Synthesis, structural investigations and biological studies on symmetrically substituted 3,3,3 ,3 -tetra-methoxyphenylimino phthalocyanine complexes

Article abstract of DOI:10.1134/S0036023608010117

The present paper describes the synthesis and characterization of novel metal (II) 3,3,3″,3-tetramethoxyphenylimino substituted phthalocyanines (M-MeOPhImPcs) of copper (II), cobalt (II), nickel (II) and zinc (II) by condensing the 3,3,3,3″-tetra amino phthalocyanines with anisaldehyde. The dark bluish green colored tetraimino substituted phthalocyanine derivatives were characterized by various physico-chemical techniques like elemental analysis, magnetic susceptibility, electronic, IR, powder X-ray diffraction and thermo gravimetric analysis (TGA) to check the structural integrity and purity. The variations of magnetic moment as a function of field strength indicated the presence of inter molecular co-operative interactions. The complexes were also evaluated for their antifungal and antibacterial activities.

Full text of DOI:10.1134/S0036023608010117

ISSN 0036-0236, Russian Journal of Inorganic Chemistry, 2008, Vol. 53, No. 1, pp. 68–77. © Pleiades Publishing, Ltd., 2008.
COORDINATION
COMPOUNDS
Synthesis, Structural Investigations and Biological Studies
on Symmetrically Substituted
3,3',3'',3'''-Tetra-methoxyphenylimino
Phthalocyanine Complexes1
M. H. Moinuddin khana, Fasiullaa, J. Keshavayyac, and K. R. Venugopala Reddyc
a Department of Chemistry, J. N. N. College of Engineering, Shimoga–577204, Karnataka, India
b Department of Studies in Chemistry, School of Chemical Sciences, Kuvempu University, Jnanasahyadri,
Shankaraghatta – 577 451, Shimoga District, Karnataka, India
c Department of Studies in Industrial Chemistry, School of Chemical Sciences, Kuvempu University,
Jnanasahyadri, Shankaraghatta – 577 451, Shimoga District, Karnataka, India
e-mail: moin_nallur yahoo.co.in; venurashmi30@rediffmail.com; jkeshavayya@rediffmail.com
Received October 10, 2006
Abstract—The present paper describes the synthesis and characterization of novel metal (II) 3,3',3'',3'''-tetra-
methoxyphenylimino substituted phthalocyanines (M-MeOPhImPcs) of copper (II), cobalt (II), nickel (II) and
zinc (II) by condensing the 3,3',3'',3'''-tetra amino phthalocyanines with anisaldehyde. The dark bluish green
colored tetraimino substituted phthalocyanine derivatives were characterized by various physico-chemical
techniques like elemental analysis, magnetic susceptibility, electronic, IR, powder X-ray diffraction and thermo
gravimetric analysis (TGA) to check the structural integrity and purity. The variations of magnetic moment as
a function of field strength indicated the presence of inter molecular co-operative interactions. The complexes
were also evaluated for their antifungal and antibacterial activities.
DOI: 10.1134/S0036023608010117
1
Phthalocyanines are planar, macrocyclic aromatic nophthalocyanines were documented [11] in the litera-
compounds, which are isoelectronic with porphyrin ture, no data are available on synthesis and structural
molecule consisting of 4 isoindole units linked together studies on metal (II) 3,3',3'',3'''-tetraimino phthalocya-
by nitrogen atoms. The aza-nitrogen and peripheral nines starting from the respective amino phthalocya-
fused benzene rings impart chemical and thermal sta- nine complexes.
bility to the phthalocyanine molecule. Various substi-
tuted metal phthalocyanines have been extensively used
in solar cells, fuel cells, electrochorism and photocho-
risim, optical memory and data storage devices, liquid
crystal color displays, as dyes and pigments, and in
photodynamic therapy of cancer [1–4]. In recent
decades, there has been renewed interest in the use of
metal phthalocyanine complexes in number of high
technological applications, including those based upon
the close structural relationships of the phthalocyanine
to porphyrin complexes. Mimicking the natural energy
cycle of chlorophyll, the oxygen binding capacity and
activation properties of the heme proteins has been a
key role in phthalocyanine research [4–6]. New appli-
cations include as photosensitizers in PDT and in anti-
scrapie treatments [7, 8], as power leads and as molec-
ular switches in nanotechnology [9], and as potential
industrial catalysts [10].
In the present paper we report the synthesis, charac-
terization and biological activities of 3,3',3'',3'''-tetra-
methoxyphenylimino phthalocyanine complexes of
cobalt (II), copper (II), nickel (II) and zinc (II). The pro-
cedure available from the literature [11–13] is suitably
modified and used for the synthesis of title complexes.
EXPERIMENTAL
3-nitrophthalic acid was synthesized by using
phthalic anhydride adopting the procedure reported
elsewhere [11]. All other chemicals were of analytical
grade and were used as such. Metal (II) 3,3',3'',3'''-tetra-
methoxyphenylimino phthalocyanines are prepared as
per the Scheme.
Preparation of Cobalt (II) 3,3',3'',3'''-tetra-
methoxyphenylimino phthalocyanine complex. The
procedure adopted for the synthesis of cobalt(II)
3,3',3'',3'''-tetra-nitro phthalocyanines (M-PcTN) was
reported elsewhere [12]. The nitro derivative of the
aforesaid complex was converted into amino derivative
quantitatively by reduction using sodium sulfide non-
Even though the information on synthesis and struc-
tural investigations of metal (II) 3,3',3'',3'''-tetraami-
1
This article was submitted by the authors in English.
68

SYNTHESIS, STRUCTURAL INVESTIGATIONS AND BIOLOGICAL STUDIES
69
ahydrate in aqueous medium [13]. The finely powdered powdered sample was dissolved in 6–10 parts of con-
cobalt(II) 3,3',3'',3'''-tetraamino phthalocyanine (M-PcTA)
(6.30 g 0.01 mole) was dissolved in DMSO and stirred
with stoichiometric quantity of anisaldehyde (5.4 mL,
0.01 mole). The above mixture was refluxed for 5 hours
in the presence of a catalytic quantity of concentrated
sulphuric acid and the contents were poured into ice
cold water. The settled bluish green colored condensed
imino phthalocyanine complex was washed with alco-
hol several times until it was free from anisaldehyde.
centrated sulphuric acid. The mixture was allowed to
stand for 1–2 h and then poured on to 45–50 parts of
crushed ice and stirred thoroughly. The pigment thus
obtained was filtered off and washed with hot water.
Finally, it was washed with distilled water and dried in
vacuum over phosphorous pentoxide.
Metal (II) 3,3',3'',3'''-tetra-methoxyphenylimino
phthalocyanines of Cu(II), Ni(II) and Zn(II) were pre-
pared by the above procedure using the respective
The pigment form of the above complex was
obtained by the acid pasting process, in which 1 part of metal amino phthalocyanines.
O2N
N
O
O2N
Metal Salt
N
N
N
CO(NH2)2
PhNO2
OH
O
M
N
N
NH4Cl
(NH4)6Mo7O24
180 5°C
N
H
NO2
NO OH
2
a
N
NO2
b
H
Reduction
OCH3
N
H2N
H3CO
N
N
H
N
N
N
N
H2N
N
N
N
N
M
N
N
M
Condensation
N
N
N
N
H
NH2
N
OCH3
N
N
NH2
c
H
d
OCH3
Scheme. Synthesis of metal(II) 3,3',3'',3'''-tetra-methoxyphenyliminophthalocyanines,
a) 3-nitrophthalic acid, b) M–PcTN, c) M–PcTA and d) M–MeOPhImPc.
Varian Cary 5000 with 1 cm width silica cell was Kochi, Kerala, India. Magnetic susceptibility studies
used for electronic absorption spectral studies. IR spec- were made at room temperature (28°C) using Gouy
tra were recorded using Nicolet MX-FT IR spectrome- magnetic balance consisting of NP–53 type electro-
ter. C, H and N elemental analyses were done by STIC, magnets with a DC power supply unit and a semi
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 53 No. 1 2008

70
MOINUDDIN KHAN et al.
microbalance. Pascal’s constants were used to calculate
the diamagnetic corrections. A Hg[Co(SCN)4] complex
was used as calibrant [14]. Philips analytical PW–1710
X-ray diffractrometer was used to study the diffraction
pattern of the complexes. The spectra were recorded
using CuKα at a voltage of 40 kV, a current of 20 mA, a
time constant of 4, a channel width of 7 mm, and a chart
speed of 10 mm/min. TGA studies were carried out by
using a Perkin Elmer, Diamond TG/DTA thermal ana-
lyzer at a heating rate of 10°/min both in the air and
nitrogen atmosphere.
RESULTS AND DISCUSSIONS
The procedure adopted for the synthesis of M-MeO-
PhImPcs yield pure complexes. The title complexes are
dark bluish green in color. These complexes give clear
solution in DMSO, DMF, pyridine and concentrated
sulfuric acid and are sparingly soluble in alcohol. The
results of elemental analysis for carbon, hydrogen, and
nitrogen and gravimetric methods for metals (Table 2)
are in good agreement with the calculated values and
are consistent with the proposed structure given below.
H
OCH3
N
H3CO
N
H
N
N
N
N
N
N
M
N
N
H
N
OCH3
N
H
OCH3
Suggested structure of symmetrically tetra substituted methoxyphenyliminophthalocyanine,
where M = Co, Cu, Ni and Zn.
Electronic Spectra
phthalocyanine molecule. A sharp and intense B-band
is observed in all the complexes in the range of 328–
339 nm. A weak L-band is observed for all metal-imino
phthalocyanines at 244–256 nm. A band observed for
all the complexes in the range of 211–218 nm may be
accounted for C-band of the phthalocyanine molecule.
The electronic spectra of M-MeOPhImPcs were
recorded in DMF in the concentration range of 1.0–1.5 ×
10–4 M and the summary of the results are presented in
Table 1, Fig. 1. The observed deep bluish green color of
the complexes may be due to a2u
eg and b2u
eg
transitions [15]. For all the complexes absorption bands
are observed in the wavelength 769–774 nm, which
are considerably higher than the corresponding par-
ent metal phthalocyanine [15]. This observed red
shift is attributed to the increase in conjugation of π-
electron of the phthalocyanine molecule with that of
peripheral substituted aromatic imino group. Also
for Cu-MeOPhImPc and Co-MeOPhImPc absorption
bands were observed at 685 nm. The origin of the
IR Spectra
IR spectral data were recorded in KBr pellets and
the results are presented in Table 2, Fig. 2. A sharp peak
at 1622–1638 cm–1 is attributed to C=N of imine group
and peaks in the range 1490–1497 cm–1 are due to C–N
aromatic stretching. The peaks in the range of 1403–
1409 cm–1 were attributed to CH3 bending. The 1248–
1256 cm–1 peaks were attributed to C–O–C asymmetric
Q-band is attributed to the a1u
eg transition of the
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SYNTHESIS, STRUCTURAL INVESTIGATIONS AND BIOLOGICAL STUDIES
71
Table 1. Spectral data of metal(II) 3,3',3'',3'''-tetra-methoxyphenyl-imino phthalocyanin
UV-Visible wavelength
IR Spectral
Data (cm–1)
Powder XRD
Data 2θ angle (d')
Relative
Intensity %
Complex
λ nm (logε )
Co–MeOPhImPc
211 (3.44)
254 (3.37)
331 (3.21)
678 (4.05)
774 (3.78)
216 (3.34)
256 (4.20)
333 (3.68)
685 (4.31)
772 (3.95)
224 (3.44)
244 (4.19)
339 (3.30)
679 (4.35)
771 (4.32)
218 (3.66)
248 (4.24)
328 (3.44)
685 (4.18)
769 (4.39)
618, 744, 1095,
1252, 1316, 1403,
1491, 1622.
8.30(10.44)
26.00(4.21)
25.85(2.21)
100.00
95.2
86.05
Cu–MeOPhImPc
Ni–MeOPhImPc
Zn–MeOPhImPc
636, 747, 1035,
1248, 1310, 1405,
1497,1638.
6.75(12.21)
8.40(10.20)
29.35(2.74)
100.00
98.16
97.44
648, 752, 1030,
1253, 1316, 1403,
1491,1631.
6.50(15.84)
8.50(10.36)
27.0(3.52)
100.00
86.36
85.98
698, 742, 1088,
1256, 1341, 1409,
1490, 1636.
6.20(14.15)
8.50(11.42)
25.85 (3.44)
100.00
96.52
98.48
a) Wavelength, b) Spectral, c) Relative Intensity.
Table 2. Elemental analysis and magnetic susceptibility data of metal(II) 3,3',3'',3'''-tetramethoxyphenyliminophthalocyanines
Empirical
formulae
(Molecular weight)
Magnetic
susceptibility
Complex (Color)
(Yield)
Field strength
K Gauss
Magnetic moments Elementalanalysis
µeff (B.M)
Found (Calcd.)
(χm × 10–6 cgs unit)
Co–MeOPhImPc
(Dark green)
(88%)
C64H44N12O4Co
(1102.93)
2.20
2.66
3.10
3.58
4.01
+3274.88
+3045.45
+2833.10
+2760.65
+2590.54
2.82
2.72
2.66
2.58
2.49
C: 69.63; (69.44)
H: 3.99; (3.92)
N: 15.23; (15.15)
Co: 5.34; (5.38)
Cu–MeOPhImPc
(Dark green)
(91%)
C64H44N12O4Cu
(1107.54)
2.20
2.66
3.10
3.58
4.01
+3120.90
+3023.12
+2824.80
+2772.60
+2555.11
2.75
2.68
2.61
2.59
2.48
C: 69.37; (68.89)
H: 3.97; (3.88)
N: 15.17; (15.21)
Cu: 5.73; (5.80)
Ni–MeOPhImPc
(Dark green)
(96%)
C64H44N12O4Ni
(1102.69)
2.66
–637.50
–
C: 69.65; (69.66)
H: 3.99; (3.79)
N: 15.23; (15.12)
Ni: 5.32; (5.36)
Zn–MeOPhImPc
(Dark green)
(82%)
C64H44N12O4Zn
(1109.39)
2.66
–785.35
–
C: 69.25; (69.05)
H: 3.96; (3.91)
N: 15.14; (15.10)
Zn: 5.89; (5.84)
stretching vibrations and 1035–1095 cm–1 were due to
C–O–C symmetric stretching vibrations. All the
remaining bands observed in the range 742–752 and
679–685 cm–1 may be assigned to various skeletal
vibrations of the phthalocyanine ring.
Magnetic Susceptibility
Magnetic susceptibility studies were carried out at
ambient temperature and summary of the results are
presented in Table 2. The magnetic moment values
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72
MOINUDDIN KHAN et al.
degenerate states and intermolecular co-operative
effect [14]. This effect decreases with the increase in
field strength and µeff value approaches spin only value
at higher field strength. The observed higher µeff value
at lower field strength is attributed to intermolecular
magnetic interaction coupled with magnetic anisotropy
of phthalocyanine π-electron cloud.
Powder XRD
4
The Powder X-ray diffraction patterns of M-MeO-
PhImPcs are taken through a range of 2θ angles 6°–70°
showed identical peaks with relatively very poor crys-
tallinity (Table 1). The observed patterns are very much
similar to that of unsubstituted parent phthalocyanines
except for the broadening of the peaks with diffused
intensity. The broadening may be due to the presence of
substituents at the periphery of the molecule, which
seems to provide hindrance for the effective stacking of
the molecule and thus the poor crystallinity of the com-
plexes.
3
2
1
Thermogravimetric and Kinetic Studies
Thermogravimetric analytical data of imino substi-
tuted metal phthalocyanine complexes are summarized
in Table 3. It is observed that the decomposition of the
above complexes occurs generally in two steps. The
first step of degradation, which takes place in the tem-
perature region of 130–360°C, may be accounted for
the loss of four imino groups. The major weight loss
was observed in the last step for all the complexes in the
temperature range of 360–545°C corresponds to the
oxidative degradation of phthalocyanine moiety.
Destruction of phthalocyanine macrocycle occurs gen-
erally in the second step. The residues remained after
the thermal decomposition were found to be the corre-
sponding metal oxides [16]. The thermal decomposi-
tion of these imino substituted complexes in the nitro-
gen atmosphere appears to be very slow. For Co-MeO-
200
400
600
800
1000
Wavelength, nm
Fig. 1. Electronic spectra: 1—Co-ImPc; 2—Cu-ImPc;
3—Ni-ImPc; and 4—Zn-ImPc
reported in the table are the average of three indepen-
dent determinations. The magnetic susceptibility stud-
ies revealed that Cu-MeOPhImPc and Co-MeOPhImPc
are paramagnetic and Ni-MeOPhImPc and Zn-MeO-
PhImPc are diamagnetic complexes. The measured
magnetic moments for Cu-MeOPhImPc and Co-MeO-
PhImPc are higher than the spin only value correspond-
ing to the one unpaired electron (1.73BM), due to the
mixing of ground state orbitals with higher energy PhImPc, 67% of the complex was found to be
Table 3. Thermodynamic degradation pattern of metal(II) 3,3',3'',3'''-tetra-methoxyphenyliminophthalocyanines
Mass loss
Probable mode of decomposition
and fragments lost
Compound
Decomposition T, °C
%Found %Calcd.
Co–MeOPhImPc
100–130
130–350
350–490
100–135
135–345
345–470
100–135
135–360
360–480
12.9
35.6
46.2
13.2
36.7
44.2
12.2
35.3
43.6
2.06
36.18
44.96
12.01
36.03
44.78
12.06
36.18
44.76
1 Imino group
3 Imino group
Pc moiety
1 Imino group
3 Imino group
Pc moiety
1 Imino group
3 Imino group
Pc moiety
1 Imino group
3 Imino group
Pc moiety
Cu–MeOPhImPc
Ni–MeOPhImPc
Zn–MeOPhImPc
100–135
135–340
340–545
12.7
36.8
44.1
11.99
35.98
44.71
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SYNTHESIS, STRUCTURAL INVESTIGATIONS AND BIOLOGICAL STUDIES
73
4
3
2
1
4000
3500
3000
2500
2000
1500
1000
500
Wave number, cm–1
Fig. 2. IR absorption spectra: 1—Co-ImPc; 2—Cu-ImPc; 3—Ni-ImPc; and 4—Zn-ImPc.
decomposed at 680°C. For Cu-MeOPhImPc, Ni-MeO- sus 1/T (where y is the fraction of the complex not
PhImPc and Zn-MeOPhImPc about 65, 62, and 55%
loss of the mass was observed even at 680°C. Above
trend confirms the relatively higher stability of these
complexes in nitrogen atmosphere than that in air. Even
though all four functional groups seem to be lost during
first and second steps, a dimer or a polymer is suspected
to be formed via the nitrogen atoms of the peripheral
end groups before the second step of decomposition
starts [17]. DTA results revealed that all degradation
steps are exothermic in nature. Kinetic and thermody-
namic parameters of the title complexes have been eval-
decomposed) were developed for the decomposition
segment where loss of functional groups occurs. From
the plots, the energy of activation (Ea) and frequency
factor (ln A) were evaluated. Enthalpy (∆H), Entropy
(∆S) and free energy (∆G) have been computed using
standard equations (Table 4).
Biological Activities
The ligand and all complexes synthesized in the
uated by Broido’s method [18]. Plots of ln (ln1/y) ver- present investigation and the respective metal salts
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 53 No. 1 2008

74
MOINUDDIN KHAN et al.
ln(ln1/y)
–1.47
ln(ln1/y)
–1.47
(‡)
(b)
–1.48
–1.49
–1.50
–1.51
–1.52
–1.53
–1.48
–1.49
–1.50
–1.51
–1.52
–1.53
–1.54
–1.54
1.0
1.0
1.5
2.0
2.5
3.0
3.5
4.0
1.5
2.0
2.5
3.0
3.5
4.0
1/T × 103, K–1
3
Fig. 3. Plots of ln(ln 1/y) vs. 1/T × 10 for the thermal degradation of Co-ImPc (
Zn-ImPc ( ) in air (a) and in nitrogen atmosphere (b)
), Cu–ImPc (
), Ni–ImPc (
), and
were evaluated for their antifungal and antibacterial temperature of 120°C and 15 psi. The hot sterilized
activity.
media was poured into petriplates in an aseptic cham-
ber and then to room temperature (26°C). The Aspergi-
lus Niger and Aspergilus Flavons were inoculated as a
point at the center of the plate and are incubated at 23
1°C for one week and the observations were made
daily. The summary of the observations of the experi-
ments was presented in Table 5. It was found that all the
complexes inhibit the radial growth of the fungi. After
2 days of inoculation, the fungi exhibited minimal
growth. It was observed that the inhibiting effects of
both M-ImPcs and tetra amino phthalocyanine were
more for Aspergilus Niger compared to Aspergilus Fla-
vons. After 5 days, all the complexes showed distinct
inhibiting effect. However, Zn-MeOPhImPc induced
maximum effect. The inhibition of growth effect was in
the order of Zn-MeOPhImPc > Co-MeOPhImPc >
Cu-MeOPhImPc > Ni-MeOPhImPc, compared to the
Antifungal Activity
The Aspergilus Niger and Aspergilus Flavons were
studied for its growth, color and sporulation character-
istics in the presence of the selected metal phthalocya-
nine complexes. The M-MeOPhImPc and complexes of
1000 ppm were prepared by dissolving the required
quantity of complexes in DMSO. The corresponding
tetra amino phthalocyanine complexes were also dis-
solved in DMSO to prepare 1000 ppm solution and
antifungal studies were carried out under similar condi-
tions for comparison. They were further diluted with
DMSO for the preparations of 500, 100, and 50 ppm
solution. Control was maintained by adding 2 mL of
DMSO to the media separately. Potato Dextrose Agar
(PDA) media with the above preparations were sealed
with aluminum foil and sterilized in an autoclave at a corresponding tetra amino phthalocyanines.
Table 4. Thermodynamic parameter of metal(II) 3,3',3'',3'''-tetramethoxyphenyliminophthalocyanines
Activation energy Frequency factor
Compound
Co–MeOPhImPc
Cu–MeOPhImPc
Ni–MeOPhImPc
Zn–MeOPhImPc
∆H, kJ/mol
∆S, J/K
∆G, kJ/mol
Ea, KJ/mole
lnA
1.10 (0.21)
3.93 (55.8)
3.541 (03.84)
5.214 (22.64)
0.65 (0.513)
3.13 (54.90)
–148.27 (–178.5)
–169.59 (334.12)
19.86 (25.53)
120.54 (–105.3)
0.94 (0.45)
3.66 (71.7)
3.542 (02.52)
5.562 (28.29)
0.42 (1.25)
2.65 (69.86)
–148.61 (–184.9)
–167.61 (444.2)
20.54 (29.22)
114.32 (–151.2)
0.87 (0.84)
3.45 (74.4)
3.910 (03.62)
5.245 (23.18)
0.31 (0.74)
2.98 (62.10)
–151.28 (–179.2)
–161.82 (352.26)
20.124 (21.44)
116.76 (–110.4)
0.94 (0.41)
3.82 (71.7)
3.541 (02.21)
5.460 (26.59)
0.24 (0.91)
3.10 (60.21)
–156.11 (–184.9)
–165.35 (414.9)
20.43 (25.22)
112.20 (–147.2)
The values in the bracket corresponds to the nitrogen atmosphere.
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SYNTHESIS, STRUCTURAL INVESTIGATIONS AND BIOLOGICAL STUDIES
75
Table 5. Anti-fungal data of metal(II) 3,3',3'',3'''-tetramethoxyphenyliminophthalocyanines
Aspergilus Niger
Radial growth in cm
Aspergilus Flavous
Radial growth in cm
Compound
Conc. (in ppm)
2 days
5 days
2 days
5 days
Control
1.50
3.90
1.35
3.50
Co–MeOPhImPc
Cu–MeOPhImPc
Ni–MeOPhImPc
Zn–MeOPhImPc
50
100
1.30(1.45)
1.15(1.35)
0.90(1.20)
0.60(1.05)
3.45 (3.85)
3.20 (3.75)
2.60 (3.55)
2.50 (3.40)
1.25(1.35)
1.10(1.30)
0.90(1.20)
0.75(1.10)
3.30 (3.40)
3.10 (3.30)
2.90 (3.25)
2.60 (3.15)
500
1000
50
100
1.35(1.50)
1.20(1.45)
1.00(1.35)
0.70(1.25)
3.50 (3.80)
3.15 (3.65)
2.65 (3.55)
1.80 (3.15)
1.25(1.30)
1.10(1.25)
0.95(1.15)
0.70(1.05)
3.30 (3.45)
3.00 (3.20)
2.60 (3.05)
1.90 (2.85)
500
1000
50
100
1.35(1.40)
1.15(1.35)
0.90(1.20)
0.55(1.05)
3.55 (3.75)
3.15 (3.70)
2.80 (3.45)
2.15 (3.25)
1.25(1.35)
1.15(1.30)
0.90(1.15)
0.65(1.05)
3.40 (3.50)
3.10 (3.40)
2.85 (3.25)
2.35 (3.10)
500
1000
50
100
1.40(1.45)
1.15(1.40)
0.90(1.25)
0.45(1.00)
3.65 (3.60)
3.15 (3.45)
2.40 (3.20)
1.35 (2.85)
1.20(1.25)
1.00(1.40)
0.75(1.25)
0.55(1.05)
3.45 (3.45)
3.05 (3.05)
2.35 (2.85)
1.30 (2.55)
500
1000
The values in the bracket correspond to the respective metal(II) aminophthalocyanines.
The interesting observation made during the investi- Sahyadri Science College, Kuvempu University, Shi-
gation was the change in the color of the fungus. moga.
Aspergilus Niger was known for its black color and
Method. The above imino phthalocyanine com-
Aspergilus Flavous for its green color. However, in the
plexes were tested against pathogenic bacteria Xanth-
presence of metal complexes the matured colonies of
omonas citri and Xanthomonas sp.
the fungus were pale brown and the new colonies were
The agar diffusion cup plate method was followed
pale green. It was confirmed by the parallel experiment
for antibacterial assay as described in Indian pharmaco-
with and with out the addition of 2 ml DMSO in the
poeia [20]. Inoculum was prepared from 24 h old cul-
media that the change in color of the fungi was not due
ture in nutrient broth. The M-ImPc complexes of
to the presence of DMSO in the medium [19]. The
1000 ppm were prepared by dissolving the required
change of color of the fungi may be due to the effect of
quantity of complexes in DMSO. The corresponding
complexes as the pigmentation properties of the grow-
tetra amino phthalocyanine complexes were also dis-
ing fungi.
solved in DMSO to prepare 1000 ppm solution and
antibacterial studies were carried out under similar con-
ditions for comparison. They were further diluted with
Antibacterial Activity
DMSO for the preparations of 500, 200, and 100 ppm
Bacterial strains. Bacterial strains of Xanthomonas solution. With the help of stainless steel well cutter
were procured from Department of Biotechnology, (6 mm) cups were cut out and into each of these cups
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 53 No. 1 2008

76
MOINUDDIN KHAN et al.
Table 6. Antifungal data of metal(II) 3,3',3'',3'''-tetramethoxyphenyliminophthalocyanines
Conc.
(in ppm)
Xanthomonas species
Zone of inhibition (in mm)
Xanthomonas citri
Zone of inhibition (in mm)
Compound
Control
05
06
Co–MeOPhImPc
Cu–MeOPhImPc
Ni–MeOPhImPc
Zn–MeOPhImPc
50
100
200
500
06 (03)
09 (05)
13 (06)
17 (08)
07 (04)
11 (05)
15 (07)
19 (09)
50
100
200
500
07 (04)
10 (06)
14 (07)
18 (10)
06 (03)
09 (05)
13 (07)
18 (10)
50
100
200
500
06 (03)
10 (05)
14 (06)
20 (08)
08 (05)
11 (06)
15 (08)
19 (10)
50
100
200
500
06 (04)
10 (06)
16 (07)
22 (10)
06 (05)
10 (07)
15 (08)
21 (11)
The values in the bracket correspond to the respective metal(II) aminophthalocyanines.
100 µL of each of the complexes of different concentra- ceptibility studies clearly revealed the structural infor-
mation of the complexes.
tions and blank (DMSO) were placed separately under
aseptic conditions with the help of a sterile micropi-
pette. The plates were then maintained at room temper-
ature (26°C) for 1 hour to allow the diffusion of the
solutions into medium and incubated at 37°C for Xan-
thomonas citri and Xanthomonas sp. Inhibition was
recorded by measuring the diameter of the inhibition
zone at the end of 24 h [21, 22]. As per the observations
made, the maximum inhibition effect was observed in
Zn-MeOPhImPc with tested organism and the least
inhibition effect was observed in Co-MeOPhImPc,
compared to the corresponding tetra amino phthalocy-
anines. The data of Zone of inhibition were presented in
Table 6.
ACKNOWLEDGMENTS
The authors are thankful to the chairman, depart-
ment of Industrial Chemistry, Principal, Sahyadri Sci-
ence College, Kuvempu University. One of the authors,
M.H. Khan, extends thanks to Principal, J.N.N. Col-
lege of Engineering-Shimoga, for providing the basic
laboratory facilities. Thanks are also given to Prof.
A.M.A. Khader, Mangalore University and Prof.
M.A. Pasha, Bangalore University, for their help in
recording spectra.
REFERENCES
CONCLUSIONS
1. P. Vazquez, G. de la Torre, F. Agullo-Lopez, and T. Torres,
Chem. Rev. 104, 3723 (2004).
The synthetic route adopted was very simple and
gives good yield. The red shift of the complexes com-
pared to the parent phthalocyanine is due to increase in
conjugation of π-electron with the π-electron cloud of
peripheral substituted imino group. The magnetic sus-
2. S. M. O' Flaherty, S. V. Hold, M. J. Cook, et al., Adv.
Mater. 15, 19 (2003).
3. W. Kobel and M. Hanack, Inorg. Chem. 25, 103 (1986).
4. P. Gregory, J. Porphyrins Phthalocyanines 4, 434 (2000).
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 53 No. 1 2008

SYNTHESIS, STRUCTURAL INVESTIGATIONS AND BIOLOGICAL STUDIES
77
5. M. W. Grinstaff, M. G. Hill, J. A. Labinger, and 14. P. W. Selwood, Magnetochemistry, 2nd ed. (Interscience,
H. B. Gray, Science 264, 1311 (1994).
New York, 1956; Inostrannaya Literatura, Moscow,
1958).
15. C. C. Leznoff andA. B. P. Lever, Phthalocyanines, Prop-
erties and Applications (VCH, New York, 1989), Vol. 1,
p. 173.
6. R. A. Sheldon, Metalloporphyrin Catalytic Oxidation
(Marcel Decker, New York), p. 1194.
7. H. Ali and J. E. Van Lier, Coord. Chem. Rev. 99, 2379
(1999).
16. I. A. Vogel, Quantitative Inorganic Analysis (Longmans,
London, 1964).
8. S. A. Priola, A. Raines, and W. S. Caughey, Science 287,
17. M. P. Somashekarappa, K.R. Venugopala Reddy, M. N.
K. Harish, and J. Keshavayya, J. T. R. Chem. 11 (1), 1
(2004).
1503 (2000).
9. M. C. Harsans, N. P. Guisinger, and J. W. Lyding, Nano-
tecnology 11, 70 (2000).
18. A. Broido, J. Polym. Sci. Part A2 7, 1761 (1969).
10. R. Jasinski, Nature 201, 1212 (1964).
19. M. H. Moinuddin Khan, Fasiulla, M. N. K. Harish, J.
Keshavayya, and K. R. Venugopala Reddy, J. T. R.
Chem. 13 (1), 70 (2006).
11. M. P. Somashekarappa and J. Keshavayya, J. Soudi.
Chem. Soc. 3 (2), 113 (1999).
20. Indian Pharmacopoeia, 3rd Edition (New Delhi, 1985).
12. M. P. Somashekarappa and J. Keshavayya, Synth. React.
21. L. Ahmed, Z. Mohammed, and F. Mohammed, J. Eth-
Inorg. Met-Org. Chem. 29 (5), 767 (1999).
nopharmacol. 62, 183 (1998).
13. B. N. Achar, Fohlen, Parker, G.M., Keshavayya, J., Poly- 22. S. N. Padhy, S. B. Mahato, and N. L. Dutta, Phytochem-
hedron 6 (6), 1463 (1987). istry 12, 217 (1973).
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 53 No. 1 2008