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International Journal of Pharmaceutical Biological and Chemical Sciences ISSN: 2278-5191 International Journal of Pharmaceutical, Biological and Chemical Sciences (IJPBCS) | Apr-Jun 2016 | VOLUME 5 | ISSUE 2 |11-22 www.ijpbcs.net or www.ijpbcs.com Original Research Article Page11 SYNTHESIS, CHARACTERIZATION, MAGNETIC INTERACTIONS AND BIOLOGICAL APPLICATIONS OF HOMO AND HETERO BINUCLEAR SCHIFF BASE COMPLEXES R.PA. Bhoopathy 1 , M. Malathy 1 , R. Jayalakshmi 1 and R. Rajavel 1 * Department of Chemistry, Periyar University, Salem- 636011, Tamilnadu, India. *Corresponding Author Email: [email protected] INTRODUCTION The interaction of organic / inorganic ligands with the metal centers is one of the most active research areas in inorganic chemistry. Coordination chemistry includes different types of coordination complexes applicable in a wide diversity of fields such as, catalysis, bioinorganic chemistry, medicine, ceramics, material science and toxicology. Inclusion of a variety of ligands in complexes has enabled their applications such as chemical analysis, catalytic activity and biological applications including antimicrobial, insecticidal, anti-HIV, antitumor and in vitro - cytotoxic activities as well as DNA binders [1, 2]. Due to their easy formation and strong metal-binding ability of Schiff base, various metal complexes were easily synthesized. Schiff bases form stable chelates with metal ions when an additional donor closes to the azomethine nitrogen. However, many side-effects such as nephrotoxicity, neurotoxicity, inherited or acquired resistance phenomena limited its comprehensive applications in the therapy of cancers. These problems had prompted chemists to research more optimal strategies based on different metals and ligands, with the wide range of coordination numbers and geometries, available redox states, thermodynamic and kinetic characteristics, and intrinsic properties of the metal ions. In this field, copper complexes were definitely considered as alternative metal-based anticancer drugs [3, 4]. As copper is an essential element for most aerobic organisms, an assumption that this endogenous metal may be less toxic for normal cells than cancer cells is raised. It is reported that the metabolism and cell response to copper between normal and tumor cells are generally different, which ground the basis of copper complexes endowed with antineoplastic characteristics. Scientists found that the concentration of copper in numerous ex-vivo cancerous tissues (e.g., breast, prostate, lung, and brain) was exceeded than that of in normal tissues. Actually, control of tumor ABSTRACT: A series of homo and hetero binuclear Schiff base metal complexes, derived from mononuclear Schiff base complex which behaves as a ligand using transition metal ions such as Cu(II), and Ni(II) with the title ligand has been prepared. The ligand and its binuclear metal complexes were characterized by FT-IR, UV-VIS, 1 HNMR, EPR spectroscopy, Cyclic voltammetry and Thermal analyses method. Antimicrobial activities of the homo and hetero binuclear complexes were also evaluated. Based on the spectroscopic results, tentative structures of the metal complexes have been proposed. Hence, from the obtained results, though all the complexes exhibited excellent biological activity, the hetero binuclear complex has effective protection and enhanced bioactivity. KEYWORDS: Homo and hetero binuclear metal complexes, Spectral studies, Thermal analysis, Antibacterial activity.
Transcript
Page 1: SYNTHESIS, CHARACTERIZATION, MAGNETIC … · SYNTHESIS, CHARACTERIZATION, ... A series of homo and hetero binuclear Schiff base metal ... The reaction of two mononuclear complex units

International Journal of Pharmaceutical

Biological and Chemical Sciences

ISSN: 2278-5191

International Journal of Pharmaceutical, Biological and Chemical Sciences (IJPBCS)

| Apr-Jun 2016 | VOLUME 5 | ISSUE 2 |11-22 www.ijpbcs.net or www.ijpbcs.com

Original Research Article

Pag

e11

SYNTHESIS, CHARACTERIZATION, MAGNETIC INTERACTIONS

AND BIOLOGICAL APPLICATIONS OF HOMO

AND HETERO BINUCLEAR SCHIFF BASE COMPLEXES

R.PA. Bhoopathy1, M. Malathy

1, R. Jayalakshmi

1 and R. Rajavel

1*

Department of Chemistry, Periyar University, Salem- 636011, Tamilnadu, India.

*Corresponding Author Email: [email protected]

INTRODUCTION

The interaction of organic / inorganic ligands with the

metal centers is one of the most active research areas

in inorganic chemistry. Coordination chemistry

includes different types of coordination complexes

applicable in a wide diversity of fields such as,

catalysis, bioinorganic chemistry, medicine, ceramics,

material science and toxicology. Inclusion of a variety

of ligands in complexes has enabled their applications

such as chemical analysis, catalytic activity and

biological applications including antimicrobial,

insecticidal, anti-HIV, antitumor and in vitro -

cytotoxic activities as well as DNA binders [1, 2]. Due

to their easy formation and strong metal-binding

ability of Schiff base, various metal complexes were

easily synthesized. Schiff bases form stable chelates

with metal ions when an additional donor closes to the

azomethine nitrogen. However, many side-effects

such as nephrotoxicity, neurotoxicity, inherited or

acquired resistance phenomena limited its

comprehensive applications in the therapy of cancers.

These problems had prompted chemists to research

more optimal strategies based on different metals and

ligands, with the wide range of coordination numbers

and geometries, available redox states, thermodynamic

and kinetic characteristics, and intrinsic properties of

the metal ions. In this field, copper complexes were

definitely considered as alternative metal-based

anticancer drugs [3, 4].

As copper is an essential element for most aerobic

organisms, an assumption that this endogenous metal

may be less toxic for normal cells than cancer cells is

raised. It is reported that the metabolism and cell

response to copper between normal and tumor cells are

generally different, which ground the basis of copper

complexes endowed with antineoplastic

characteristics. Scientists found that the concentration

of copper in numerous ex-vivo cancerous tissues (e.g.,

breast, prostate, lung, and brain) was exceeded than

that of in normal tissues. Actually, control of tumor

ABSTRACT:

A series of homo and hetero binuclear Schiff base metal complexes, derived from mononuclear Schiff base complex which

behaves as a ligand using transition metal ions such as Cu(II), and Ni(II) with the title ligand has been prepared. The

ligand and its binuclear metal complexes were characterized by FT-IR, UV-VIS, 1HNMR, EPR spectroscopy, Cyclic

voltammetry and Thermal analyses method. Antimicrobial activities of the homo and hetero binuclear complexes were also

evaluated. Based on the spectroscopic results, tentative structures of the metal complexes have been proposed. Hence,

from the obtained results, though all the complexes exhibited excellent biological activity, the hetero binuclear complex

has effective protection and enhanced bioactivity.

KEYWORDS: Homo and hetero binuclear metal complexes, Spectral studies, Thermal analysis, Antibacterial activity.

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R. Rajavel* et al; Synthesis, Characterization, Magnetic Interactions And Biological Applications…………..

International Journal of Pharmaceutical, Biological and Chemical Sciences (IJPBCS) | APR-JUN 2016 |VOLUME 5 | ISSUE 2 | 11-22 | www.ijpbcs.net

Pag

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growth and metastasis could be attained by chelating

the excess of copper with several small molecules. At

present, many researches are focusing on the

synthesis, DNA cleavage activity and anticancer

mechanism of copper-based complexes [5,6]. The

redox behaviour of the Schiff base metal complexes

were performed by using electrochemical techniques

[7-9].

However, significant increasing drug resistance has

limited the clinical applications of metal compounds.

Nickel (II) complexes containing nitrogen and oxygen

donor ligands are highly important. In this line,

analogues Nickel complexes are found to be potent in

various therapeutic applications. Nickel is a lighter

congener of platinum and several Nickel complexes

have been found to be potent in various therapeutic

applications [10-13]. Based on that new Ni(II)

complex has been screened for their antibacterial

activity against various pathogenic bacteria. These

types of new therapeutic approach are rapidly

emerging and further research may go to designing

more specific chelates. Moreover, this complex is

going to be a member of new larger family of complex

with Nickel (II) ion [14- 20].

In the present study, we have synthesized some homo

and hetero binuclear Schiff base complexes with the

titled ligand(6,6’-((1,2-

phenylenebis(azanylylidene))bis(ethan-1-yl-1-

ylidene))bis(2,4-dichlorophenol)) and reported to the

characterization and biological properties. The

bimetallic complexes have been isolated in multi-step

reactions. The reaction of two mononuclear complex

units with homo or hetero metal ions has been

interacted in the first step. The resulting binuclear

complexes contain nitrogen and oxygen groups in

close locality are encapsulated by in mononuclear the

step resulting in the formation of binuclear complexes.

The antibacterial activity of ligand, mono and

binuclear complexes was tested against some

bacteria’s and it was proved that the inhibition zones

were improved on increasing the concentration.

EXPERIMENTAL SECTION

Materials

The chemicals, 3, 5-dichloro-2-hydroxy acetophenone

and O- Phenylene diamine were purchased from sigma

Aldrich and used as recceived. The metal salts used

were of reagent grade and used without further

purification. The solvents were commercially

available, purchased from Merck.

General methods

Elemental analyses (C, H, N and S) were carried out

on a Vario EL III CHNS analyzer at SAIF-Cochin,

India. Physical measurements, Magnetization of a

sample powder of Cu-Ni-L was measured between 2

and 300 K with an applied magnetic field H = 10 k Oe

using a Cryogenic S600 SQUID magnetometer. The

effective magnetic moments were calculated by the

equation μeff. = 2.828 (Vm/T) ½

, where Vm is the

molar magnetic susceptibility was set equal to Mm/H.

FT-IR spectra were recorded as KBr pellets using a

FT-IR 1650 Shimadzu Spectrometer in the range

4000-400 cm-1

. Electronic spectra have been obtained

on a Schimadzu UV–3101PC UV-VIS NIR scanning

spectrophotometer at room temperature. 1H-NMR

spectra was carried out at room temperature on a 500

MHz Bruker advanced DPX spectrophotometers using

CDCl3 as a solvent and TMS as an internal reference.

The Molar conductance was of 10-3

M solutions of the

solid complexes in DMF were measured using

Corning conductivity meter NY 14831 model 441.

Thermal analyses (TGA/DTA) of the complexes were

carried out under nitrogen atmosphere in the

temperature from 40ºC to 900ºC using Shimadzu

DTG-60, heating rate of 20° C/min. EPR spectra of the

complexes were carried out using Bruker EMX Plus

with Microwave Frequency, 9.865832 GHz at room

temperature. Antibacterial activity was studied by disc

diffusion method.

Synthetic procedure for ligand (HL)

A solution of O-Phenylene diamine (0.1081g;1 mmol)

in 20 mL ethanol was added drop wise to a solution of

3, 5-dichloro-2-hydroxy acetophenone (0.4101g;2 m

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R. Rajavel* et al; Synthesis, Characterization, Magnetic Interactions And Biological Applications…………..

International Journal of Pharmaceutical, Biological and Chemical Sciences (IJPBCS) | APR-JUN 2016 |VOLUME 5 | ISSUE 2 | 11-22 | www.ijpbcs.net

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mol) in an ethanol (20 mL). The mixture was gently

heated under reflux for 3 h, which resulted in a rapid

change of color from brown to orange yellow crystals.

After refluxing, the resulting solution was filtered and

the filtrate was left unperturbed for the slow

evaporation of the solvent. After four days orange

yellow colored crystals were obtained [21].

Characterization data:

Yield: 70% (0.34 mg); color: yellowish orange; MP:

120–125°C; micro analytical data: C22H14Cl5N2O2

required: C, 54.87; H, 2.90; N, 5.82. Found: C, 53.12;

H, 2.45; N, 5.60; IR (KBr pellet, cm−1) 3426 ν(–OH);

1637 ν(C=N); 1438 ν(C–O), 1442 ν{Ph(P–Ph)}; UV-

vis (EtOH), λmax (nm): 203,345. 1HNMR (500 MHz,

CDCl3, ppm): δ=1.5 (s, 6H, –CH3); 7.6 (s,2H, –

CH=N); 10.8 (s, 2H, –OH); 6.5–7.3 (m, 8H, Ar).

Synthetic procedure for mono nuclear Copper (II)

complex [Cu-L]

A solution of Copper (II) acetate (0.1816g;1mmol) in

20 mL ethanol was added drop wise to a solution of

ligand (0.4811g;1mmol) in an ethanol(20 mL). The

mixture was gently heated under reflux for 3 h [22],

which resulted in a rapid change of color from brown

to yellowish brown crystals. After refluxing, the

resulting solution was filtered and the filtrate was left

unperturbed for the slow evaporation of the solvent.

After four days orange yellow colored crystals were

obtained.

Characterization data:

Yield: 75% v (0.50 mg); color: yellowish brown; MP:

142–146°C; micro analytical data: CuC22H12Cl5N2O2

required: C, 48.64; H, 2.21; N, 5.16;Cu, 11.71. Found:

C, 46.78; H, 2.05; N, 5.01; IR (KBr pellet, cm−1)

1604 ν(C=N); 1425 ν(C–O), 548 (νM-O); 450(νM-N)

UV-vis (EtOH), λmax (nm): 206,375,647; Conductance

(ohm-1

cm2 mol

-110

-6): Λm=11

Synthesis of homobinuclear Copper (II) complex

[Cu2-L]

The homo binuclear Copper (II) complex was

synthesized by slow addition of 20ml ethanolic

solution of CuCl2 (0.1345g;1 mmol) to 20ml ethanolic

solution of Cu-L(0.5427g;mmol). The resulting

mixture was heated under reflux for 4 hrs [22]. After

refluxing, the resulting solution was filtered and the

filtrate was left undisturbed for the slow evaporation

of the solvent. After five days brown colored crystals

were obtained.

Characterization data:

Yield: 65%(0.46mg); color: brown; MP: 152–157°C;

micro analytical data: Cu2C22H12Cl7N2O2 required: C,

38.98; H,1.77; N, 4.13;Cu, 18.76. Found: C, 37.41.78;

H, 1.24; N, 3..98; IR (KBr pellet, cm−1) 1619 ν(C=N);

1428 ν(C–O), 519 (νM-O); 464 (νM-N) UV-vis (EtOH),

λmax (nm): 209, 378, 591; Conductance (ohm-1

cm2

mol-1

10-6

): Λm=20

Synthesis of heterobinuclear copper (II) and Nickel

(II) complex [Cu-Ni-L]

30 mL solution of NiCl2(0.1296g;1mmol) in ethanol

was added drop by drop to 30mL hot solution of

mono nuclear Copper(II) complex(0.5427g;1mmol) in

ethanol and the resulting mixture was heated under

reflux for 5 h by refluxing the contents for 3 hrs [22].

After refluxing, the resulting solution was filtered,

washed with ethanol and the filtrate was left

undisturbed for the slow evaporation of the solvent.

After five days brown colored crystals were obtained.

Characterization data:

Yield: 60%(0.41mg); color: brown; MP: 160–164°C;

micro analytical data: CuNiC22H12Cl7N2O2 required:

C, 39.26; H,1.78; N, 4.16;Cu, 9.45;Ni,8.73. Found: C,

37.24; H, 1.32; N, 3..78; IR (KBr pellet, cm−1) 1630

ν(C=N); 1427 ν(C–O), 612 (νM-O); 460 (νM-N) UV-vis

(EtOH), λmax (nm): 210, 370, 505; Conductance

(ohm-1

cm2 mol

-110

-6): Λm=24

RESULTS AND DISCUSSION

Synthesis and characterization

A new series of homo and hetero binuclear complexes

of the type [ML, M2L, M-M’-L-X2] (M = Cu (II), M’ –

Ni (II), L = ligand and X = Cl) were synthesized as

shown in Scheme 1. All the complexes are soluble in

ethanol but insoluble in water.

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R. Rajavel* et al; Synthesis, Characterization, Magnetic Interactions And Biological Applications…………..

International Journal of Pharmaceutical, Biological and Chemical Sciences (IJPBCS) | APR-JUN 2016 |VOLUME 5 | ISSUE 2 | 11-22 | www.ijpbcs.net

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Scheme- I

Scheme- II

The molar conductance values are in the range 10-24

Ω-1

cm2 mol

-1 which is perfectly near to non-

electrolytes values (20-30 Ω-1

cm2 mol

-1) in 10

-3 M

DMF solution were shown in Table 1. The neutrality

of the complexes can be related by the deprotonated

nature of the ligand with most complexes.

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R. Rajavel* et al; Synthesis, Characterization, Magnetic Interactions And Biological Applications…………..

International Journal of Pharmaceutical, Biological and Chemical Sciences (IJPBCS) | APR-JUN 2016 |VOLUME 5 | ISSUE 2 | 11-22 | www.ijpbcs.net

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Table 1: Analytical and physical data of Schiff base ligand and its metal complexes

Table 2: IR and UV Spectral data of the ligand and its metal complexes

Compounds υ (O-H) cm-1

υ (C=N) cm-1

υ (C-O) cm-1

υ (M-O) cm-1

υ (M-N) cm-1

λmax nm

L 3426 1637 1438 - - 203,345

CuL - 1604 1425 548 450 206,375,647

Cu2L - 1619 1428 519 464 209,378,591

Cu-Ni-L - 1630 1427 612 460 210,350,505

Table 3: Cyclic voltammetric data of homo and hetero binuclear metal complexes

Complexes

Reduction Oxidation

Epc(V) Epa(V) E1/2(V) ΔEp

(mV) Epc(V) Epa(V) E1/2(V)

ΔEp

(mV)

[Cu-CuL] -1.8 -1.6 -1.7 200 0.9 1.3 1.1 400

[Cu-NiL] -1.2 -0.9 -1.05 300 0.3 0.65 0.475 350

Table 4.Thermo Analytical data of the metal complexes

Complexes Temperature range of

decomposition(ºC) % of weight loss Remarks

CuL

235-450 6.7 Loss of chloride ion from complex

450-540 34.5 Partial decomposition of organic part of ligand

590-735 50.3 Complete decomposition with the formation of

mixed metal oxide

Cu2L

170-290 16 Loss of chloride ion

300-450 39.33 Partial decomposition of organic part of ligand

550-740 77 Complete decomposition with the formation of

mixed metal oxide

Cu-Ni-L

145-340 25 Loss of chloride ion

400-575 62 Partial decomposition of organic part of ligand

610-690 87 Complete decomposition with the formation of

mixed metal oxide

FT-IR Spectra

The FT-IR analysis of Ligand (HL), mono nuclear

(Cu-L) and binuclear complexes (Cu2-L and Cu-Ni-L)

was carried out and the corresponding spectra are

shown in Fig. 1(a-d) and Table 2. In the IR spectrum

of the ligand, the –O-H stretching vibration band was

observed at 3427 cm -1

, as well as the C-N band at

1438 cm−1

, the C=N sharp band at 1637 cm−1

, and the

C-O band at 1243 cm−1

. Fig. 1(b) shows IR spectra of

the mono nuclear complex (Cu-L), similar to that of

Compounds Molecular

formula

Color

Found (calcd) % Λm

ohm-1

cm2

mol-1

10-6

C H N M

Cu Ni

L C22H14Cl5N2O2 Yellowish

Orange

53.12

(54.87)

2.45

(2.9)

5.60

(5.82)

- - -

CuL CuC22H12Cl5N2O2 Yellowish

brown

46.78

(48.64)

2.05

(2.21)

5.01

(5.16)

11.56

(11.71)

- 11

Cu2L Cu2C22H12Cl7N2O2 Brown 37.41

(38.98)

1.24

(1.77)

3.98

(4.13)

18.59

(18.76) - 20

Cu-Ni-L CuNiC22H12Cl7N2O2 Brown 37.24

(39.26)

1.32

(1.78)

3.78

(4.16)

9.36

(9.45)

8.61

(8.73) 24

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R. Rajavel* et al; Synthesis, Characterization, Magnetic Interactions And Biological Applications…………..

International Journal of Pharmaceutical, Biological and Chemical Sciences (IJPBCS) | APR-JUN 2016 |VOLUME 5 | ISSUE 2 | 11-22 | www.ijpbcs.net

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the ligand but with a slight change in the wave

numbers. The spectrum of mono nuclear complex (Cu-

L) shows the C=N sharp band, the C-N and the C-O

band at 1625 cm-1

, 1425 cm−1

, and 1224 cm−1

respectively. Fig. 1(c) and 1(d) shows IR spectra of

homo and hetero binuclear complexes respectively

which represent the characteristic peaks corresponding

to the mono nuclear complex but with slight change in

the wave number. In the IR spectra of these complexes

(-OH) stretching vibrations disappeared which shows

coordination of oxygen to the metal. The band

assigned to ν(C-O) shifted to lower frequency i.e.19

cm−1

upon coordination in the complexes. The band

assigned to ν(C-N) shows a shift of 13 cm−1

towards a

lower frequency [23-25]. IR data confirm the copper

(II) metal atom binding together with both O and N

donor groups of the Schiff base ligand and support the

tentative structure of the complexes. The stronger

bands appearing at 450 - 460 cm-1

were assigned to M

- N and M - O stretching frequencies for all the

complexes respectively [26-28].

Fig. 1: FT-IR spectra of (a) Ligand (HL) (b) mono nuclear complex (Cu-L) (c) homo binuclear complex

(Cu2-L) (d) hetero binuclear complex (Cu-Ni-L).

UV-Visible Spectra

The UV spectral analysis of Ligand (HL), mono

nuclear complex (Cu-L) and binuclear complexes

((Cu2-L) & (Cu-Ni-L)) was carried out and shown in

Fig. 2(A-D). Fig.2 (A), the absorption spectral data for

Schiff base ligand shows the peaks around 203 nm and

345 nm were assigned to ligand-centred (LC) π→π*

and n→π* transitions. Fig.2 (B) shows the absorption

spectrum of complex 1 in alcohol solution at room

temperature exhibits a band at 647 nm, due to d–d

transition. This type of absorption band has been

previously assigned to copper (II) complex with

square–planar geometry. Bands below 400 nm are due

to intraligand transitions. Fig.2 (C) and Fig. 2(d) show

the absorption spectrum of homo and hetero binuclear

complexes respectively. The broad band at 591 nm

and 505 nm regions, which are attributed to the d-d

transition bands of d9 (Cu(II)) and spin-paired d

8

(Ni(II)) with a square-planar structure [29].

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R. Rajavel* et al; Synthesis, Characterization, Magnetic Interactions And Biological Applications…………..

International Journal of Pharmaceutical, Biological and Chemical Sciences (IJPBCS) | APR-JUN 2016 |VOLUME 5 | ISSUE 2 | 11-22 | www.ijpbcs.net

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Fig. 2: UV-VIS spectra of (A) Ligand (HL) (B) mono nuclear complex (Cu-L) (C) hetero binuclear

complex (Cu2-L) (D) hetero binuclear complex (Cu-Ni-L).

1H NMR spectra

The 1H NMR spectrum of the ligand (HL) in CDCl3

(Fig. 3) shows the phenyl multiplet at δ= 6.5–7.3 ppm

and the azomethine proton at δ= 7.6 ppm (singlet).

The peak at δ= 10.8 ppm is attributed to the phenolic -

OH group present in the ligand and an additional peak

at δ=1.5 ppm is attributed to the -CH3 protons of the

ligand (HL).

Thermal Analyses (TGA/DTA)

Thermo gravimetric analyses of the Schiff base metal

complexes were investigated using TGA and DTA

analysis (Fig. 4(a-c)). The thermal analyses (TGA)

were performed in a nitrogen atmosphere with a

heating rate of 20oC/min over a temperature range of

20–800oC/min. The mono and binuclear copper

complexes have a different decomposition process.

The high thermal stability investigated complexes may

correspond to whether any solvent/water molecules

were inner/outer coordination sphere of the central

metal ion. The TG weight loss of the first stage,

exhibit decomposition between 335 and 420oC/min,

correspond to loss of chloride ion from complexes.

The second stage indicates (450oC) the partial

decomposition of organic part of ligand and the final

stage possess to complete decomposition together with

the formation of mixed metal oxide as final product

[30]. The differential thermal analysis (DTA) curves

of the mono and binuclear copper complexes shows

endothermic peak in the temperature range 180–

200oC/min assigned to loss of coordinated chloride

ion. The DTA curves that contained one sharp

exothermic peak falling in the temperature range of

350–415oC/min and conclude the formation of metal

oxides [31]. From the results, it is well evident that the

hetero binuclear complex decomposes at higher

temperature than compared to mononuclear and homo

binuclear complexes.

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Figure 3: 1H NMR spectra of ligand

EPR spectra

The X-band EPR spectra of mono nuclear complex

(Cu-L) as well as homo binuclear complex (Cu2-L)

were recorded at room temperature using DPPH as a

reference standard and the corresponding spectra are

shown in Fig. 5 (a-b). EPR spectra of homobinuclear

Complex (Fig. 5(b)), the hyperfine lines could not be

resolved which indicate the exchange interaction and

strong dipolar between copper (II) ions in the

complex. The reported complexes gave g‖ and g+

values in the regions 2.15–2.28 and 2.05–2.11

respectively. The exchange interaction between copper

centers, which measures by g values are related by the

expression G = (g‖ 2)/ (g+

2). The calculated G values

for these complexes appeared the parameters in the

range 2.18–3.00 which predicts the weak exchange

interaction. The g|| value is an important function for

indicating covalent character of M-L bonds [33]. For

ionic character, g‖ > 2.30 while for covalent character

g‖ < 2.30. In the present compounds, the g‖ < 2.30

indicating appreciable covalent character for Cu-L

bond. Such a spectrum is expected in complexes with

square planar geometry.

Cyclic voltammetry:

The electro chemical behavior of metal complexes was

studied by using cyclic voltammetry in DMSO

containing TBAP as supporting electrolyte beyond the

range of 2.0 to -2.0 V. The obtained electrochemical

data of the metal complexes were shown in Fig. 6 (a-

b) and summarized in Table 3. The cyclic

voltammogram of the Cu-CuL complex showed a

quasi-reversible reduction peak and the E1/2 values

indicate that each couple corresponds two step one

electron transfer process. Likewise oxidation process

as well quasireversible in nature [32]. So, the

processes were designated as follows.

CuII Cu

II ↔ Cu

II Cu

I ↔ Cu

I Cu

I

The representative cyclic voltammogram of the hetero

binuclear complex (Cu-NiL) was shown in Fig. 6 (b).

Based on these observations, both the E1/2 and ΔE

values suggest that the reduction process may involve

the two step one-electron transfer and quasireversible

and the processes were expressed as follows: CuII Ni

II

↔ CuII Ni

I ↔ Cu

I Ni

I

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Fig.4. TG/DTA of (a) mono nuclear complex (Cu-L) (b) homo binuclear complex (Cu2-L) (c) hetero

binuclear complex (Cu-Ni-L).

Fig.5. EPR spectra of (a) mono nuclear complex (Cu-L) and (b) homo binuclear complex (Cu2-L).

Magnetic properties

The magnetic susceptibility measurements (XM) and

its product with temperature (T) is shown in Fig. 7.

The variable temperature magnetic susceptibilities of

hetero binuclear complex were measured in the 2–300

K temperature range. The XM vs T value (1.26 cm3

mol-1 K) at room temperature slightly lower than the

spin-only value (1.38 cm3 mol-1 K) anticipated for the

uncoupled Cu(II)-Ni(II) unit. On cooling it decreases

smoothly and reaches a plateau below 40 K with XM

Vs T between 0.41 and 0.50 cm3 mol

-1 K. These

features are typical of Cu(II)-Ni(II) pairs with

antiferromagnetic intramolecular interaction. At low

temperature the plateaus below 40 K indicate that only

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International Journal of Pharmaceutical, Biological and Chemical Sciences (IJPBCS) | APR-JUN 2016 |VOLUME 5 | ISSUE 2 | 11-22 | www.ijpbcs.net

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the doublet ground state is thermally populated. It

decreases smoothly on cooling. These features are

typical of Cu (II)-Ni (II) pairs with antiferromagnetic

intramolecular interaction [34].

Figure 6 :( a) Cyclicvoltammogram of Cu2L; (b)Cyclicvoltammogram of Cu-Ni-L

Figure 7: Magnetic Susceptibility of hetero binuclear metal Complex.

Figure 8 (a): Antibacterial activity of Schiff base ligand and its metal complexes

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Figure 8(b): Antibacterial activity of Schiff base ligand and its metal complexes

Antibacterial activity

S. aureus, Bacillus (Gram-positive) and E. coli,

Proteus (Gram-negative) are the general bacterias that

are found in the contaminated wound. The synthesized

homo and hetero binuclear complexes were tested

against S. aureus, E. coli, Proteus and Bacillus stains

at different concentrations like 25, 50 and 75 (µg/mL)

which are compared with control (Fig.9(a-b)). From

the figure, it is well evident that heterobinuclear

complex has higher antibacterial activity versus both

the Gram-positive and Gram-negative bacteria stains.

Because of this, it is concluded that the substitution of

hetero atom to the binuclear complex can react with

the nuclear content of bacteria and destroy them

easily. Hence the hetero binuclear complex showed

excellent anti-bacterial activity. The variation in the

effectiveness of different compounds against different

organisms depends either on the impermeability of the

cells of the microbes or on divergence in ribosome of

microbial cells. In particular the complex showed

excellent activity against E. coli which is due to the

differences in the cell wall structure. The cell wall of

the gram-positive bacteria is made of a thick layer of

peptidoglycan, consisting of linear polysaccharide

chains leading to difficult penetration compared to the

gram-negative bacteria where the cell wall possesses

thinner layer of peptidoglycan. Therefore, changes in

the membrane structure of bacteria follows in the

increased anti-bacterial activity for the coatings

against E. coli. From the results it is well evident that

the binuclear complex not only retards the bacterial

adhesion, but also effectively kills the adhered bacteria

suggesting effective and long lasting antibacterial

activity against S. aureus, E. coli, Proteus and Bacillus

[35].

CONCLUSION

In this paper, we have shown the successful synthesis

of Schiff base ligand and its mononuclear, homo and

hetero binuclear complexes have been characterized

using spectroscopic methods, molar conductivity,

thermal analysis, cyclic voltammetry, EPR and

magnetic measurements. The square planar

environment of the metal complexes was confirmed by

electronic spectral data and magnetic moment values.

The cyclic voltammetry result supported that both the

mono and binuclear metal complexs exhibits with one

electron transfer and quasi-reversible nature. The

stability of metal complexes was ratified by using

thermal analyses. The EPR g|| values indicate high

energy d-d transition typical for planar CuN2O2

complexes. From the result of antibacterial activity

test, we concluded that the hetero binuclear complex

plays an effective role in improving the bioactivity.

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*Corresponding author Email address:

[email protected]


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