`

ESSENC
CE - Interna
ational Jourrnal for Envvironmentaal Rehabilitaation and Conservation
n
Volume VI: No. 2 2015 [28
[ – 34] [ISS
SN 0975 - 62722]
[ww
ww.essence-jouurnal.com]

Cyclic vooltammetricc and antim

microbial stu
udies of Co((II) and Fe(IIII) dibenzootetrazaanulene [12]
complexxes

Tevatia, Prashant; Kumar,

K Anuj; Sweety and Singh, Randhir

3 2015  Accepted: Novvember 28, 20015  Onlinee: December 31,

Received: September 30, 3 2015

Abstractt
In thhis comm munication, synthessis, actiivity against C. albicanss. The antim
microbial
characterrization an nd electrocchemistry of actiivity was coompared witth a standarrd drug,
Dimethyl-dibenzo[b,,h]tetraphenyyl - 2, 3, 8, 9- Genntamycin.
tetraazacyclododeca - 1, 3, 7,, 9 - tetraeene Keyywords: Macrocyclicc compleexes |
macrocycclic complexes of Fe(IIII) and Co((II) elecctronic specttral studies | cyclic voltaammetry
complexees have been n carried ouut. The specttral | anttibacterial acctivity.
studies are in good agreem ment with the t Intrroduction
octahedraal geometry y of thesee macrocycclic In Recent advances inn chemistryy have
complexees. Cyclic voltammetric
v c studies were provvided the abbility to dessign and syynthesise
carried out
o on Pt dissh (0.031 cm m2) electrodee in mimmics of natuural macrocyyclic systems and to
DMSO. Cyclic vo oltammetric studies haave preddict their properties. Chemistts have
shown onne electron riversible reedox processes surmmounted delicate
d moolecular sttructures
for thesee macrocycliic complexees on the baasis throough the deevelopment of novel synthetic
s
of their peak
p seperattion and peakk current rattio. metthods (Costees, 1987; Baldwin et al., a 1975
The hetterogeneous electron transfer rate r andd Reddy et al.,
a 2012). Thhere has beeen much
0
constant (K ) was also determ mined with thet inteerest in thet field of mixed--valence
help of Nicholson and Kochi’s method and a maccrocyclic compounds,, especiallly the
found inn the orderr K0Co(II) > K0Fe(III). The T appearance of thhe classificaation system devised
macrocycclic com
mplexes a
also show
wed by scientists and
a theoretical treatise on the
antimicroobial activities againstt E. coli, P. elecctronic confiiguration. Prrussian blue, a three
aeruginoosa, B. cereu us, S. aureus and antifunggal dim
mensional arrray of Fe (IIII) center bridged
For corresspondence: by [Fe(CN)6]4-- units, hass been useed as a
Departmennt of Chemistry
y, Gurukula Kaangri pigm ment in ink and dyes beecause of itss intense
Vishwaviddyalaya, Haridw
war, India
bluee colour whiich arises duue to metal-tto-metal
E-mail: prashant_tevatia@yahoo.co.in

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 Tevatia et al. /Vol. VI [2] 2015/28 – 34 

charge transfer (MMCT) transition (Malik et electronic and IR spectra of these macrocyclic
al., 1983; Ma et al., 2006 and Verani et al., complexes were recorded on Double Beam
2000) whereby an electron is transferred from Spectrophotometer (Shimadzu 2450
an Fe (II) to Fe(III) center. The MMCT spectrophotometer) in methanol and
transition is not possible in the oxidized Fe (II) Schimadzu-8400S double beam
- Fe (III) or reduced Fe (II) - Fe (I) states spectrophotometer by KBr DRS method
resulting in loss of the blue coloration making respectively. The electrochemical studies of
this compound brown and white respectively. these macrocyclic complexes were carried on
The significant roles played in living systems the Platinum electrode (0.031 cm2) using Auto
by metal ions depend on their confinement lab Metrohm 663 VA Stand Instrument. Tetra
within approximately planar tetradentate ethyl ammoniumperchlorate (TEAP) used as
totally enclosed macrocyclic systems which are supporting electrolytes. The pre-treatment of Pt
themselves, highly conjugated species. Much electrode was carried out before every
of the mystique associated with the binding of experiment.
molecular oxygen by naturally occurring heme, Preparation of the Macrocyclic complexes
has been removed by successful challenge to The macrocyclic complexes have been
this field (Lonibala et al., 2006; Soderberg,
synthesized according to the literature method
2008; Nunez et al., 2010 and Chen et al.,
using 2 moles of 3,4  -  diaminotoluene (0.244
2012). The ability of synthetic macrocyclic
complexes to mimic the properties of naturally g), 2 moles of benzyl (0.420 g) and 1 mole of
occurring macrocyclic systems is now well iron (III) chloride (0.162 g) (Tevatia et al.,
recognized. Keeping all views, in this 2014 and Singh et al., 2002).
communication, synthesis, characterization and Ph Ph
Cl

electrochemistry of Dimethyl-dibenzo [b,h] Me NH2 O Ph Me N N Me

MCl2.xH2O
tetraphenyl-2,3,8,9-tetraazacyclo dodeca -1, 3, 2 2
M = Fe(III) and Co(II)
M

7, 9 - tetraene macrocyclic complexes of

NH2 O Ph N N
Cl

Fe(III) and Co(II) complexes have been carried Ph Ph

out. Fig. 1: The synthesis scheme of these tetra-

Materials and methods azamacrocyclic complexes
The elemental (C, H, N) and mass spectral Macrocyclic >C=N C=C str.
C―H
M―N
str.
complexes str. (Aromatic) str.
studies of these macrocycles were carried out (Methyl)
[FeC42H32N4Cl2]Cl 1645 1235, 2935 495
at Central Instrumental Laboratory (CIL) 1125, 780
Panjab University, Chandigarh (Eager [CoC42H32N4Cl2] 1630 1355, 2985 515
1230,865
Xperience and TOF MS ES+6018e3). The Table 1: Physical properties of tetra-
azamacrocyclic complexes of
molar conductance of these macrocycles Fe(III) and Co(II).
complexes was recorded on Auto ranging
Conductivity/TDS Meter (TCM 15+). The
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 Tevatia et al. /Vol. VI [2] 2015/28 – 34 

Results and discussion may be assigned for the vibrations of aromatic

IR spectra rings and C-H stretching of CH3 group
The IR spectra of these macrocyclic complexes respectively (Ma et al., 2006; Chaudhary et al.,
2002 and Prasad et al., 2007). The other
showed a strong band near 1620-1650 cm–1
absorption characteristics appeared in the
due to C=N group. The other characteristic
region 520-490 cm-1 may be assigned for ν(M-
bands for these macrocyclic complexes
N) vibrations. The IR data for these complexes
observed in the region 1230-1370 cm-1, 1050-
1260 cm-1, 690-890 cm-1 and 2930-3000 cm-1 is given in table 2.
Complexes Colour Molar M.P. Mol. Wt. C H N
conductance (0C) (found) (found) (found)
(ohm-1cm- (%) (%) (%)
2
mol-1)
Light 67.65 4.24 7.42
[FeC42H32N4Cl2]Cl 65 230 755
yellow (65.21) (3.39) (7.16)
69.81 4.43 7.75
[CoC42H32N4Cl2] Brown 30 220 722
(68.73) (4.73) (8.16)
Table 2: IR data of tetraazamacrocyclic complexes of Fe(III) and Co(II)

Electronic spectral studies complexes using Orgel energy and Tanabe-

The electronic studies of these macrocyclic Sugano diagrams using ν3/ν1 and ν2/ν1 ratio.
complexes were carried out in methanol. The The nephelauxetic parameter (β) was
observed data for these macrocyclic complexes calculated using the relation. β = B' / B where
are given in the following table 3. On the basis the values of B for free metal ions are taken as
of results, the octahedral geometry has been Fe (III) = 1153 cm-1 and Co(II) = 971 cm-1
assigned for both tetraazamacrocyclic (Chandra and Kumar, 2013). The calculated
complexes. The ligand field parameters studies values of nephelauxetic parameter (β) of these
for these macrocyclic complexes (Dq, B' and β) macrocyclic complexes are given in table 3.
have been calculated for these macrocyclic
Electronic Spectra Ligand Field Parameter
Stereoche
Complexes Energy Dq
Transition mistry ν 3/ ν 1 B' (cm-1) β
(cm-1) (cm-1)
5
[C42H32N4FeCl2] 27983 T2g(D) →5Eg(D)
Octahedral 1756 1.3 1035 0.76
Cl
4 4
[C42H32N4CoCl2] 15635 T1g(F) → T2g(F)
4
14575 T1g(F) → 4A2g Octahedral 975 1.5 956 0.81
4
23356 T1g(F) → 4T1g(P)
Table 3: Electronic spectral data of tetra-azamacrocyclic
complexes of Fe(III) and Co(II).
Mass Spectra m/z 684 and 669 which may be assigned to the
The mass spectrum of Fe(III) macrocyclic cleavage of CH3 and Cl units respectively.
complex [FeC42H32N4Cl2]Cl showed molecular Co(II) macrocyclic complex [CoC42H32N4Cl2]
ion peak (M+1) at m/z 756 and other peaks at showed molecular ion peak (M+1) at m/z 723
and other peaks at m/z 651 and 636 assignable
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 Tevatia et al. /Vol. VI [2] 2015/28 – 34 

to the cleavage of CH3 and Cl units (Chandra
et al., 2013).
Electrochemical studies
Cyclic voltammetry of these macrocyclic
complexes have been carried out in DMSO
containing 0.1M TEAP as supporting
electrolyte. Cyclic voltammograms of these
macrocyclic complexes are shown in fig. 2. In
this communication, the diffusion coefficient
(D0) and heterogeneous electron transfer rate
constant (K0) for these macrocyclic complexes
have been calculated with the help of
Nicholson and Kochi methodologies (Anuj et
al., 2015 and Nicholson and Shain, 1964). The
cyclic voltammogram (Fig. 2a) of Fe(III)
macrocyclic complex at 200 mVs-1 scan rate
exhibited two anodic peaks corresponding to
the cathodic peak and one anodic peak without
corresponding cathodic peak. The first redox
process of Fe (III) macrocyclic complex is a
reversible redox couple Fe+2/Fe+1 corresponds
to peak separation ∆E = -0.07 V and formal
potential E1/2 = -0.95 V while the second redox
process is a quasi-reversible with the
corresponding to peak separation ∆E = 0.15 V
and formal potential E1/2 = 0.65 V for the
couple, which is also supported by the peak
current ratio (ipa/ipc) that is close to unity. The
cyclic voltammogram (Fig. 2b) of [Co(II)L]
complex showed a reversible redox couple
L/L-1 corresponding to peak separation ∆E = -
0.13 V and formal potential E1/2 from -1.01 V
at 200 mV s-1 scan rate. The reversibility of
this couple is also supported by the ratio ipa/ipc
that is close to unity while the second redox
couple for Co+2/Co+3 is found at formal
potential +0.80 V with peak separation ∆E =
0.20 V. This redox process is the
quasirreversible as also indicated by the peak
current ratio ipa/ipc. The redox process,
Co+2/Co+1 of this macrocyclic complex is also
found the quasirreversible redox process,
supported by corresponding peak separation
∆E and the peak current ratio. Further, the
plots of ip against v1/2 were found to be linear,
indicating that the redox process was
controlled by diffusion, following the Randles-
Sevcik equation for reversible electrochemical
reactions.
i = -2.69 × 105 n3/2AD1/2cv1/2
Where n is the number of electrons transferred,
A is the area of the electrode, D is the diffusion
coefficient, c is the analyte concentration and v
is the scan rate.
The diffusion coefficient (D0) and
heterogeneous electron transfer rate constant
(K0), as calculated are in the order D0Co(II)
(2.11× 10-5 cm2/s) > D0Fe(III) (1.7 × 10-5 cm2/s)
and K0Co(II) (5.41 × 10-3 cm/s) > K0Fe(III) (3.41 ×
10-3 cm/s).
.
(a)
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measured after 48 h of incubation at 28ᵒC.

Antimicrobial activity of these macrocyclic
complexes were evaluated by measuring the
zone of growth inhibition against the test
organisms with zone reader (Hi Antibiotic
Zone Scale) (Mallie et al., 2005; Chohan et al.,
2004; Roy et al., 1999 and Tagg and Giben,
1971).
The tetraazamacrocyclic complex of Co(II)
showed maximum zone of inhibition against E.
coli (20 mm) followed by S. aureus (14 mm),
B. subtilis (15 mm) and P. aeruginosa (16
(b) mm). Fe(III) macrocyclic complex exhibit
Fig. 2: Cyclic voltammograms of (a) Fe(III) and (b) Co(II) maximum zone of inhibition against E. coli (18
macrocyclic complexes. mm) followed by B. subtilis (16 mm) and S.
Biological activity aureus (16 mm), P. aeruginosa (15 mm).
The antimicrobial activities of these Against fungal pathogen C. albicans,
macrocyclic complexes of Fe(III) and Co(II) macrocyclic complexes of Fe(III) were found
were studied by agar well diffusion method. most effective (18 mm) followed by the Co(II)
The microbial cultures for these macrocyclic macrocyclic complexes (17 mm) as showed in
complexes were adjusted to 0.5 McFarland fig. 3.
standards, which are visually comparable to a Complex Diameter of inhibition zone (mm)
microbial pathogen suspension of (100 mg/ml)
P. B. S. C.
8 E.
approximately 1.5 × 10 cfu/ ml. Now 25 ml of coli
aerug subtil aure albican
inosa is us s
agar media was poured into petri plates and [C42H32N4FeCl2]
18 15 16 16 18
was swabbed with 100 µl microbial inoculums Cl
[C42H32N4CoCl2] 20 16 15 14 17
of the test microorganisms and kept for 20 Gentamycin 24 24 24 24 20
minutes. A 6 mm well was cut at the centre of Table 4: Antimicrobial activity of the
synthesized macrocyclic complexes
the all agar plates and were filled with test
30

complexes (Asiri et al., 2011; Al-Bishri et al., 25

2011; Hunter et al., 2004 and Cushine et al., 20

15
2005). Solvent medium was used as a negative Fe(III)
10 Co(II)

control where as media with Gentamycin used 5

Gentamycin

as positive control. After 24 h of incubation at 0

37ᵒC each plate was observed for the

measurement of diameter at inhibition zone and
Fig. 3: Graphical presentation of antimicrobial activity of these
in case for fungus, inhibition zone was macrocyclic complexes against pathogens

32 
 Tevatia et al. /Vol. VI [2] 2015/28 – 34
Conclusions
In this communication, tetraazamacrocyclic
complexes of Fe(III) and Co(II) have been
synthesized by the template method using 2,4-
diaminotoluene and benzyl. The spectral
studies have confirmed the octahedral
geometry for these tetraazamacrocyclic
complexes. Cyclic voltammetric studies also
showed the interesting results for their unusual
oxidation state and also showed the
heterogeneous rate constant found in the order
K0Co(II) > K0Fe(III). These macrocyclic
complexes have shown good promise for
antimicrobial activity against both Gram +ve
and Gram –ve bacteria.
Acknowledgments
The authors are thankful to CSIR New Delhi
for financial support in the past projects and
support is also acknowledged for completion
the studies from SAIF Panjab University
Chandigarh.
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