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Department of Chemistry, Zakir Husain College (University of Delhi), J.L. Nehru Marg, New Delhi 110002, India
Department of Applied Science and Humanities, FET, Mody Institute of Technology and Science, Lakshmangarh 332311, Rajasthan, India
a r t i c l e
i n f o
Article history:
Received 28 July 2011
Received in revised form
16 November 2011
Accepted 15 December 2011
Keywords:
Macrocycles
Ni(II) and Cu(II) complexes
UVvis
EPR spectra
Molecular modeling
Cyclic voltammetry
a b s t r a c t
Ni(II) and Cu(II) complexes were synthesized with a hexadentate macrocyclic ligand [3,4,8,9tetraoxo2,5,7,10tetraaza-1,6dithio-(3,4,8,9) dipyridinedodecane(L)] and characterized by elemental analysis,
molar conductance measurements, mass, NMR, IR, electronic, EPR spectral, thermal and molecular modeling studies. All the complexes are 1:2 electrolytes in nature and may be formulated as [M(L)]X2 [where,
M = Ni(II) and Cu(II) and X = Cl , NO3 , SO4 2 , CH3 COO ]. On the basis of IR, electronic and EPR spectral
studies an octahedral geometry has been assigned for Ni(II) complexes and tetragonal geometry for Cu(II)
complexes. The antimicrobial activities and LD50 values of the ligand and its complexes, as growth inhibiting agents, have been screened in vitro against two different species of bacteria and plant pathogenic
fungi.
2012 Elsevier B.V. All rights reserved.
1. Introduction
The eld of coordination chemistry of tetraaza macrocycles
has been studied extensively [15]. Macrocyclic compounds are
similar in structure and reactions to many naturally occurring
compounds, which are known to exhibit selective cation complexation [6,7]. Investigations of transition metal complexes with the
cyclic polyamine ligands are of current interest because they are
used as antiviral drugs [810] and as catalysts for various reactions (e.g., epoxidation or hydrolysis of DNA [1113]) and can
bind dioxygen [14,15]. The chemical properties of macrocyclic
complexes can be tuned to force metal ions to adopt unusual coordination geometry. Transition metal macrocyclic complexes have
been received much attention as an active part of metalloenzymes
[16] as biomimic model compounds [17] due to their resemblance with natural proteins like hemerythrin and enzymes. Also,
Schiff-bases have played an important role in the development
of coordination chemistry as they readily form stable complexes
with most of the transition metals. Synthesis of transition metal
complexes of new aza macrocycles with different cavity sizes,
donor types, ring substituents, etc., under different experimental
conditions have resulted in a large number and variety of compounds [1822]. Because of the numerous areas of chemistry where
aza-macrocyclic complexes have found a niche, the preparation of
new macrocyclic ligands with ever more elaborate structures is also
a vital area of research. In the present paper we report the synthesis and characterization of nickel(II) and copper(II) complexes
of 3,4,8,9tetraoxo-2,5,7,10tetraaza-1,6dithio-(3,4,8,9) dipyridinedodecane(L) (Scheme 1).
2. Experimental
All the chemicals used were of Anala R grade and procured from
SigmaAldrich. Metal salts were purchased from E. Merck and were
used as received.
313
314
Table 1
Molar conductance and elemental analysis data of the complexes.
Complexes
[Ni(L)]Cl2
NiC16 H14 N6 O4 S2 Cl2
[Ni(L)](NO3 )2
NiC16 H14 N8 O10 S2
[Ni(L)]SO4
NiC16 H14 N6 O10 S3
[Ni(L)](CH3 COO)2
NiC18 H20 N6 O8 S2
[Cu(L)]Cl2
CuC16 H14 N6 O4 S2 Cl2
[Cu(L)](NO3 )2
CuC16 H14 N8 O10 S2
[Cu(L)]SO4
CuC16 H14 N6 O10 S3
[Cu(L)](CH3 COO)2
CuC18 H20 N6 O8 S2
Molar conductance
(1 cm2 mol1 )
Colour
Yield (%)
m.p./dec. ( C)
35.89
(35.80)
32.21 (32.17)
1.90
(1.86)
1.61
(1.67)
1.79
(1.75)
2.75
(2.70)
1.88
(1.82)
1.62
(1.66)
1.77
(1.74)
1.71
(1.67)
15.62
(15.66)
18.70
(18.76)
14.71
(14.77)
14.27
(14.21)
15.36
(15.31)
18.65
(18.62)
14.71
(14.64)
14.15
(14.10)
176
Green
64
270
10.88 (10.94)
188
Green
60
202
192
Green
58
210
9.88
(9.83)
10.27 (10.32)
191
Green
62
255
158
Light
Blue
Sky
Blue
Blue
67
260
65
254
69
250
63
258
161
166
170
Shiny
Blue
Fig. 4. Electrostatic potential surface of the PM6 geometry optimised structure (red
negative, green neutral and blue positive) of the ligand. (For interpretation of the
references to colour in this gure legend, the reader is referred to the web version
of the article.)
9.89
(9.93)
11.51 (11.57)
10.61
(10.55)
11.02
(11.07)
10.60
(10.66)
33.81
(33.76)
40.67 (40.60)
35.05
(35.00)
31.99 (31.92)
33.41 (33.47)
33.15 (32.24)
Fig. 5. (a) HOMO orbitals of the PM6 geometry optimised structure of the ligand.
(b) LUMO orbitals of the PM6 geometry optimised structure of the ligand.
315
Table 5
Electrochemical data of Cu(II) complexes in DMSO.
Complexes
eff (B.M.)
max (cm1 )
Complexes
Ec (mV)
Ea (mV)
E1/2 (mV)
[Ni(L)]Cl2
[Ni(L)](NO3 )2
[Ni(L)]SO4
[Ni(L)](CH3 COO)2
[Cu(L)]Cl2
[Cu(L)](NO3 )2
[Cu(L)]SO4
[Cu(L)](CH3 COO)2
2.91
2.97
3.08
2.97
1.95
1.94
2.04
1.96
[Cu(L)]SO4
[Cu(L)](CH3 COO)2
700
410
95
270
340
Table 6
Antibacterial activities data of the ligand (L) and their [Ni(L)](CH3 COO)2 ,
[Cu(L)](CH3 COO)2 complexes.
Bacterial inhibition (%) (conc. in g mL1 )
Compounds
Basillus subtilis
Table 3
Ligand eld parameters of Ni(II) complexes.
1
Complexes
Dq
B (cm
[Ni(L)]Cl2
[Ni(L)](NO3 )2
[Ni(L)]SO4
[Ni(L)](CH3 COO)2
971
928
966
929
388
295
370
374
0.37
0.35
0.28
0.35
139
133
138
133
L
[Ni(L)](CH3 COO)2
[Cu(L)](CH3 COO)2
Streptomycin
Xenthomonas compestris
0.05
0.075
0.1
15.29
16.47
32.94
17.64
20
37.64
22.35
23.52
41.17
0.05
0.075
0.1
16.47
21.17
80
20
23.52
85.88
25.88
31.76
91.76
The thermal stability of the complexes with ligand was investigated using TGA. The thermogravimetric analyses (TGA) were
carried out at a heating rate of 10 C/min in a nitrogen atmosphere
Table 4
EPR spectral data of the Cu(II) complexes in DMSO at room temperature and liquid nitrogen temperature.
Complxes
[Cu(L)]Cl2
[Cu(L)](NO3 )2
[Cu(L)]SO4
[Cu(L)](CH3 COO)2
At RT
At LNT
g1
g2
g3
g||
giso
g1
g2
g3
g||
giso
45
36
96
92
3240
3201
3190
3071
3290
3235
3220
2980
3350
3263
3250
3142
2.09
2.12
2.23
2.21
2.02
2.08
2.09
2.16
2.04
2.10
2.14
2.17
3.63
1.44
2.40
1.31
30
48
36
56
2900
2910
2920
3141
3000
2990
2950
3250
3100
3080
3100
3327
2.24
2.23
2.12
2.07
2.09
2.11
2.08
2.04
2.14
2.15
2.10
2.05
2.48
2.11
1.44
1.78
316
Table 7
Antifungal activities data of the ligand (L) and their [Ni(L)](Cl)2 , [Cu(L)](Cl)2 complexes.
Fungal inhibition (%) (conc. in g mL1 )
Compounds
Rizactonia solani
0.05
L
[Ni(L)](Cl)2
[Cu(L)](Cl)2
Ciplooxamin for
R. solani (standard)
Tricyclozole for
R. blast (standard)
5.88
15.29
10.58
0.075
15.29
20
21.63
Rice blast
0.1
22.35
36.47
31.76
0.5
69.95
85.88
76.47
12
1
100
100
100
0.05
24.70
37.64
29.41
0.075
36.47
45.88
38.82
0.1
0.5
41.17
54.70
43.52
74.11
85.88
76.47
100
100
100
0.2391/0.1766
0.2126/
0.2139/0.01766
28
17
>500 C
257 C
>500 C
Bacillus sublitis Gram (+) and Xanthomonas compestris Gram () bacteria, as growth inhibitor by the DUAL CULTURE METHOD [45]. NSA
(nutrient sucrose agar) medium (nutrient broth 8 g L1 , sucrose
50 g L1 and agar 18 g L1 ) is used for isolation, cutting and maintenance of bacterial culture. Streptomycin is used as standard drug
[Graph 1]. The results of the antibacterial screening show the order
of percentage inhibition has been observed to be presented in
Table 6. Antibacterial studies data show that metal complexes show
moderate activities as compared to free ligands.
4.7.2. Antifungal screening
The ligand (L) and their complexes with NiCl2 and CuCl2 for antifungal studies were screened against Rhizoctonia solani and Rice
blast fungi, as growth inhibitor by FOOD POISON TECHNIQUE [46].
Potato dextrose agar (39 g L1 ) for Rhizoctonia solani and oat meal
(50 g L1 oatmeal, 20 g L1 agar) sucrose medium for Rice blas are
used for are used for isolation, cutting and maintenance of fungal culture. Amphotericin-B and Tricyclozole are used as standard
drugs [Graph 2]. The results of the antibacterial screening show the
order of percentage inhibition has been observed to be presented
in Table 7. Antifungal studies and their (Probit analysis) LD50 data
show that metal complexes show moderate activities as compared
to free ligands. The Probit analysis studies are shown in Graph 3, 4
and 5.
5. Conclusion
Ni(II) and Cu(II) complexes with a hexadentate macrocyclic ligand have been prepared and characterized. On the basis of above
spectral studies and molecular modeling a distorted octahedral
geometry has been assigned for Ni(II) and tetragonal geometry for
Cu(II) complexes. Various ligand eld and bonding parameters have
been calculated and discussed. Electrochemical, thermal, antimicrobial studies have been discussed.
Acknowledgements
We thank the Principal, Zakir Husain College for providing laboratory facilities, SAIF, IIT (Bombay) for recording ESR spectra and
DRDO, New Delhi for nancial support, the Head, App Sci. and Dean
FET for recording molecular modeling data.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.saa.2011.12.028.
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