{Spectral, NLO and antimicrobial studies of Co(II), Ni(II) and Cu(II) complexes of Schiff base ligands of 2-amino-6-nitrobenzothiazole}
J. Serb. Chem. Soc. 84 (3) 267–275 (2019) UDC 546.732’742’562:542.9+547.571’551+
JSCS–5182 543.422.25:57–188
Original scientific paper
267
Spectral, NLO and antimicrobial studies of Co(II), Ni(II) and
Cu(II) complexes of Schiff base ligands of
2-amino-6-nitrobenzothiazole
CHINNARAJ KANAGAVALLI1, MURUGESAN SANKARGANESH2, JEYARAJ
DHAVEETHU RAJA2 and MANIVANNAN KALANITHI3*
1Department of Chemistry, Theni College of Arts and Science, Veerapandi, Theni-625534,
Tamil Nadu, India, 2Chemistry Research Centre, Mohamed Sathak Engineering College,
Kilakarai, Ramanathapuram-623806, Tamil Nadu, India and 3PG and Research Centre of
Chemistry, Jayaraj Annapackium College for Women, Periyakulam, Theni-62560,
Tamil Nadu, India
(Received 18 May, revised 2 November, accepted 16 November 2018)
Abstract: Novel series of Co(II), Ni(II) and Cu(II) transition metal complexes were
synthesized from the Schiff base ligands HL1–HL4 derived from 2-amino-6-
nitrobenzothiazole with various aromatic aldehydes, i.e., 4-methylbenzaldehyde, 4-
ethylbenzaldehyde, 2-hydroxybenzaldehyde and 4-hydroxybenzaldehyde,
respectively. The ligands HL1–HL4 and their metal (II) complexes were
characterized by atomic absorption spectroscopy (AAS), magnetic susceptibility
and molar conductance measurements, and UV–Vis, FT-IR and NMR
spectroscopic techniques. The spectroscopic studies revealed that the complexes of
HL1–HL3 coordinated in an octahedral environment and L4 in square
planar/tetrahedral geometry. The ligands HL1–HL4 and their metal(II) complexes
were screened for their antimicrobial activities against Staphylococcus aureus,
Escherichia coli, Pseudomonas aeruginosa and Candida albicans. The results
suggest that the complexes of HL4 possess greater inhibition activity towards C.
albicans. The nonlinear optics (NLO) activities of ligands HL1–HL4 were
determined. The obtained results showed that ligands HL1 and HL2 have greater
second harmonic generation (SHG) efficiency than HL3and HL4.
Keywords: aldehydes; metal(II) complexes; spectroscopic; AAS; biological
activity.
INTRODUCTION
In the last five decades, Schiff bases have emerged as the most preferred
compounds in the field of coordination chemistry and medicinal chemistry. The
azomethine group of Schiff bases makes it a potential donor for the formation of
complexes. Besides the chelating ability of Schiff bases of heterocyclic com-
*Corresponding author E-mail: kalacharle@gmail.com
https://doi.org/10.2298/JSC180521101K
268 KANAGAVALLI et al.
pounds containing 5- and 6-membered rings, they also find potential applications
in the field of therapeutics.1 Benzothiazole is a privileged bicyclic ring system
with significant biological properties, such as antimicrobial2–5 and anticancer.6
Transition metal complexes of Schiff bases of 2-amino-6-nitrobenzothiazole
enabled a study of the different ligation behaviors of Schiff bases. In this respect,
a structure activity relationship may also be studied. In recent years, organic mat-
erials have been studied for their nonlinear optical (NLO) properties, which are
of use in optical communications. A large number of organic compounds have
been tested for their NLO property in order to design effective communication
materials.7 In this context, the synthesis of the Schiff bases of 2-amino 6-nitro-
benzothiazole with various aromatic aldehydes and also of the corresponding
Co(II), Ni(II) and Cu(II) metal complexes are reported. The antimicrobial activity
and NLO property of the synthesized compounds are compared.
EXPERIMENTAL
All the chemicals used in the present work, viz. 2-amino-6-nitrobenzothiazole, 4-methyl-
benzaldehyde, 4-ethylbenzaldehyde, 4-hydroxybenzaldehyde, 2-hydroxybenzaldehyde, and
cobalt(II), nickel(II) and copper(II) chlorides were of analytical reagent grade. Commercial
solvents were distilled and then used for the preparation of the ligands and metal(II) com-
plexes. Elemental analyses and ESI-MS were performed at SAIF, CSIR-CDRI-Lucknow,
India. Molar conductivities in DMSO (10-3 mol dm-3) were measured at room temperature on
an ELICO CM-180 digital conductivity meter. Magnetic susceptibility measurements of the
complexes were realized on a Gouy balance using copper sulfate pentahydrate as the calibrant.
The IR spectra were recorded on a Shimadzu FT-IR IR Affinity-1 spectrophotometer in the
4000–400 cm-1 range using KBr pellets. The NMR spectra were recorded on a Bruker DRX –
300 MHz NMR spectrometer in DMSO-d6 and CDCl3 as solvents with tetramethylsilane
(TMS) as the internal reference. The absorption spectra were recorded using a Shimadzu UV-
-1800 spectrophotometer between 200–1100 nm by using a suitable solvent. The SHG (sec-
ond harmonic generation) conversion efficiency of the ligands was determined by a modified
version of powder technique in IISC, Bangalore, India.
Synthesis of ligands HL1–HL4
An ethanolic solution (30 mL) of 2-amino-6-nitrobenzothiazole (0.050 mol) was mixed
with ethanolic solution (20 mL) of aldehyde (0.050 mol; 4-methylbenzaldehyde, 4-ethylben-
zaldehyde, 4-hydroxybenzaldehyde and 2-hydroxybenzaldehyde) and the mixture was stirred.
Completion of the reaction was monitored by TLC. The precipitated yellow colored Schiff
bases were filtered, washed and dried. The scheme of the synthesis is shown in Fig. 1.
Synthesis of metal(II) complexes
All the complexes were prepared from hydrated metal salts. To a solution of 20 mmol of
Schiff bases (HL1–HL4) in 25 mL ethanol was added to 10 mmol of MCl2·nH2O (M = Co(II),
Ni(II) or Cu(II); n = 6, 6 and 2, respectively). The solution was stirred for 2 h and the resulting
solid product was filtered, washed with ethanol and dried under vacuum.
Estimation of percentage of metal
The percentage of metal in the complexes was estimated by atomic absorption spectro-
scopy at the BSR Laboratory, Jayaraj Annapackiam College for Women, India. A complex (5
METAL(II) COMPLEXES OF SCHIFF-BASE LIGANDS OF 2-AMINO-6-NITROBENZOTHIAZOLE 269
mg) was dissolved in 2 mL of DMSO and the solution is made up to 50 mL with double
distilled (DD) water. Standard solutions (1000, 100, 10 and 1 ppm, respectively) of metal salts
of cobalt, nickel and copper were prepared in DD water. Different metal filters were used for
running the analysis for estimation. Comparing with the amount of metal ion present in the
standard solutions, the amount of metal ion in the metal complexes was estimated graphically.
Fig. 1. Scheme of the synthesis of ligands HL1–HL4.
Antimicrobial activity screening
Antimicrobial activity of the compounds was tested in vitro by the well diffusion
method8 against the bacteria Staphylococcus aureus, Escherichia coli and Pseudomonas aeru-
ginosa using agar nutrient as the medium. Antifungal activity was evaluated against Candida
albicans cultured on potato dextrose agar as medium. All the mentioned bacterial strains were
incubated in nutrient broth (NB) at 37 °C for 24 h and fungal isolate was incubated in PDA
broth at 28 °C for 2 to 3 days. Wells each of 5 mm in diameter were made in Muller–Hinton
agar using a cork borer. The test solution was prepared at 10-3 mol L-1 concentration in
DMSO and then 100 µL of the solution was transferred into each well. The plates were incub-
ated for 24 h at 37 °C and examined for a clear inhibition zone around the well. Standard
drugs ampicillin and ketoconazole were used for antibacterial and antifungal testing, respect-
ively.
NLO properties of ligands HL1–HL4
In a nonlinear process, the oscillation of electrons becomes inharmonic and the re-emit-
ted light may differ in frequency and amplitude from the incident light. Inorganic materials
have dominated the field of NLO, for example, lithium niobate (LiNbO3) has been used for
electro-optic modulation.9 In organic materials, electrons are more accessible and NLO-
-effects arise from the interaction between light and electrons within individual molecular
units. Especially, organic structures with large delocalized π-systems have proven to be use-
ful. The reason for this is that π-electrons are more easily affected by an external optical field
as they are relatively loosely bound to the nucleus, and that the delocalized orbitals may
extend over the entire molecule enabling large and fast polarization.10,11 In the present work,
the second harmonic generation (SHG) efficiency of the ligands was determined by a modi-
fied version of the powder technique developed by Kurtz and Perry.12 The efficiency of the
sample was compared with microcrystalline powder of potassium dihydrogen phosphate
(KDP) and urea. The input energy used in this particular setup was 2.2 mJ per pulse.
270 KANAGAVALLI et al.
RESULTS AND DISCUSSION
The Schiff bases HL1–HL4 were obtained as low melting solids and stored in
vacuum desiccators. The ligands form stable complexes in ethanol medium. The
percentage of metal in the complexes was estimated by atomic absorption spec-
troscopy technique. The analytical data of the HL1 to HL4 and their metal(II) com-
plexes together with their physical properties are given in the Table I. All the lig-
ands coordinate in a bidentate fashion. The metal(II) complexes are partially sol-
uble in ethanol, chloroform and acetonitrile but soluble in polar solvents, such as
DMF and DMSO. The low values of conductance in DMSO indicate that the com-
plexes are non-electrolytes.13 The estimated percentage data of metal ion (II) in the
complexes were in good agreement with the calculated data for a 1:2 (M:L) ratio.
TABLE I Physical characterization and molar conductance of HL1–HL4 and their metal(II)
complexes
Compound FW / g mol-1 Calculated (observed) metal content, % Color ΛM / S cm
2 mol-1
HL1 297 – Yellow –
[Co(HL1)2Cl2] 723.8 8.14 (7.67) Light green 07
[Ni(HL1)2Cl2] 723.6 8.11 (7.62) Dark green 06
[Cu(HL1)2Cl2] 728.4 8.72 (8.06) Brown 07
HL2 311 – Yellow –
[Co(HL2)2Cl2] 751.8 7.83 (7.51) Green 04
[Ni(HL2)2Cl2] 751.6 7.80 (7.38) Green 05
[Cu(HL2)2Cl2] 756.4 8.40 (7.92) Brown 05
HL3 299 – Yellow –
[Co(HL3)2Cl2] 727.8 8.09 (7.81) Green 09
[Ni(HL3)2Cl2] 727.6 8.06 (7.58) Dark green 06
[Cu(HL3)2Cl2] 732.4 8.67 (8.12) Brown 10
HL4 299 – Yellow –
[Co(HL4)2] 655.5 8.97 (8.44) Light green 07
[Ni(HL4)2] 656.6 8.93 (8.42) Green 05
[Cu(HL4)2] 661.5 9.60 (9.11) Brown 07
IR spectra
In the IR spectrum of the free ligands (HL1–HL4) the frequencies at 1653–
–1649 cm–1 are assigned to the azomethine group (ν(CH=N)). The bands at
1523–517 cm–1 are attributed to the stretching vibration of the C=N group of the
thiazole ring (ν(C=N)). In the spectra of the metal(II) complexes of HL1–HL3,
the frequencies at 1653–1649 cm–1 and 1523–1517 cm–1 are shifted to lower
values (1651–1504 cm–1 and 1517–1493 cm–1) confirming the coordination of
the azomethine nitrogen and ring nitrogen14 of the benzothiazole group, respect-
ively, to the metal ion. In the spectra of metal(II) complexes of HL1–HL4, the
frequencies at 653–516 cm–1 are assigned to the M–N stretching mode.15–17 The
METAL(II) COMPLEXES OF SCHIFF-BASE LIGANDS OF 2-AMINO-6-NITROBENZOTHIAZOLE 271
spectrum of the ligand HL4 shows a band at 3454 cm–1 due to phenolic OH
group. The absence of this band in the spectrum of metal(II) complexes evid-
ences the coordination of deprotonated phenolic group to the metal(II) ion. In the
spectra of the metal(II) complexes of HL4, the stretching frequencies at 712–742
cm–1 are assigned to M–O vibrations.18
NMR spectra
The 1H-NMR and 13C-NMR data for the Schiff base ligands HL1–HL4 are
given in the Supplementary material to this paper.
Electronic absorption spectra
The UV–Vis spectra of the complexes were recorded in DMSO solution. The
copper(II) complexes of HL1–HL3 exhibit a d–d band in the region 10000–9267
cm–1. This band may be assigned to a 2B1g→2A1g transition, characteristic for a
distorted octahedral structure.19 In addition, the complexes of Co(II) and Ni(II)
exhibited two bands at 14684 and 16977 cm–1 and at 9354 and 10405 cm–1,
assigned to 4T1g(F)→4A2g(F), 4T1g(F)→4T2g(F) and 3A2g(F)→3T2g(F),
3A2g(F)→3T1g(F) transitions, respectively, suggesting octahedral coordination.
The copper(II) complex of HL4 shows a band at 12650 cm–1, assignable to a
2B1g→2A1g transition, characteristic for a distorted square–planar geometry.20 The
electronic spectrum of cobalt(II) complex of HL4 shows band at 15,880 cm–1,
which may be tentatively assigned to a 4A2(F)→4T1(P) transition for tetrahedral
geometry.21 The nickel(II) complex exhibits an absorption band at 13897 cm−1 due
to a 3T1(F)→3T1(P) transition, corresponding to tetrahedral geometry.
Magnetic moments of metal(II) complexes
Magnetic susceptibility measurements gave sufficient data to characterize
the structure of the metal complexes. Magnetic moment measurements of com-
pounds were performed at 25 °C. The magnetic moment values of the copper(II)
complex of HL4 was 1.75 µB, suggesting a square planar environment.22 The
tetrahedral structure of the nickel(II) complex of HL4 was evidenced by the mag-
netic moment value 2.81 µB. The magnetic moment value of cobalt(II) complex
of HL4 was 4.35 µB, suggesting a tetrahedral structure. The high spin nature and
the octahedral structure of cobalt(II) complexes of HL1–HL3 was further evid-
enced by the magnetic moment values of 4.79–5.40 µB. The magnetic moment
values of the copper(II) complexes of HL1–HL3 were in the range 1.81–2.08 µB,
indicating octahedral coordination. That the magnetic moment values were
higher than the spin only value (1.73 µB) might be due to an orbital contribution.
The octahedral structure of the nickel(II) complexes of HL1–HL3 was further
supported by the magnetic moment values 3.05–3.10 µB.22 Based on the above
discussion, the proposed structures of the complexes are shown in Fig. 2.
272 KANAGAVALLI et al.
X = CH3, C2H5, OH
M = Co(II), Ni(II) and Cu(II)
HL1 to HL3
M = Co(II), Ni(II) and Cu(II)
HL4
M
Cl
N N
Cl
NN
S
S
X
X
O2N
NO2
M
ON
NO
S
N
NO
2
NS
O2N
Fig. 2. Proposed geometry of the complexes.
Antimicrobial screening
The ligands and the complexes exhibited antifungal activity. From the zone
of inhibition, it was shown that some of the ligands and complexes have very low
inhibition activity towards Escherichia coli, Staphylococcus aureus, Pseudomo-
nas aeruginosa and Candida albicans. Some of the metal complexes were found
to be more potent than the ligands against bacterial and fungal strains. The dif-
ferent substituents in the Schiff bases had very low effects on the antimicrobial
activity. The metal complexes of HL2 exhibited no antifungal activity. The data
showing the zone of inhibition are given in the Table II. It is observed that, in a
TABLE II. Antimicrobial activity data of HL1–HL4 and their metal(II) complexes (zone of
inhibition in mm); R = resistant
Compound E. coli P. aeruginosa S. aureus C. albicans
HL1 4 5 3 10
[Co(HL1)2Cl2] R R R 11
[Ni(HL1)2Cl2] R R 12 R
[Cu(HL1)2Cl2] R 10 12 12
HL2 R R R R
[Co(HL2)2Cl2] R 10 R R
[Ni(HL2)2Cl2] R R R R
[Cu(HL2)2Cl2] R R R 10
HL3 R R 12 12
[Co(HL3)2Cl2] 10 12 R 11
[Ni(HL3)2Cl2] 8 R R 14
[Cu(HL3)2Cl2] R 12 10 14
HL4 R R 12 12
[Co(HL4)2] 10 12 R 14
[Ni(HL4)2] 8 R R 14
[Cu(HL4)2] R 12 14 14
METAL(II) COMPLEXES OF SCHIFF-BASE LIGANDS OF 2-AMINO-6-NITROBENZOTHIAZOLE 273
complex, the positive charge of the metal is partially shared with the donor atoms
present in the ligand and there may be π-electron delocalization over all the
chelating system.23,24 This increases the lipophilic character of the metal chelate
and favors its permeation through the lipoid layer of the bacterial membranes. So
the metal complex could become more active than the free ligand. Therefore, the
metal complexes showed greater antifungal activities than the uncoordinated lig-
and and free metal ion.
The bacterial strains are resistant towards the alkyl substituted ligands HL1
and HL2 and their metal complexes. The activity may be related to the length of
carbon chain25 present and they do not show an appreciable antifungal activity.
The hydroxyl-substituted ligands HL3 and HL4 showed a moderate antibacterial
and antifungal activity. From SAR studies, it is known that electron withdrawing
groups increase the antibacterial activity and this supports the resistant nature of
all the ligands and complexes towards most of the antibacterial strains.26 Although
the ligand contains the nitro group in the aromatic ring that is electron withdraw-
ing group, the antimicrobial activity was suppressed due to electron releasing
groups, such as alkyl and hydroxyl groups. The solubility of the compound, type
of the strain and the coordinating nature of the Schiff base determine the inhi-
bition activity. The hydrogen bonding ability27 of the azomethine group with the
microbial strain may improve the antimicrobial activity of the synthesized com-
pounds. In this regard, the complexes of HL3 and HL4 with a hydroxyl group
showed better inhibition compared to the metal complexes of HL1 and HL2.
Some of the complexes were inactive against E. coli, which may be due to
the bulkiness of the complexes.2
NLO activity
The synthesized ligands possess NLO properties. The methyl-substituted lig-
ands (HL1 and HL2) show greater SHG efficiency than the hydroxyl-substituted
ligands. The more pronounced electron donating nature of alkyl groups makes
ligands more polarized and show enhanced NLO activity.28 The ligand HL3 is
more NLO active than HL4, due to the para position of the hydroxyl group. The
SHG efficiency was found to be lower when compared with urea and KDP.29–31
The activity data is given in Table III.
TABLE III. NLO properties of the ligands
Ligand
SHG efficiency, %, with respect to
KDP Urea
HL1 15 8
HL2 20 10
HL3 14 6
HL4 13 5
274 KANAGAVALLI et al.
CONCLUSIONS
In this work, transition metal(II) complexes of Schiff bases of 2-amino-6-nit-
robenzothiazole were synthesized and characterized. The ligands and their metal
complexes were studied by various physical and chemical techniques, i.e., metal
estimation by AAS, UV–Vis, 1H-NMR and IR. All the synthesized ligands and
complexes were screened for their antimicrobial activity. All the metal (Co(II),
Ni(II) and Cu(II)) complexes of the synthesized ligands HL1–HL3 show octa-
hedral geometry. Distorted square planar geometry is proposed for the copper
complex of HL4. The other complexes of HL4 coordinate in a tetrahedral fash-
ion. Ligands and complexes possess lower antimicrobial activity than the stan-
dard drugs. The synthesized compounds possess very small antibacterial activity
and appreciable antifungal activity. All the ligands were found to possess NLO
activity. The alkyl-substituted Schiff bases (HL1 and HL2) have greater SHG
efficiency than the hydroxyl substituted Schiff bases HL3 and HL4.
SUPPLEMENTARY MATERIAL
Characterization data of the ligands and complexes are available electronically at the
pages of journal website: http://www.shd.org.rs/JSCS/ or from the corresponding author on
request.
Acknowledgements. The authors express their sincere thanks to the College Management,
Principal and BSR Laboratory, Department of Chemistry, Jayaraj Annapackiam College for
Women, Periyakulam, India, for providing the necessary research facilities.
И З В О Д
СПЕКТРОСКОПСКА, NLO И АНТИМИКРОБНА ИСПИТИВАЊА Co(II), Ni(II) И Cu(II)
КОМПЛЕКСА СА ШИФОВИМ БАЗАМА 2-АМИНО-6-НИТРОБЕНЗОТИАЗОЛА
КАО ЛИГАНДИМА
CHINNARAJ KANAGAVALLI1, MURUGESAN SANKARGANESH2, JEYARAJ DHAVEETHU RAJA2
и MANIVANNAN KALANITHI3
1
Department of Chemistry, Theni College of Arts and Science, Veerapandi, Theni-625534, Tamil Nadu, India,
2
Chemistry Research Centre, Mohamed Sathak Engineering College, Kilakarai, Ramanathapuram-623806,
Tamil Nadu, India и
3
PG and Research Centre of Chemistry, Jayaraj Annapackium College for Women,
Periyakulam, Theni-62560, Tamil Nadu, India
Синтетисана је нова серија комплекса прелазних метала, Co(II), Ni(II) и Cu(II), са
Шифовим базама као лигандима (HL1–HL4) који су добијени из 2-амино-6-нитробензо-
тиазола и различитих ароматичних алдехида, као што су 4-метилбензалдехид, 4-етил-
бензалдехид, 2-хидроксибензалдехид и 4-хидроксибензалдехид. Лиганди (HL1–HL4) и
њихови комплекси су окарактерисани помоћу AAS, мерења магнетне и моларне
проводљивости, као и UV–Vis, FT-IR и NMR спектроскопских техника. На основу
спектроскопских испитивања нађено је да лиганди HL1–HL4 граде комплексе
октаедарске геометрије, док у случају HL4 лиганда настају комплекси који имају и
квадратно-планарну, односно тетраедарску геомтерију. Лиганди HL1–HL4 и
одговарајући метал(II)-комплекси су испитивани на антимикробну активност према
микроорганизмима Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa и
Candida albicans. Добијени резултати ових испитивања су показали да комплекси са
METAL(II) COMPLEXES OF SCHIFF-BASE LIGANDS OF 2-AMINO-6-NITROBENZOTHIAZOLE 275
лигандом HL4 показују већу инхибиторску активност према C. albicans. Одређена је NLO
активност лиганада HL1–HL4. Добијени резултати су 11 показали да је у случају
лиганада HL1 и HL2 SHG ефикасност већа у односу на лиганде HL3 и HL4.
(Примљено 18. маја, ревидирано 2. новембра, прихваћено 16. новембра 2018)
REFERENCES
1. A. Achson, An introduction to the chemistry of heterocyclic compounds, 3rd ed., Wiley
Interscience, New Delhi, 2009
2. E. Yousif, A. Majeed, K. Al-Sammarrae, N. Salih, J. Salimon, B. Abdullah, Arab. J.
Chem. 10 (2017), S1639
3. S. E. Etaiw, D. A. EI-Aziz, E. A. EI-Zaher, E. Ali, Spectrochim. Acta, A 79 (2011) 1331
4. H. C. Sakarya, K. Gorgun, C. Ogretir, Arab. J. Chem. 9 (2016) S1314
5. M. A. Neelakantan, M. Esakkiammal, S. S. Mariappan, J. Dharmaraja, T. Jeyakumar,
Indian J. Pharm. Sci. 72 (2010) 216
6. P. Chandersharma, A. Sinhmar, A. Sharma, H. Rajak, D. P. Pathak , J. Enzyme Inhib.
Med. Chem. 28 (2013) 240
7. J. P. Costes, J. F. Lamere, C. Lepetti, P. G. Lacroix, F. Dahan, Inorg. Chem. 44 (2005) 1973
8. N. Raman, L. Mitu, A. Sakthivel, M. S. S. Pandia, J. Iran. Chem. Soc. 6 (2009) 738
9. H. S. Nalwa, T. Watanabe, S. Miyata, in Nonlinear Optics of Organic Molecules and
Polymers, H. S. Nalwa, S. Miyata, Eds., CRC Press, Boca Raton, FL, 1997, p. 89
10. H. S. Nalwa, in Nonlinear Optics of Organic Molecules and Polymers, H. S. Nalwa, S.
Miyata, Eds., CRC Press, Boca Raton, FL, 1997, p. 611
11. P. N. Prasad, D. J. Williams, Introduction to Nonlinear Optical Effects in Molecules and
Polymers. Wiley, New York, 1991
12. S. K. Kurtz, T. T. Perry, J. Appl. Phys. 39 (1968) 3798
13. W. G. Geary, Coord. Chem. Rev. 7 (1971) 81
14. R. C. Maurya, R. Verma, H. Singh, Synth. React. Inorg. Met. - Org. Chem. 33 (2003) 1063
15. K. Singh, M. S. Barwa, P. Tyagi, Eur. J. Med. Chem. 41 (2006) 147
16. G. G. Mohamed, M. A. Zayed, S. M. Abdallah. J. Mol. Struct. 62 (2010) 979
17. L. Xu, M. Hong, Y. Yang, J. Cui, C. Li, J. Coord. Chem. 69 (2016) 2598
18. S. Budagumpi, G. S. Kurdekar, V. K. Revankar, J. Coord. Chem. 63 (2010) 1430
19. M. Gulcan, Y. Karatas, S. Isik, G. Ozturk, E. Akbas, E. Sahin, J. Fluoresc. 24 (2014) 1679
20. C. J. Dhanaraja, M. S. Nair, J. Coord. Chem. 62 (2009) 4018
21. M. Kalanithi, M. Rajarajan, P. Tharmaraj, C. D. Sheela, J. Coord. Chem. 87 (2012) 155
22. A. B. P. Lever, Inorganic Electronic Spectroscopy, 2nd ed., Elsevier, New York, 1968
23. P. S. Patil, S. M. Dharmaprakash, K. Ramakrishna, H.-K. Fun, R. S. S. Kumar, D. N.
Rao. J. Cryst. Growth 303 (2007) 520
24. A. P. Zambre, V. M. Kulkarni, S. Padhye, S. K. Sandur, B. B. Aggarwal. Bioorg. Med.
Chem. 14 (2006) 7196
25. R. Sharma, L. Yadav, J. Lal, P. K. Jaiswal, M. Mathur, A. K. Swami, S. Chaudhary,
Bioorg. Med. Chem. Lett. 27 (2017) 4393
26. S. Alyar, N. Karacan, J. Enzyme Inhib. Med. Chem. 24 (2009) 986
27. F. N. Ejiah, T. M. Fasina, O. B. Familoni, F. T. Ogunsola, Adv. Biol. Chem. 3 (2013) 475
28. L. H. Abdel-Rahman, A. M. Abu-Die, H. Moustafa, A. Hassan Abdel-Mawgoud, Arab. J.
Chem. (2017) S1878
29. M. N Uddin, D. A Chowdhury, K. Hossain, J. Chin. Chem. Soc. 59 (2012) 1520
30. M. N. Uddin, D. A Chowdhury, M. T. Islam, F. Hoque, Orbital: Electron J. Chem. 4 (2012) 273
31. N. Chattopadhyay, A. Mallick, S. Sengupta, J. Photochem. Photobiol. A 177 (2006) 55.
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/HRV (Za stvaranje Adobe PDF dokumenata najpogodnijih za visokokvalitetni ispis prije tiskanja koristite ove postavke. Stvoreni PDF dokumenti mogu se otvoriti Acrobat i Adobe Reader 5.0 i kasnijim verzijama.)
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/NLD (Gebruik deze instellingen om Adobe PDF-documenten te maken die zijn geoptimaliseerd voor prepress-afdrukken van hoge kwaliteit. De gemaakte PDF-documenten kunnen worden geopend met Acrobat en Adobe Reader 5.0 en hoger.)
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/ENU (Use these settings to create Adobe PDF documents best suited for high-quality prepress printing. Created PDF documents can be opened with Acrobat and Adobe Reader 5.0 and later.)
>>
/Namespace [
(Adobe)
(Common)
(1.0)
]
/OtherNamespaces [
<<
/AsReaderSpreads false
/CropImagesToFrames true
/ErrorControl /WarnAndContinue
/FlattenerIgnoreSpreadOverrides false
/IncludeGuidesGrids false
/IncludeNonPrinting false
/IncludeSlug false
/Namespace [
(Adobe)
(InDesign)
(4.0)
]
/OmitPlacedBitmaps false
/OmitPlacedEPS false
/OmitPlacedPDF false
/SimulateOverprint /Legacy
>>
<<
/AddBleedMarks false
/AddColorBars false
/AddCropMarks false
/AddPageInfo false
/AddRegMarks false
/ConvertColors /ConvertToCMYK
/DestinationProfileName ()
/DestinationProfileSelector /DocumentCMYK
/Downsample16BitImages true
/FlattenerPreset <<
/PresetSelector /MediumResolution
>>
/FormElements false
/GenerateStructure false
/IncludeBookmarks false
/IncludeHyperlinks false
/IncludeInteractive false
/IncludeLayers false
/IncludeProfiles false
/MultimediaHandling /UseObjectSettings
/Namespace [
(Adobe)
(CreativeSuite)
(2.0)
]
/PDFXOutputIntentProfileSelector /DocumentCMYK
/PreserveEditing true
/UntaggedCMYKHandling /LeaveUntagged
/UntaggedRGBHandling /UseDocumentProfile
/UseDocumentBleed false
>>
]
>> setdistillerparams
<<
/HWResolution [2400 2400]
/PageSize [612.000 792.000]
>> setpagedevice