Microwave-assisted and conventional synthesis of new phthalocyanines containing 4-(p-fluorophenyl)-3-methyl-4,5-dihydro-1H-1,2,4-triazol-5-one moieties

Article abstract of DOI:10.1016/j.jorganchem.2007.06.067

New metal-free and metal (Zn, Ni, Cu and Co) phthalocyanines containing 4-(p-fluorophenyl)-3-methyl-4,5-dihydro-1H-1,2,4-triazol-5-one moiety have been prepared from 1-(3,4-dicyanophenyl)-4-(p-fluorophenyl)-3-methyl-4,5-dihydro-1H-1,2,4-triazol-5-one by b

Full text of DOI:10.1016/j.jorganchem.2007.06.067

Journal of Organometallic Chemistry 692 (2007) 4835–4842
www.elsevier.com/locate/jorganchem
Microwave-assisted and conventional synthesis of new
phthalocyanines containing 4-(p-fluorophenyl)-3-methyl-
4,5-dihydro-1H-1,2,4-triazol-5-one moieties
a,
a
a
a
b
Bahittin Kahveci *, Musa Ozil , Cihan Kantar , Selami Sasmaz , Samil Isık ,
ß ß
¨
ß
ß
b
Yavuz Ko¨ysal
a
Department of Chemistry, Faculty of Art and Science, Rize University, 53050 Rize, Turkey
Department of Physics, Faculty of Art and Science, Ondokuz Mayıs University, 55139 Samsun, Turkey
b
Received 12 April 2007; received in revised form 21 June 2007; accepted 28 June 2007
Available online 15 July 2007
Abstract
New metal-free and metal (Zn, Ni, Cu and Co) phthalocyanines containing 4-(p-fluorophenyl)-3-methyl-4,5-dihydro-1H-1,2,4-triazol-
5-one moiety have been prepared from 1-(3,4-dicyanophenyl)-4-(p-fluorophenyl)-3-methyl-4,5-dihydro-1H-1,2,4-triazol-5-one by both
conventional and microwave-assisted methods. All of these compounds are soluble in CHCl3, DMF and DMSO. The new compounds
have been characterized by elemental analysis, IR, NMR, UV–Vis spectroscopies. The crystal structures of compounds I and II were also
determined by the single crystal diffraction technique.
Ó 2007 Elsevier B.V. All rights reserved.
Keywords: Microwave; Synthesis; Phthalocyanine; Triazol-5-one
1. Introduction
ents on the periphery enhance the solubility and the
donor atoms such as N and O of the substituents are capa-
ble of solving the phthalocyanines [2–5].
1,2,4-Triazols and 4,5-dihydro-1H-1,2,4-triazol-5-ones
have been found to be associated with diverse pharmaco-
logical activities [6,7].
High-speed synthesis by microwaves has attracted a
considerable amount of attention in recent years. Using a
microwave oven in microwave-assisted organic synthesis
(MAOS), not only reduces chemical reactions times from
hours to minutes, but also reduces side reactions, increases
the yield, and improves reproducibility. Therefore, many
academic and industrial research groups are already using
MAOS as a forefront technology for rapid optimization
of reactions, for the efficient synthesis of new chemical enti-
ties, and for discovering and probing new chemical reactiv-
ity [8]. We have previously synthesized phthalocyanines
containing macrocyclic substituents by using the micro-
wave irradiation method [9–12].
Phthalocyanines are known as excellent functional
materials. They have been studied in detail for many years,
especially with regard to their properties as pigments for
printing inks and for plastics and in paints and coatings.
In the coming decade, their commercial utility is expected
to have significant ramification.
Thus future potential uses of metal phthalocyanines,
currently under study, include sensing elements in chemical
sensors, electrochromic display devices, photodynamic
reagents for cancer therapy and other medical applications,
applications to optical computer read/write discs and
related information storage systems, laser dyes, and molec-
ular metals and conducting polymers [1]. Bulky substitu-
*
Corresponding author. Tel.: +90 464 223 53 75; fax: +90 464 223 53
76.
E-mail address: bahittin@yahoo.com (B. Kahveci).
0022-328X/$ - see front matter Ó 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2007.06.067

4836
B. Kahveci et al. / Journal of Organometallic Chemistry 692 (2007) 4835–4842
The present paper reports both microwave-assisted and
the appearance of a new Aromatic band at 1600–
1450 cmÀ1, and the formation of compound II by the dis-
appearance of the NH band at 3204 cmÀ1 in I and the
appearance of a new CN band at 2226 cmÀ1, and the for-
mation of the metal-free 1 and metal phthalocyanines 2–5
by the disappearance of the CN band at 2226 cmÀ1 in II.
The IR spectra of metal-free 1 and metal phthalocyanines
2–5 (M = Ni, Zn, Cu or Co) were very similar. The only
difference was the presence of m(NH) vibration assigned
to the band at 3429 cmÀ1 in the free phthalocyanine. This
band was absent in the spectra of the metal complexes.
The M–N vibrations were expected to appear at 400–
100 cmÀ1 but they were not observed in KBr pellets [15].
conventional synthesis methods of starting compound (II),
metal-free and metal (Zn, Ni, Cu and Co) phthalocyanines
containing four 4-(p-fluorophenyl)-3-methyl-4,5-dihydro-
1H-1,2,4-triazol-5-one moieties.
2. Results and discussion
4-Nitrophthalonitrile has been recently used to prepare
monosubstituted phthalonitrile derivatives through base
catalysed electrophilic aromatic substitution reaction
[13]. 1-(3,4-Dicyanophenyl)-4-(p-fluorophenyl)-3-methyl-4,
5-dihydro-1H-1,2,4-triazol-5-one (II) was synthesized by
treating 1,2-dicyanobenzene with 4-(p-fluorophenyl)-3-
methyl-4,5-dihydro-1H-1,2,4-triazol-5-one (I) by using
both microwave and conventional methods (Scheme 1).
The reaction conditions for conventional method were at
room temperature in dimethylformamide (DMF) with
K2CO3 as the base for 24 h [14], for microwave method
were at 350 W for 5 min in DMF [9–12] and the yields were
more than conventional method. The metal-free phthalocy-
anine was obtained by treating a mixture of the dicyano
derivative with hydroquinone by both conventional and
microwave methods. The reaction times are 24 h under
N2 for conventional method and at 350 W for 8 min for
the microwave method. Also the metallo phthalocyanines
were prepared from the dicyano derivative and the corre-
sponding metal salts in dimethylaminoethanol (DMAE)
by both conventional and microwave methods. The yields
for microwave irradiation were more than the conventional
method. In the conventional method for the NiPc, the pht-
halonitrile and NiCl2 were heated for 24 h under N2; for
the ZnPc, the phthalonitrile and Zn(CH3COO)2 were
heated for 24 h under N2; for the CuPc, the phthalonitrile,
CuCl and urea was heated for 24 h under N2 and; for the
CoPc, the phthalonitrile, CoCl2 and ammonium molybdate
were heated for 24 h under N2. In the microwave-assisted
synthesis, for all of these complexes the mixtures were irra-
diated at 350 W for 8 min in the microwave oven. The new
synthesized compounds were soluble in common organic
solvents such as chloroform, DMF and DMSO.
2.2. NMR spectra
1
In the H NMR spectrum of I, the NH proton as a sin-
glet at 11.63 ppm, CH3 protons as a singlet at 2.01 ppm
and the aromatic protons as a multiplet were assigned on
the basis of the results of a previous work on macrocyclic
ligands. The 13C NMR spectrum of I shows one signal
for the C@O carbon at 163.89 ppm, one signals for the
CH3 at 12.14 ppm and multiple signal for the aromatic car-
bons at 154.16–115.89 ppm.
1
Comparison of the H NMR and 13C NMR spectral
data clearly indicated the formation of II by the disappear-
ance of the NH band at 11.63 ppm and the appearance of a
new aromatic band as a multiplet at 8.50–7.40 ppm. The
1
other H NMR data of II were the CH3 band as a singlet
at 2.19 ppm. The 13C NMR spectrum of II shows signals
at 164.52 (C@O), 159.61, 150.97, 146.87, 140.96, 135.44,
129.94, 129.76, 128.18, 121.06, 120.97, 116.73, 116.27,
115.84, 115.49, 109.46 and 12.15 (CH3).
1
The H NMR spectrum of 1 (metal-free Pc) shows the
aromatic protons at 8.56–7.26 ppm and the CH3 protons
at 2.25 ppm. A common feature of the spectra of the
metal-free phthalocyanines is the broad absorptions prob-
ably caused by aggregation of the phthalocyanine. The NH
protons of compound 1 could not be observed, due to this
phenomenon. Because of the ring current of the 18 p elec-
tron system of the inner phthalocyanine core, the protons
are shifted to low or high field [16]. In the 1H NMR spectra
of 1 (metal-free), 2 (Ni) and 3 (Zn), the chemical shifts for
aromatic systems are at 7.26 ppm and 8.56 ppm, and for
the CH3 protons at 2.10 ppm and 2.25 ppm, respectively.
1H NMR measurement was precluded owing to the para-
magnetic nature of the copper phthalocyanine 4 and cobalt
phthalocyanine 5 [1].
1
Elemental analysis, IR, H NMR, 13C NMR, UV–Vis
spectra, and X-ray (for I and II) confirm the proposed
structures of the compounds. These products were
obtained in sufficient purity after successive washing with
different solvents and by column chromatography (silica
gel, chloroform–methanol (80:1)).
13C NMR spectra of the complexes were similar to the
metal-free phthalocyanine.
2.1. IR spectra
Spectral investigations of the newly synthesized interme-
diates and phthalocyanines are in accordance with the pro-
posed structures. By comparing the IR spectra of each step
some information as to the nature of the products were
obtained. In this context, comparison of the IR spectral
data clearly indicated the formation of compound I by
2.3. UV–Vis spectra
The phthalocyanines 1–5 showed typical electronic spec-
tra with two strong absorption regions. One of them was in
the UV region at about 351 nm (B band) and the other in

B. Kahveci et al. / Journal of Organometallic Chemistry 692 (2007) 4835–4842
4837
F
CH3
O
C
CH3
O
C
C
N
NH
OC2H5
C
N
NH
OC2H5
+
NH
OC2H5
- C2H5OH
NH2
Hydrazone
F
Intermediate product
- C2H5OH
CN
CN
N
NH
N
N
CN
CN
(i,ii)
H3C
N
O
+
H3C
N
F
O
O2N
F
(i) DMSO, K2CO3, room temperature
(ii) Microwave, 5-8 min.
I
II
ii
F
CH3
N
Complex
M
2H
Ni
Zn
Cu
Co
N
1
2
3
4
5
O
N
F
N
N
N
N
N
M
N
O
N
H3C
N
N
N
N
N
CH3
N
O
N
F
N
O
N
N
H3C
F
Scheme 1. Synthesis of the ligand and the complexes.
the visible region at 706 nm (Q band), respectively.
Although the symmetry of the phthalocyanines is lowered
by the heteroatom substituent on each phenyl group, com-
pound 1 still shows Q band absorption of D2h symmetry in
CHCl3 [1]. These complexes showed an intense absorption
at 706 nm and a shoulder band of lower intensity at 638 nm
(Fig. 5). The thermal decomposition temperatures of these
complexes were higher than 200 °C.

4838
B. Kahveci et al. / Journal of Organometallic Chemistry 692 (2007) 4835–4842
3. X-ray spectra
The title compounds, C9H8FN3O (I) and C15H10FN5O
(II), containing the triazole ring display the characteristic
features of 1,2,4-triazole derivatives (Figs. 1 and 3). In a
three-dimensional network, molecules (I and II) are linked
by van der Waals interaction (Figs. 2 and 4). From an anal-
ysis of the values there in, it can be concluded that for both
structures C8@N2 (I) and C8@N3 (II) are well defined
double bonds, and are the shortest bonds in the heterocycle
ring (Tables 1 and 3).
For both compounds the triazole system is essentially
planar. The maximum deviation from the plane of the five
membered ring is, C7 atom for I and II. The triple C„N
bond distance in the cyano groups is in good agreement
with our previous report, 4-(4-benzyloxyphenoxy)phthalo-
nitrile [17].
Fig. 3. Crystal structure for II.
Fig. 4. The packing diagram for II.
Fig. 1. Crystal structure for I.
The structure of the title compound I contains weak C–
HÁ Á ÁO and C–HÁ Á ÁN type contacts namely C11–H11Á Á ÁO1
and C15–H15Á Á ÁN2 (Table 2). In addition to, it does exhi-
bit weak C–HÁ Á Áp interaction [C9–H9BÁ Á ÁCg1, Cg1 is the
centroid of the C1–C6 ring]. The structure of the title com-
pound II contains medium strength, N2–H2NÁ Á ÁO1, C6–
H6Á Á ÁO1 and C9–H9CÁ Á ÁF1 type hydrogen bonds (Table
4), where O1 atom, added to triazole ring, accepts hydro-
gen bonds from C–H donors.
4. Experimental
Routine IR spectra were recorded on a Mattion Fou-
rier-transform spectrometer as KBr pellets, UV–Vis spectra
1
on a Unicam UV–Vis spectrometer and H NMR and 13C
NMR spectra on a Brucer AC-200 Fourier-transform spec-
trometer. Elemental analysis was performed by the Instru-
_
¨
mental analysis Laboratory of TUBITAK Gebze Research
Center. 4-Nitrophthalonitrile was synthesized according to
the reported procedure [18]. Domestic microwave oven was
used for all synthesis of phthalocyanines and dinitrile
compounds. For the X-ray study, X-ray data collection:
Fig. 2. The packing diagram for I.

B. Kahveci et al. / Journal of Organometallic Chemistry 692 (2007) 4835–4842
4839
Table 1
Bond distances (A) for I
˚
C(13)–C(14)
C(10)–C(15)
N(2)–C(8)
C(8)–C(9)
N(1)–C(4)
C(11)–C(12)
C(4)–C(3)
C(12)–C(16)
C(3)–C(2)
C(5)–H(5)
C(1)–C(6)
1.3835(17)
1.3892(16)
1.2924(15)
1.4823(17)
1.4327(14)
1.3826(15)
1.3816(17)
1.4336(16)
1.3854(19)
0.9300
C(13)–C(12)
C(10)–C(11)
N(2)–N(3)
O(1)–C(7)
N(3)–C(7)
C(11)–H(11)
C(14)–C(15)
C(16)–N(4)
C(3)–H(3)
F(1)–C(1)
1.4033(16)
1.3912(16)
1.3940(13)
1.2109(14)
1.3778(14)
0.9300
1.3806(16)
1.1402(16)
0.9300
C(13)–C(17)
C(10)–N(3)
C(8)–N(1)
N(1)–C(7)
C(17)–N(5)
C(4)–C(5)
C(14)–H(14)
C(15)–H(15)
C(5)–C(6)
1.4381(16)
1.4074(14)
1.3810(15)
1.3900(15)
1.1401(17)
1.3795(18)
0.9300
0.9300
1.3822(17)
1.363(2)
1.3520(14)
0.9300
0.9600
C(1)–C(2)
C(9)–H(9B)
C(6)–H(6)
1.370(2)
0.9600
C(2)–H(2)
C(9)–H(9C)
0.9600
0.9300
C(9)–H(9A)
Table 2
Hydrogen bonds (A, °) for I
recrystallized from water. A single crystal of compound I
was obtained from ethanol at room temperature via slow
evaporation. Yield: 0.96 g (50%). This compound was solu-
ble in common organic solvents such as ethyl acetate, dichlo-
romethane, CHCl3, DMF and DMSO. M.p: 210 °C. IR
(mmax/cmÀ1): 3204 (NH), 3067, 2813, 1697 (C@O), 1603,
1589, 1515, 1427, 1384, 1313, 1223, 1061, 848, 800, 603,
˚
N2–H2NÁ Á ÁO1
C6–H6Á Á ÁO1
C9–H9CÁ Á ÁF1
0.86
0.93
0.96
2.01
2.57
2.33
2.850(2)
3.451(3)
3.169(3)
165.1 2_456
157.2 2_557
145.3 2_667
Table 3
Bond distances (A) for II
1
˚
518. H NMR (CDCl3): d 11.63 (1H, s, NH), 7.52–7.32
(4H, m, Ar), 2.01 (3H, s, CH3) ppm. 13C NMR (CDCl3):
d 163.89, 159.01, 154.16, 143.72, 129.42, 129.23, 116.34,
115.89 and 12.14 ppm. Crystal data: C9H8FN3O, MW:
C(13)–C(14)
C(13)–C(12)
C(13)–C(17)
C(10)–C(15)
C(10)–C(11)
C(10)–N(3)
N(2)–C(8)
N(2)–N(3)
C(8)–N(1)
C(8)–C(9)
O(1)–C(7)
N(1)–C(7)
N(1)–C(4)
N(3)–C(7)
C(17)–N(5)
C(1)–C(6)
1.3835(17)
1.4033(16)
C(11)–C(12)
C(11)–H(11)
C(4)–C(5)
1.3826(15)
0.9300
1.3795(18)
1.3816(17)
1.3806(16)
0.9300
1.4336(16)
1.1402(16)
0.9300
1.3854(19)
0.9300
1.3822(17)
0.9300
1.3520(14)
1.363(2)
0.9300
1.4381(16)
1.3892(16)
1.3912(16)
1.4074(14)
1.2924(15)
1.3940(13)
1.3810(15)
1.4823(17)
1.2109(14)
1.3900(15)
1.4327(14)
1.3778(14)
1.1401(17)
1.370(2)
C(4)–C(3)
˚
˚
193.18 g/mol, triclinic, a = 6.7625(11) A, b = 7.1914(12) A,
C(14)–C(15)
C(14)–H(14)
C(12)–C(16)
C(16)–N(4)
C(15)–H(15)
C(3)–C(2)
C(3)–H(3)
C(5)–C(6)
C(5)–H(5)
F(1)–C(1)
3
˚
˚
c = 9.6173(15) A, V = 446.35(13) A , T = 293 K, space
group P1, Z = 2, l(Mo Ka) = 0.113 mmÀ1, Rint = 0.0348.
ꢀ
Summary of data containing CCDC 297124 is presented in
[23].
4.2. 1-(3,4-Dicyanophenyl)-4-(p-fluorophenyl)-3-methyl-
4,5-dihydro-1H-1,2,4-triazol-5-one (II)
C(1)–C(2)
C(2)–H(2)
C(9)–H(9A)
C(6)–H(6)
4.2.1. Method A
C(9)–H(9B)
C(9)–H(9C)
0.9600
0.9600
0.9600
0.9300
Compound I (0.5 g, 2.50 mmol) was dissolved in
dry DMF (100 ml), and 4-nitrophthalonitrile (0.44 g,
2.50 mmol) was added. After stirring for 10 min. at room
temperature, finely ground anhydrous K2CO3 (excess)
was added portion wise in 2 h. With efficient stirring for
24 h at room temperature, the reaction mixture was poured
into ice-water (500 g). The crude product was hold for 2 h
and filtered off. The mixture was washed with HCl (50 ml,
5%) and then washed with water until the filtrate became
neutral, and dried. The product was crystallized from eth-
anol. A single crystal of compound II was obtained from
ethanol at room temperature via slow evaporation. Yield:
0.5 g (60%). This compound was soluble in hot ethanol,
ethyl acetate, chloroform, DMF and DMSO. mp 209 °C.
IR (mmax/cmÀ1): 3105, 2928, 2226 (CN), 1722 (C@O),
1593, 1560, 1513, 1493, 1404, 1388, 1371, 1228, 844, 596
and 525. 1H NMR (CDCl3): d 8.50–7.40 (7H, m, Ar),
2.19 (3H, s, CH3) ppm. 13C NMR (CDCl3): d 164.52,
159.61, 150.97, 146.87, 140.96, 135.44, 129.94, 129.76,
128.18, 121.06, 120.97, 116.73, 116.27, 115.84, 115.49,
109.46 and 12.15 ppm. Crystal data: C15H10FN5O, MW:
Table 4
Hydrogen bonds (A, °) for II
˚
C(11)–H(11) Á Á ÁO(1)
C(15)–H(15) Á Á ÁN(2)
0.93
0.93
2.23
2.45
2.8737(15)
2.7864(17)
126
101
X-AREA, cell refinement: X-AREA and data reduction: X-RED
[19], program used to solve structure: SHELLXS-97 and pro-
gram used to refine structure: SHELLXL-97 [20], molecular
graphics: ORTEP 3 [21] and used to prepare material for
publication: WinGX [22] was used.
4.1. 4-(p-Fluorophenyl)-3-methyl-4,5-dihydro-1H-1,2,4-
triazol-5-one (I)
A mixture of the corresponding hydrazone (1.74 g,
0.01 mol) and p-nitroaniline (1.01 ml, 0.01 mol) was heated
to 190 °C for 3 h. The crystal formed on cooling was

4840
B. Kahveci et al. / Journal of Organometallic Chemistry 692 (2007) 4835–4842
˚
˚
295.28 g/mol,monoclinic,a = 12.5350(6) A, b = 7.9498(5)A,
4.3.2. Method B
3
˚
˚
c = 15.2826(8) A, V = 1452.52(14) A , T = 293 K, space
group P21/c, Z = 4, l(Mo Ka) = 0.099 mmÀ1, Rint = 0.0302,
summary of data containing CCDC 297125 is presented in
[24].
Compound II (0.5 g, 1.56 mmol) and DBU (1 ml) were
added in dimethylaminoethanol (DMAE) (5 ml). The mix-
ture was well stirred, and then irradiated by microwave at
350 W for 8 min. The above purification methods were also
applied to this material.
4.4. Nickel (II) phthalocyaninate (2)
4.2.2. Method B
Compound I (0.5 g, 2.50 mmol) and 4-nitrophthalonitri-
le (0.44 g, 2.50 mmol) were dissolved in DMF (5 ml).
K2CO3 (excess) were added into this solution in 2 min. with
efficient stirring. The mixture was irradiated by microwave
at 350 W for 5 min. The above purification methods were
also applied to this material.
4.4.1. Method A
A mixture of compound II (0.5 g, 1.56 mmol), DBU
(1 ml), anhydrous NiCl2 (0.05 g, 0.39 mmol) and DMAE
(10 ml) was heated to 200 °C under N2 and held at that
temperature for 2 h. After cooling to room temperature,
the dark green mixture was refluxed with ethanol (50 ml,
three times) and ethyl acetate (50 ml, three times). The
green product was filtered off, and then washed with boil-
ing water (100 ml), dried and purified by column chroma-
tography (silica gel, CH3OH:CHCl3, 1:80). Yield: 0.22 g
(42%). The green product was soluble in chloroform,
DMF and DMSO. mp >300 °C. IR (mmax/cmÀ1): 3119,
2932, 2841, 1719, 1585, 1559, 1492, 1421, 1363, 1252,
847, 584 and 531. UV–Vis (knm): 256, 638 (shoulder),
682. 1H NMR (CDCl3): d 8.50–7.90 (28H, m, Ar) and
2.20 (12H, s, CH3). 13C NMR (CDCl3): d 164.21, 161.25,
151.93, 146.88, 142.24, 135.90, 131.36, 131.28, 129.77,
122.67, 121.54, 118.02 and 29,72 ppm. Anal. Calc. for
C68H40N20O4F4Ni (1335.89 g/mol): C, 61.14; H, 3.02; N,
20.97. Found: C, 62.83; H, 3.17; N, 21.14%.
4.3. Metal-free phthalocyanine (1)
4.3.1. Method A
A mixture of compound II (0.5 g, 1.56 mmol) and hydro-
quinone (2 g, excess) was gently heated under N2 and cooled.
The mixture was heated to 200 °C under N2 and held at this
temperature for 2 h. After cooling to room temperature, the
reaction mixture was treated with boiling ethanol (50 ml)
for 1 h (tree times) and hot water (50 ml) (tree times), dried
and purified by column chromatography (silica gel,
CH3OH:CHCl3, 1:80). Yield: 0.2 g (40%). The green product
was soluble in chloroform, DMF and DMSO. mp >300 °C.
IR (mmax/cmÀ1): 3429 (NH), 3104, 2925, 2851,1722 (C@O),
1594, 1556, 1514, 1493, 1404, 1371, 1227, 844, 581 and 525.
1
4.4.2. Method B
UV–Vis (knm): 267, 673, 706. H NMR (CDCl3): d 8.56–
7.26 (28H, m, Ar) and 2.25 (12H, s, CH3). 13C NMR (CDCl3):
d 164.64, 159.81, 151.26, 146.45, 141.04, 135.36, 131.03,
130.51, 129.08, 122.06, 121.22, 117.01 and 29,71 ppm. Anal.
Calc. for C68H42N20O4F4 (1279.21 g/mol): C, 63.85; H,
3.31; N, 21.90. Found: C, 65.27; H, 3.45; N, 20.16%.
Compound II (0.5 g, 1.56 mmol) and NiCl2 (0.05 g,
0.39 mmol) were added in dimethylaminoethanol (DMAE)
(5 ml). Then the mixture was irradiated by microwave at
350 W for 8 min. The above purification methods were also
applied to this material.
2.5
2
1.5
1
0.5
0
200
300
400
500
600
700
800
900
λ ( nm )
Fig. 5. UV–Vis spectra of compounds 1 (Á Á ÁÁ Á Á), 2 (——), 3 (–Æ–Æ–), 4 (–––) and 5 (–ÆÆ–) in chloroform.

B. Kahveci et al. / Journal of Organometallic Chemistry 692 (2007) 4835–4842
4841
4.5. Zinc (II) phthalocyaninate (3)
The above purification methods were also applied to this
material.
4.5.1. Method A
A mixture of compound II (0.5 g, 1.56 mmol), DBU
(1 ml), anhydrous zinc acetate (0.071 g, 0.39 mmol) and
DMAE (10 ml) was heated to 200 °C under N2 and held
at that temperature for 2 h. After cooling to room temper-
ature, the green mixture was refluxed with ethanol (50 ml,
three times) and ethyl acetate (50 ml, three times), and
filtered off. The product was washed with boiling water
(100 ml) and boiling methanol (50 ml). The green product
was soluble in chloroform and filtered off, dried and
purified by column chromatography (silica gel, CH3OH:
CHCl3, 1:80). Yield: 0.30 g (57%). The green product was
soluble in chloroform, DMF and DMSO. mp >300 °C.
IR (mmax/cmÀ1): 3104, 2926, 2854,1722,1593, 1561,
1513,1493, 1371, 1228, 844, 585 and 525. UV–Vis (knm):
4.7. Cobalt (II) phthalocyaninate (5)
4.7.1. Method A
A mixture of compound II (0.5 g, 1.56 mmol), DBU
(1 ml), anhydrous CoCl2 (0.05 g, 0.39 mmol), ammonium
molybdate (excess) and DMAE (10 ml) was heated to
200 °C under N2 and held at that temperature for 2 h. After
cooling to room temperature, the green mixture was
refluxed with ethanol (50 ml, three times) and ethyl acetate
(50 ml, three times), and filtered off, dried and purified by
column chromatography (silica gel, CH3OH:CHCl3,
1:80). The green product was soluble in chloroform and fil-
tered off, and dried. Yield: 0.20 g (38%). The green product
was soluble in chloroform, DMF and DMSO. mp >300 °C.
IR (mmax/cmÀ1): 3105, 2927, 2854, 1723, 1594, 1560, 1513,
1490, 1373, 1227, 845, 586 and 525. UV–Vis (knm): 257,
648 (shoulder), 682. Anal. Calc. for C68H40N20O4F4-
Co(1336.13 g/mol): C, 61.13; H, 3.02; N, 20.97. Found:
C, 63.17; H, 3.19; N, 22.53%.
1
288, 351, 655 (shoulder), 689. H NMR (CDCl3): d 8.50–
7.83 (28H, m, Ar) and 2.10 (12H, s, CH3). 13C NMR
(CDCl3): d 164.76, 160.12, 151.89, 146.78, 141.75, 135.88,
131.25, 131.02, 129.27, 122.21, 121.35, 117.12 and
28,89 ppm. Anal. Calc. for C68H40N20O4F4Zn (1342.59
g/mol): C, 60.83; H, 3.00; N, 20.86. Found: C, 61.21; H,
3.19; N, 20.18%.
4.7.2. Method B
Compound II (0.5 g, 1.56 mmol) and CoCl2 (0.05 g,
0.39 mmol) were well stirred in DMAE (5 ml). Then the
mixture was irradiated by microwave at 350 W for 8 min.
The above purification methods were also applied to this
material.
4.5.2. Method B
Compound II (0.5 g, 1.56 mmol) and anhydrous
Zn(CH3COO)2 (0.071 g, 0.39 mmol) were added in dimeth-
ylaminoethanol (DMAE) (5 ml). Then the mixture was
irradiated by microwave at 350 W for 8 min. The above
purification methods were also applied to this material.
5. Supplementary material
4.6. Copper (II) phthalocyaninate (4)
CCDC 297124 and 297125 contain the supplementary
crystallographic data for 4-(p-fluorophenyl)-3-methyl-4,5-
dihydro-1H-1,2,4-triazol-5-one and 1-(3,4-dicyanophenyl)-
4-(p-fluorophenyl)-3-methyl-4,5-dihydro-1H-1,2,4-triazol-
5-one. These data can be obtained free of charge via http://
www.ccdc.cam.ac.uk/conts/retrieving.html, or from the
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or
e-mail: deposit@ccdc.cam.ac.uk.
4.6.1. Method A
A mixture of compound II (0.5 g, 1.56 mmol), CuCl
(0.038 g, 0.39 mmol), urea (1 g, excess) and DMAE
(10 ml) was heated at 180–190 °C for 2 h under N2. After
cooling to room temperature, the mixture was diluted with
ethanol (50 ml), refluxed and filtered off. The resultant
green product was washed with NH4OH (50 ml, 24%)
and then with water until the filtrate was neutral. The prod-
uct was refluxed with ethanol (50 ml, three times) and ethyl
acetate (50 ml, three times), then the liquor filtered, dried
and purified by column chromatography (silica gel,
CH3OH:CHCl3, 1:80). Yield: 0.25 g (48%). The product
was soluble in chloroform, DMSO and DMF. mp
>300 °C. IR (mmax/cmÀ1): 3103, 2925, 2852, 1721, 1596,
1557, 1515, 1494, 1403, 1372, 1228, 845, 582 and 524.
UV–Vis (knm): 283, 634 (shoulder), 685. Anal. Calc. for
C68H40N20O4F4Cu (1340.74 g/mol): C, 60.92; H, 3.01; N,
20.89. Found: C, 62.54; H, 3.19; N, 22.14%.
Acknowledgement
This work was supported by the research fund of the
Karadeniz Technical University of Trabzon.
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ac.uk/data_request/cif.
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