Novel metallophthalocyanines bearing 3-(p-chlorophenyl)-5-p-tolyl-4H-1,2,4-triazole bulky substituents by microwave irradiation

Article abstract of DOI:10.1016/j.jorganchem.2008.08.007

The synthesis of metallophthalocyanines [6-9; M = Ni(II), Zn(II), Co(II) and Cu(II)] with four 1,2,4-triazole units obtained from 4-{(4-chloro-2-fluorobenzyl)[3-(4-chlorophenyl)-5-(4-methylphenyl)-4H-1,2,4-triazol-4-yl]amino}phthalonitrile (5) in the presence of dimethylaminoethanol and the corresponding anhydrous metal salts is described. The thermal stabilities of the Pc compounds were determined by thermogravimetric analysis. The new compounds were characterized by a combination of IR, ¹H NMR, ¹³C NMR, UV-Vis, elemental analysis.

Full text of DOI:10.1016/j.jorganchem.2008.08.007

Journal of Organometallic Chemistry 693 (2008) 3425–3429
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Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Novel metallophthalocyanines bearing 3-(p-chlorophenyl)-5-p-tolyl-4H-1,2,
4-triazole bulky substituents by microwave irradiation
*
Olcay Bekircan , Zekeriya Bıyıklıog˘lu, Irfan Acar, Hakan Bektas, Halit Kantekin
Department of Chemistry, Faculty of Arts and Sciences, Karadeniz Technical University, 61080 Trabzon, Turkey
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 25 June 2008
Received in revised form 29 July 2008
Accepted 4 August 2008
Available online 11 August 2008
The synthesis of metallophthalocyanines [6–9; M = Ni(II), Zn(II), Co(II) and Cu(II)] with four 1,2,4-triazole
units obtained from 4-{(4-chloro-2-fluorobenzyl)[3-(4-chlorophenyl)-5-(4-methylphenyl)-4H-1,2,4-tria-
zol-4-yl]amino}phthalonitrile (5) in the presence of dimethylaminoethanol and the corresponding anhy-
drous metal salts is described. The thermal stabilities of the Pc compounds were determined by
thermogravimetric analysis. The new compounds were characterized by a combination of IR, 1H NMR,
13C NMR, UV–Vis, elemental analysis.
Keywords:
Ó 2008 Elsevier B.V. All rights reserved.
Cyclotetramerization
Metallophthalocyanine
Synthesis
Microwave
1,2,4-Triazole
1. Introduction
In last years, much effort has been dedicated to the microwave
assisted synthesis of metal-free and metallophthalocyanines [29–
1,2,4-Triazole and its derivatives belong to a class of exception-
ally active compounds possessing a wide spectrum of biological
properties, including anticonvulsant [1], antimicrobial [2,3], anti-
hypertensive [4], analgesic [5], antiviral [6], antioxidant [7], anti-
inflammatory [8], antitumor [9,10], anti-HIV [11], pesticidal [12],
insecticidal [13], herbicidal [14] and fungicidal activity [15]. In
addition, it was reported that compounds having triazole moieties,
such as vorozole, letrozole and anastrazole appeared to be very
effective aromatase inhibitors, which in turn prevented breast can-
cer [16–18]. Apart from their pharmacological significance, 1,2,4-
triazole derivatives exhibit interesting chemical properties. The
ability of triazoles to form a bridge between metal ions makes such
ligands very important for magnetochemical applications [19,20].
Some complexes containing substituted 1,2,4-triazole ligands have
potential uses as optical sensors or molecular-based memory de-
vices [21,22].
Phthalocyanines, a family of a aromatic macrocycles depend on
delocalized 18-p electron system, are known not only as classical
dyes in practical use, but also as modern functional materials in
scientific research [23,24].
The importance of phthalocyanines in many fields, including
photodynamic reagents for cancer therapy [25], laser dyes, new
red-sensitive photocopying applications [26], optical computer
read/write discs [27], is increasing rapidly as a result of the synthe-
sis of new compounds [28].
43]. In this paper, we describe the synthesis and characterization
of metallophthalocyanines 6, 7, 8 and 9 by microwave irradiation
containing 1,2,4-triazole bulky substituents.
2. Experimental
All reagents and solvents were of reagent grade quality and
were obtained from commercial suppliers. All solvents were dried
and purified as described by Perrin and Armarego [44]. The IR spec-
tra were recorded on a Perkin–Elmer 1600 FT-IR Spectrophotome-
ter, using KBr pellets or NaCl disc. 1H and 13C NMR spectra were
recorded on a Varian Mercury 200 MHz spectrometer in CDCl3,
DMSO, and chemical shifts were reported (d) relative to Me4Si as
internal standard. Mass spectra were measured on a Micromass
Quatro LC/ULTIMA LC-MS/MS spectrometer. The elemental analy-
ses were performed on a Costech ECS 4010 instrument. A Seiko II
Exstar 6000 thermal analyzer was used to record DTA curves under
nitrogen atmosphere with a heating rate of 20 °C minÀ1 in the tem-
perature range 30–900 °C using platinum crucibles. Melting points
were measured on an electrothermal apparatus and are uncor-
rected. Optical spectra in the UV–Vis region were recorded with
a Unicam UV2-100 spectrophotometer, using 1 cm pathlength cuv-
ettes at room temperature.
2.1. Ethyl p-methylbenzoate p-chlorobenzoylhydrazone (1)
A solution of p-chlorobenzhydrazide (0.01 mol) in 25 mL of
absolute ethanol was added to a solution of ethyl imido-p-meth-
* Corresponding author. Tel.: +90 505 6153107; fax: +90 462 325 3196.
E-mail address: obekircan@gmail.com (O. Bekircan).
0022-328X/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2008.08.007

3426
O. Bekircan et al. / Journal of Organometallic Chemistry 693 (2008) 3425–3429
ylbenzoate hydrochloride (0.01 mol) in 25 mL of absolute ethanol.
The mixture was stirred for 6 h at 0–5 °C and subsequently for 2 h
at room temperature. The reaction mixture was poured into a bea-
ker containing 40 mL of cold water and 10 g of ice. The precipitate
formed was washed with 50 mL of ice-water and then dried. The
product was recrystallized from benzene–petroleum ether (1:2)
to give pure compound 1. Yield 78%, m.p. 105–106 °C. IR (KBr tab-
d = Ar–H: [7.83 (d, 2H, J = 8.8 Hz), 7.64 (d, 2H, J = 8.4 Hz), 7.42 (d,
2H, J = 8.8 Hz), 7.31 (d, 2H, J = 8.4 Hz), 6.87–6.82 (m, 1H), 6.73–
6.67 (m, 1H), 6.61-6.53 (m, 1H)], 5.68 (t, 1H, J = 4.4 Hz, NH), 3.77
(d, 2H, J = 4.4 Hz, CH2), 2.45 (s, 3H, CH3). 13C NMR (CDCl3)
d = 164.57 (C@N), 154.05 (triazole C-5), 152.51 (triazole C-3), Ar–
C: [163.38, 140.65, 136.09, 135.49, 131.83, 129.73, 129.46,
129.24 (2C), 128.78 (2C), 127.73 (2C), 124.42, 123.34, 120.21,
116.36], 49.47 (CH2), 21.50 (CH3).
let), m
max/cmÀ1: 3178 (N–H), 3067 (Ar–H), 2976–2925 (Aliph. C–H),
1646 (C@O), 1564, 1456, 1398, 1378, 1299, 1089, 1070, 1014, 847,
814, 793. 1H NMR (DMSO-d6) d = 10.27 (s, 1H, NH), Ar–H: [7.83
(2H, J = 8.40 Hz), 7.66 2H, J = 8.00 Hz), 7.45 (2H, J = 8.40 Hz), 7.21
(2H, J = 8.00 Hz)], 4.29 (q, 2H, J = 3.60 Hz, OCH2CH3), 2.28 (s, 3H,
CH3), 1.27 (t, 3H, J = 3.60 Hz, OCH2CH3). 13C NMR (DMSO-d6)
d = 165.92 (C@O), 162.06 (C@N), Ar–C: [140.87, 136.47, 130.38,
129.97 (2C), 129.68 (2C), 129.05 (2C), 128.50 (2C), 128.33], 67.40
(OCH2CH3), 21.64 (CH3), 14.87 (OCH2CH3).
2.5. 4-{(4-chloro-2-fluorobenzyl)[3-(4-chlorophenyl)-5-(4-
methylphenyl)-4H-1,2,4-triazol-4-yl]amino}phthalonitrile (5)
N-(4-chloro-2-fluorobenzyl)-3-(4-chlorophenyl)-5-(4-methyl-
phenyl)-4H-1,2,4-triazol-4-amine
4 (1.5 g, 3.51 mmol) and 4-
nitrophthalonitrile (607 mg, 3.51 mmol) were dissolved in dry
DMF (10 mL) under N2 atmosphere. After stirring for 10 min at
50 °C, dry fine-powdered potassium carbonate (968 mg,
7.02 mmol) was added portionwise within 2 h with efficient stir-
ring. The reaction mixture was stirred under N2 at 50 °C for
3 days. Then the mixture was poured into 150 mL ice-water,
and precipitate was filtered off, washed with water, diethyl ether
and dried in vacuo. The residue was crystallized from ethanol.
Yield: 1.03 g (53%), m.p. 162–163 °C. Anal. Calc. for C30H19N6Cl2F:
C, 65.11; H, 3.46; N, 15.19. Found: C, 65.10; H, 3.86; N, 15.14%. IR
2.2. 4-Amino-3-(p-chlorophenyl)-5-p-tolyl-4H-1,2,4-triazole (2)
Compound 1 (0.005 mol) was added to a solution of hydrazine
hydrate (0.01 mol) in 50 mL of 1-propanol and the mixture was re-
fluxed for 24 h. On cooling, a precipitate was formed. This product
was filtered and, after drying, was washed with 20 mL of benzene.
The remaining solid was recrystallized from 1-propanol to afford
pure compound 2. Yield 85%, m.p. 314–315 oC. IR (KBr tablet),
(KBr tablet),
m
max/cmÀ1: 3071 (Ar–H), 2921–2862 (Aliph. C–H),
m
max/cmÀ1: 3360–3206 (NH2), 3035, 2921, 1619 (C@N), 1474,
2228 (C„N), 1600, 1581, 1531, 1488, 1411, 1345, 1269, 1185,
1093, 1015, 896, 821, 731, 592, 521. 1H NMR. (DMSO-d6),
(d:ppm): Ar–H: [8.03 (d, 2H), 7.91 (m, 2H), 7.81 (m, 2H), 7.73
(s, 1H), 7.55 (d, 2H, J = 5.0 Hz), 7.27 (d, 2H, J = 4.7 Hz), 7.04–6.99
(m, 1H), 6.94-6.87 (m, 1H), 6.78–6.70 (m, 1H)], 3.73 (s, 2H,
CH2), 2.48 (s, 3H, CH3). 13C NMR. (DMSO-d6), (d:ppm): 163.22,
161.52, 158.34, 150.08, 139.74, 135.28, 134.50, 133.59, 132.46,
129.58, 129.22, 128.41, 127.68, 127.38, 125.98, 125.61, 124.19,
123.87, 121.74, 121.44, 117.44, 116.72, 115.77, 115.26, 105.80,
48.24, 21.42.
1269, 1093, 1015, 968, 911, 823, 727. 1H NMR (DMSO-d6) d = Ar–
H: [8.02 (d, 2H, J = 7.4 Hz), 7.92 (d, 2H, J = 6.8 Hz), 7.52 (d, 2H,
J = 6.8 Hz), 7.34 (d, 2H, J = 7.4 Hz)], 6.26 (s, 2H, NH2), 2.38 (s, 3H,
CH3). 13C NMR (DMSO-d6) d = 154.93 (triazole C5), 154.81 (triazole
C3), Ar–C: [139.91, 130.22, 129.73 (2C), 129.16 (2C), 128.98 (2C),
128.88 (2C), 127.99, 125.09], 21.70 (CH3).
2.3. 3-(p-chlorophenyl)-5-p-tolyl-4-(2-fluoro-4-
chlorobenzylidenamino)-4H-1,2,4-triazole (3)
4-Chloro-2-fluorobenzaldehyde (0.005 mol) was added to a
solution of compound 2 (0.005 mol) in 20 mL of glacial acetic acid
and the mixture was refluxed for 4 h. After cooling, the mixture
was poured into a beaker containing 100 mL of ice-water. The pre-
cipitate formed was filtered. After drying in vacuo, the solid was
recrystallized from ethanol–water (1:2) to afford pure compound
3. Yield 87%, m.p. 175–176 oC; Anal. Calc. for C22H15Cl2FN4: C:
62.13, H: 3.55, N: 13.17. Found: C: 62.12, H: 3.57, N: 13.19%. IR
2.6. General procedures for phthalocyanine derivatives (6–9)
A mixture of 4-{(4-chloro-2-fluorobenzyl)[3-(4-chlorophenyl)-
5-(4-methyl phenyl)-4H-1,2,4-triazol-4-yl]amino}phthalonitrile 5
(230 mg, 0.41 mmol), anhydrous metal salt [NiCl2 (14 mg),
Zn(CH3COO)2 (19 mg), CoCl2 (13 mg), CuCl2 (14 mg)] and 2-
(dimethylamino)ethanol (3 mL) was irradiated in a microwave
oven at 175 °C, 350 W for 8 min. After cooling to room temperature
the reaction mixture was refluxed with ethanol to precipitate the
product which was filtered off. The green solid product was
washed with hot ethanol, water, diethyl ether and dried in vacuo
over P2O5.
(KBr tablet),
m
max/cmÀ1: 1608, 1565 (C@N), 909, 823, 724 (arom.
ring) cmÀ1 1H NMR (CDCl3) d = 8.37 (s, 1H, N@CH), Ar–H: [8.07–
;
7.99 (m, 1H), 7.86 (d, 2H, J = 8.4 Hz), 7.69 (d, 2H, J = 8.0 Hz), 7.44
(d, 2H, J = 8.4 Hz), 7.32–7.24 (m, 3H), 7.17–7.11 (m, 4H)], 2.39 (s,
3H, CH3). 13C NMR (CDCl3) d = 160.43 (C@N), 154.42 (triazole C-
5), 151.57 (triazole C-3), Ar–C: [164.23, 140.40, 136.14, 134.75,
129.83 (2C), 129.71 (2C), 129.60, 129.11 (2C), 128.53 (2C),
125.91, 124.89, 123.13, 117.53, 117.04, 21.46 (CH3).
2.7. Phthalocyaninato nickel(II) (6)
Yield: 142 mg (60%). Anal. Calc. for C120H76N24Cl8F4Ni: C, 63.43;
H, 3.37; N, 14.79. Found: C, 63.40; H, 3.31; N, 14.76%. IR (KBr tab-
2.4. 3-(p-chlorophenyl)-5-p-tolyl-4-(2-fluoro-4-chlorobenzylamino)-
4H-1,2,4-triazole (4)
let) m
max/cmÀ1: 3060 (Ar–H), 2923–2857 (Aliph. C–H), 1608, 1484,
1472, 1410, 1218, 1093, 1056, 894, 820. 1H NMR. (DMSO), (d:ppm):
7.83–7.33 (m, 56H, Ar–H), 3.79 (s, 8H, CH2–N), 2.25 (s, 12H, CH3).
Compound 3 (0.005 mol) was dissolved in 50 mL of dried meth-
anol, and NaBH4 (0.005 mol) was added in small portions to this
solution. The mixture was refluxed for 30 min and then allowed
to cool. After evaporation at 25–30 oC under reduced pressure,
the solid residue was washed with cold water. After drying in va-
cuo, the solid product was recrystallized from an ethanol to afford
pure compound 4. Yield 95%, m.p. 202–203 oC; Anal. Calc. for
2.8. Phthalocyaninato zinc(II) (7)
Yield: 125 mg (53%). Anal. Calc. for C120H76N24Cl8F4Zn: C, 63.24;
H, 3.36; N, 14.75. Found: C, 63.20; H, 3.30; N, 14.59%. IR (KBr tab-
let) m
max/cmÀ1: 3060 (Ar–H), 2917–2846 (Aliph. C–H), 1608, 1580,
1486, 1448, 1407, 1341, 1215, 1182, 1091, 1012, 894, 820. 1H NMR.
(DMSO), (d:ppm): 7.90–7.41 (m, 56H, Ar–H), 3.85 (s, 8H, CH2–N),
2.23 (s, 12H, CH3).
C
22H17Cl2FN4: C: 61.84, H: 4.01, N: 13.11. Found: C: 61.87, H:
4.02, N: 13.16%. IR (KBr tablet),
max/cmÀ1: 3250 (NH), 1610,
1581 (C@N), 895, 819, 731 (arom. ring) cmÀ1 1H NMR (CDCl3)
m
;

O. Bekircan et al. / Journal of Organometallic Chemistry 693 (2008) 3425–3429
3427
2.9. Phthalocyaninato cobalt(II) (8)
The phthalonitrile derivative 5 was obtained through displacement
reaction of 4-nitrophthalonitrile with compound 4. Metallopht-
halocyanines 6–9 were prepared from the corresponding phthalo-
Yield: 134 mg (57%). Anal. Calc. for C120H76N24Cl8F4Co: C, 63.42;
H, 3.37; N, 14.79. Found: C, 63.37; H, 3.28; N, 14.77%. IR (KBr tab-
nitrile
5 and corresponding metal salts (Ni, Zn, Co, Cu) in
let)
m
max/cmÀ1: 3065 (Ar–H), 2923–2851 (Aliph. C–H), 1607, 1580,
dimethylaminoethanol for 8 min 175 °C, 350 W by microwave
(Scheme 1). The structures of novel compounds were characterized
by a combination of 1H NMR, 13C NMR, IR, UV–Vis, elemental anal-
ysis Scheme 2.
1484, 1410, 1382, 1218, 1179, 1092, 894, 820.
2.10. Phthalocyaninato copper(II) (9)
Yield: 149 mg (63%). Anal. Calc. for C120H76N24Cl8F4Cu: C, 63.29;
H, 3.36; N, 14.76. Found: C, 63.33; H, 3.38; N, 14.71%. IR (KBr tab-
3.1. IR spectra
let)
m
max/cmÀ1: 3027 (Ar–H), 2923–2851 (Aliph. C–H), 1603, 1488,
The IR spectra of compound 1 showed absorption bands in the
3178, 1649 and 1619 cmÀ1 regions resulting from the NH, C@O
and C@N functions, respectively. Compound 2 showed two peaks
in the regions 3343–3206 cmÀ1 due to asymmetric and symmetric
vibration of the primary amino group. Compound 3 showed char-
1454, 1410, 1341, 1262, 1220, 1179, 1091, 1009, 896, 821.
3. Results and discussion
acteristic C@N stretching bands between 1565 and 1608 cmÀ1
.
In the current study, ethyl p-methylbenzoate p-chloro-
benzoylhydrazone 1 was synthesized from the reaction of ethyl
imido-p-methylbenzoate hydrochloride with p-chlorobenzhydraz-
ide. 4-amino-3-(p-chlorophenyl)-5-p-tolyl-4H-1,2,4-triazole 2 was
obtained from the reaction of compound 1 with hydrazine hydrate
in 1-propanol. Compound 2 was treated with 4-chloro-2-fluoro-
benzaldehyde in acetic acid to give 3-(p-chlorophenyl)-5-p-tolyl-
4-(2-fluoro-4-chlorobenzylidenamino)-4H-1,2,4-triazole 3. Then
compounds 3 were converted to 3-(p-chlorophenyl)-5-p-tolyl-4-
(2-fluoro-4-chlorobenzylamino)-4H-1,2,4-triazole 4 by treatment
with NaBH4 in methanol. Next step in the synthetic procedure
was to obtain 4-{(4-chloro-2-fluorobenzyl)[3-(4-chlorophenyl)-5-
(4-methylphenyl)-4H-1,2,4-triazol-4-yl]amino}-phthalonitrile 5.
Characteristic NH stretching bands of
4 was observed at
3250 cmÀ1. The formation of dinitrile derivative 5 was clearly indi-
cated by the appearance in its FT-IR spectrum of the C„N band at
2228 cmÀ1. After conversion of dinitrile derivative 5 to metallopht-
halocyanine 6–9, the sharp C„N vibration around 2228 cmÀ1
disappeared.
3.2. NMR spectra
In the 1H NMR spectra of compound 1 characteristic OCH2CH3
signals appeared at d 4.29 ppm (q, 2H, CH2) and d 1.27 ppm (t,
3H, CH3). Characteristic amino proton (NH2) of compound 2 was
Cl
Cl
NH.HCl
O
C
H3C
OC2H5
0-5 oC
NH
N
H2NNH .H2O
2
NH2
N
N
1-propanol
H5C2O
Ethanol
N
O
H2N NH
C
Cl
CH3
CH3
2
1
F
CHO
Cl
Cl
Cl
Cl
Cl
Cl
Cl
F
F
F
NC
NC
NO2
CN
N
CH3OH
NH
N
N
N
N
N
N
N
NaBH
4
dry K2CO3, dry DMF
N
N
N
CN
CH3
CH3
CH3
5
3
4
Scheme 1. The synthesis of dinitrile compound.

3428
O. Bekircan et al. / Journal of Organometallic Chemistry 693 (2008) 3425–3429
H3C
Cl
Cl
N
N
Cl
N
N
Cl
N
N
F
N
N
Cl
F
N
F
H3C
Cl
CN
CN
N
N
N
N
N
N
DMAE
350W 175 ºC
N
N
M
N
N
N
Cl
CH3
F
N
Cl
N
F
N
N
CH3
5
N
N
N
N
Cl
Cl
CH3
8
6
7
Compound
M
9
Ni Zn
Co Cu
Scheme 2. The synthesis of metallophthalocyanines.
detected at d 6.26 ppm. The 1H NMR characteristic signals of Schiff
base (3) were observed at d 8.37 ppm (s, 1H, N@CH). The 1H NMR
signals for the –CH2– group of compound 4 were observed as a
doubled at d 3.77 (J = 4.4 Hz) ppm and the proton signals of
–NH– group was recorded as a triplet at d 5.68 (J = 4.4 Hz) ppm.
In the 1H NMR spectrum of 5, NH group of compound 4 disap-
peared as expected. In the 13C NMR spectra of compound 1 charac-
teristic C@O signal appeared d 165.92 ppm. The Triazole C-3 and
C-5 signals of compound 2 were recorded at d 154.81 ppm and d
154.93 ppm, respectively. The 13C characteristic N@CH carbon sig-
nal of compound 3 was recorded at d 160.43 ppm. Characteristic
1.5
1
0.5
0
200
300
400
500
600
700
800
900
λ (nm )
NH–CH2 carbon signal of compound
4 was recorded at d
Fig. 2. UV–Vis spectra of compounds 8 (–), 9 (. . .) in pyridine.
49.47 ppm. In the 13C NMR spectrum of 5 indicated the presence
of nitrile carbon atoms in 5 at d = 115.26 and 115.77 ppm.
absorptions at 641, 643, 633 and 637 nm, respectively. The single
Q bands in metallo derivatives 6–9 are characteristic. This result
is typical of metal complexes of substituted and unsubstituted
metallophthalocyanines with D4h symmetry [45]. B band absorp-
tions of compounds 6–9 were observed at kmax = 271, (280, 357),
300, 293 nm as expected, respectively.
3.3. UV-Vis spectra
The electronic absorption spectrum of the metallophthalocya-
nines 6,7 and 8,9 in pyridine at room temperature is shown in
Figs. 1 and 2, respectively. UV–Vis spectra of phthalocyanine core
is dominated by two intense bands, the Q band around 600–
710 nm and the B band in the near UV region at about 300–
3.4. TG/DTA
*
400 nm, both correlated
p–p transitions. The UV–Vis absorption
spectra of metallophthalocyanines 6–9 in pyridine show intense
Q absorption at kmax = 701, 709, 703 and 704 nm, with a weaker
The thermal behaviour of the metallophthalocyanines were
investigated by TG/DTA. Although the thermal stabilities of phthal-
ocyanines is well known, the phthalocyanines compounds are not
stable above 338 °C. The initial and main decomposition tempera-
tures are given in Tables 1 and 2. The initial decomposition tem-
perature decreased in the order: 8 > 9 > 6 > 7.
1.5
1
Table 1
0.5
UV–Vis data for the phthalocyanines
Compound
Solvent
kmax/nm: [10À5 (dm3 molÀ1 cmÀ1)]
e
0
6
7
8
9
Pyridine
Pyridine
Pyridine
Pyridine
271 (5.04), 641 (4.50), 701 (5.00)
280 (5.08), 357 (4.92), 643 (4.50), 709 (5.04)
300 (5.03), 633 (4.56), 703 (5.12)
293 (5.01), 637 (4.54), 704 (5.08)
200
300
400
500
600
λ (nm )
700
800
900
Fig. 1. UV–Vis spectra of compounds 6 (–), 7 (. . .) in pyridine.

O. Bekircan et al. / Journal of Organometallic Chemistry 693 (2008) 3425–3429
3429
Table 2
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Breast Cancer Res. Tr. 60 (2000) 117.
Thermal properties of the phthalocyanines
[17] T.E. Delea, K. El-Ouagari, J. Karnon, O. Sofrygin, Breast Cancer Res. Tr. 108
(2008) 375.
Compound
M
Initial decom. temp. (°C)
Main decom. temp. (°C)
[18] M. Kurosumi, Y. Takatsuka, T. Watanabe, S. Imoto, H. Inaji, H. Tsuda, F.
Akiyama, G. Sakamoto, T. Ikeda, S. Noguchi, J. Cancer Res. Clin. 134 (2008) 715.
[19] L.G. Lavrenova, O.G. Shakirova, G.Yu Shvedenkov, V.N. Ikorskii, V.A. Varnek,
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L.G. Lavrenova, Inorg. Chem. Commun. 5 (2002) 690.
6
7
8
9
Ni
343
338
371
359
398
399
422
412
Zn
Co
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Acknowledgement
This study was supported by the Research Fund of Karadeniz
Technical University, Trabzon, Turkey.
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