, 922-927 (2004).
39. V.K. Gupta, R.N. Goyal, A.K. Jain, R.A. Sharma. Electrochimica Acta, 54, 32183224
(2009).
40. V.K. Gupta, A.K. Jain, G. Maheshwari. Talanta, 72, 49-53 (2007).

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