Synthesis and characterization of a new organo-soluble metal-free and metallophthalocyanines bearing flexible moieties

Article abstract of DOI:10.1016/j.poly.2011.01.005

This paper describes a new symmetric metal-free phthalocyanine and its transition metal complexes which were prepared by a condensation of 1,2-dihydroacenaphthylen-1-ol 1 and 4-nitro phthalonitrile 2 with Co(II), Ni(II), Cu(II), and Zn(II) salts in 2-(dim

Full text of DOI:10.1016/j.poly.2011.01.005

Polyhedron 30 (2011) 1085–1090
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Polyhedron
journal homepage: www.elsevier.com/locate/poly
Synthesis and characterization of a new organo-soluble metal-free
and metallophthalocyanines bearing flexible moieties
⇑
Asiye Nas, Halit Kantekin
Department of Chemistry, 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:
This paper describes a new symmetric metal-free phthalocyanine and its transition metal complexes
which were prepared by a condensation of 1,2-dihydroacenaphthylen-1-ol 1 and 4-nitro phthalonitrile
2 with Co(II), Ni(II), Cu(II), and Zn(II) salts in 2-(dimethylamino)ethanol, respectively. The novel phthal-
ocyanines bearing oxygen donor atoms on peripheral position have been characterized by IR, UV–Vis, 1H
NMR, 13C NMR, Mass spectra and elemental analysis. The thermal behaviours of 4–8 were investigated by
TG/DTA.
Received 30 September 2010
Accepted 9 January 2011
Available online 19 January 2011
Keywords:
1,2-Dihydroacenaphthylen-1-ol
Metallophthalocyanine
Microwave-assisted
4-Nitrophthalonitrile
Thermal stability
Ó 2011 Elsevier Ltd. All rights reserved.
1. Introduction
used in photodynamic cancer therapy (PDT) and other processes
by visible light [23–27].
Since their first synthesis early in the last century, phthalocya-
nines, which are also called as blue-green products, are produced
with increasing amount and diversity in many countries per year.
The syntheses of metal-free and metallophthalocyanines play an
extremely important role not only in the development of chemistry
and its related branches but also in the development of current
economy.
Phthalocyanines (pcs) and their derivatives have attracted a
good deal of interest due to their fascinating features such as high
thermal stability [1], semi-conductivity [2], and besides in several
application areas such as laser dyes, new red-sensitive photocopy-
ing applications [3,4], and optical computer read/write discs. [5].
Pcs are an important industrial commodity which was firstly used
in productions of inks, and also colouring for plastics, metal sur-
faces, dye stuffs for jeans and other clothing [3]. Phthalocyanines’
electronic and optical properties for use in many applications, such
as chemical sensors [6–9], liquid crystals [10–12], catalysis, consid-
erably depend upon the peripheral and axial substitution patterns
[13,14]. Besides, pcs can also be subsequently used in various
implementation areas, for instance, production of solar energy con-
versions [15,16], antimycotic materials [17], corrosion inhibitors
[18,19], for the prevention and treatment of infectious diseases
[20], eye [21] and neurodegenerative diseases [22]. In the last
few years, substituted phthalocyanine derivatives have also been
Pcs can be obtained by the classical template reactions of pht-
halonitrile, cyano-benzamide, phthalic acid and phthalamide with
metal salts in high-boiling nonaqueous solvents at required tem-
peratures [28,29]. On the other hand, microwave processing tech-
niques have attracted
a great deal of potential interest as
alternatives to classical thermal processing techniques because of
the diverse and convenient advantages of microwave heating,
which is selective, direct, rapid, internal, and controllable [30,31].
It is well known that microwave (MW) irradiation can accelerate
a great number of chemical processes; in particular, the reaction
time and energy input are supposed to be mostly reduced in the
chemical processes that are run for a long time at high tempera-
tures under conventional conditions [32].
The present work contains the preparation and the character-
ization of metal-free (4) and metallophthalocyanines (5–8)
containing 1,2-dihydroacenaphthylen-1-ol moieties by the micro-
wave irradiation. Additionally, we have carried out the thermo-
gravimetric study of tetrasubstituted metal-free phthalocyanine
(4) and metallophthalocyanines (5–8) to compare their thermal
stabilities.
2. Experimental
All reactions were carried out under a dry nitrogen atmosphere
using Standard Schlenk techniques. All chemicals, solvents, and
reagents were of reagent grade quality and were obtained from
commercial suppliers. All reagents and solvents were dried and
⇑
Corresponding author. Tel.: +90 462 377 25 89; fax: +90 462 325 31 96.
E-mail address: halit@ktu.edu.tr (H. Kantekin).
0277-5387/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2011.01.005

1086
A. Nas, H. Kantekin / Polyhedron 30 (2011) 1085–1090
OH
CN
CN
CN
dry DMF
50 oC
N2
O
O2N
CN
(3)
(2)
(1)
n-pentanol
DBU
160 oC
O
O
N
NH
N
N
N
N
HN
N
O
O
Scheme 1. The synthesis of the metal-free phthalocyanine (4) by using classical method.
purified before use as described by Perrin and Armarego [33]. FT-IR
spectra were obtained using a Perkin–Elmer 1600 FTIR spectropho-
tometer with the samples prepared as KBr pellets. Elemental anal-
yses and metal contents of novel compounds were performed on a
Vario MICRO Elemental Analyser at Anadolu University in Turkey.
A Seiko II Exstar 6000 thermal analyzer was used to record the DTA
curves under a nitrogen atmosphere with a heating rate of
20 °C minÀ1 in the temperature range of 30–900 °C using platinum
crucibles. UV–Vis spectra were recorded using a Unicam UV–Vis
spectrometer operating in the wavelength range of 200–850 nm
with quartz cells. All 1H and 13C NMR spectra were recorded in
CDCl3 on a Varian Mercury NMR spectrometer operating at
200 MHz. Chemical shifts are expressed in ppm relative to TMS
as an internal standard. Mass spectra were recorded using a
Micromass Quatro LC/ULTIMA LC–MS/MS spectrometer. Melting
points were measured on an electrothermal apparatus. Domestic
microwave oven was used for carrying out all synthesis of
phthalocyanines.
uct precipitated. This product was filtered off, washed with dis-
tilled water and diethylether. Finally, obtained crude product was
crystallized from ethanol. Yield: 1.2 g (69%), m.p.: 176–177 °C.
Anal. Calc. for C20H12N2O: C, 81.07; H, 4.08; N, 9.45. Found: C,
81.03; H, 4.05; N, 9.48%. IR (KBr tablet) vmax/cmÀ1: 3081 (Ar-H),
2920–2850 (Aliph. C–H), 2227 (C„N), 1594, 1497, 1325, 1253,
1165, 1019, 838, 780. 1H NMR (CDCl3) (d: ppm): 7.85–7.81 (d,
3H, Ar-H), 7.64 (s, 1H, Ar-H), 7.59–7.56 (t, 2H, Ar-H), 7.43–7.34
(m, 3H, Ar-H), 6.31 (t, 1H, CH), 3.70 (d, 2H, CH2). 13C NMR (CDCl3)
(d: ppm): 161.32, 140.58, 140.18, 137.90, 135.62, 131.52, 128.73,
128.29, 126.48, 123.59, 121.85, 120.72, 120.55, 120.49, 117.85,
115.90, 115.51, 107.78, 80.41, 38.87. MS (FAB), (m/z): 296[M]+.
2.2. Metal-free phthalocyanine (4)
A standard Schlenk tube was charged with 4-(1,2-dihydroace-
naphthylen-1-yloxy)phthalonitrile 3 (0.2 g, 0.675 mmol), 3 ml of
anhydrous n-pentanol and 1,8-diazabicyclo[5.4.0] undec-7-ene
(DBU, 2 drops) under a nitrogen atmosphere and degassed several
times. Then the reaction mixture was stirred at 160 °C for 12 h.
After cooling to room temperature, the reaction mixture was stir-
red with ethanol (30 ml) to precipitate the product. The precipi-
tated dark green product 4 was filtered off, washed with hot
ethanol (3 Â 50 ml) and dried in vacuo over P2O5. Finally, it was
purified by preparative thin layer chromatography (TLC) using so-
lely chloroform solvent system. This product is soluble in CHCl3,
CH2Cl2, THF, DMF, DMSO and pyridine. Yield: 40 mg (20%), m.p.:
269–292 °C. Anal. Calc. for C80H50N8O4: C, 80.93; H, 4.24; N, 9.44.
2.1. 4-(1,2-Dihydroacenaphthylen-1-yloxy)phthalonitrile (3)
1,2-Dihydroacenaphthylen-1-ol 1 (1 g, 5.88 mmol) was dis-
solved in anhydrous DMF (8 ml) under a nitrogen atmosphere at
50 °C and 4-nitrophthalonitrile 2 [34] (1.02 g, 5.88 mmol) was
added to the solution. After stirring for 15 min, finely ground dry
K2CO3 (2.84 g, 20.58 mmol) was added portionwise within 2 h with
efficient stirring. The reaction mixture was stirred under a nitrogen
atmosphere at 50 °C for 3 days. The reaction mixture was moni-
tored by thin layer chromatography (TLC) using chloroform solvent
system. At the end of the elapsed period, the obtained mixture was
poured into ice (100 g) and it was shown that the light-green prod-
Found: C, 80.90; H, 4.26; N, 9.49%. IR (KBr tablet) vmax/cmÀ1
:
3285 (N–H), 3039 (Ar-H), 2916–2847 (Aliph. C–H), 1602, 1520,
1477, 1418, 1344, 1236, 1096, 1015, 936, 776, 746. 1H NMR (CDCl3)

A. Nas, H. Kantekin / Polyhedron 30 (2011) 1085–1090
1087
745. 1H NMR (CDCl3) (d: ppm): 7.84–7.70 (d, 4H, Ar-H), 7.58–7.53
(d, 20H, Ar-H), 7.36–7.33 (m, 12H, Ar-H), 6.38 (t, 4H, CH), 3.75 (d,
8H, CH2). 13C NMR (CDCl3) (d: ppm): 173.30, 167.81, 163.57,
163.32, 141.35, 140.71, 135.51, 131.50, 128.60, 128.29, 126.17,
125.82, 123.42, 122.17, 121.83, 120.34, 109.59, 80.32, 39.09,
CN
CN
O
29.35. UV–Vis (CHCl3): kmax/nm: [(10À5
e
dm3 molÀ1 cmÀ1)]: 691
(3)
(5.27), 620 (4.60), 360 (4.98). MS (FAB), (m/z): 1251[M+1]+.
2.4. Copper(II) phthalocyanine (6)
175 oC
350 W
DMAE
4-(1,2-Dihydroacenaphthylen-1-yloxy)phthalonitrile
3 (0.2 g,
0.675 mmol) was dissolved in 2-(dimethylamino)ethanol (2 ml)
and dry CuCl2 (22.69 mg, 0.168 mmol) was added to this solution.
The reaction mixture was irradiated in a microwave oven at
175 °C, 350 W, for 9 min. After the reaction mixture was cooled to
room temperature, 30 ml of ethanol was added to the mixture
and stirred overnight. At the end of this period, this mixture was fil-
tered off. The green crude product was refluxed with ethanol for
5 h. Then it was filtered off again. Obtained dark green product
was dried in vacuo over P2O5. Finally, it was purified by preparative
thin layer chromatography (TLC) using solely chloroform solvent
system. This product is soluble in CHCl3, CH2Cl2, THF, DMF, DMSO
and pyridine. Yield: 60 mg (28%), m.p.: 364–414 °C. Anal. Calc. for
O
O
N
N
N
N
M
N
N
N
C
80H48N8O4Cu: C, 76.94; H, 3.87; N, 8.97. Found: C, 76.90; H, 3.85;
N, 8.96%. IR (KBr tablet) vmax/cmÀ1: 3032 (Ar-H), 2923–2846 (Aliph.
N
O
C–H), 1596, 1477, 1341, 1270, 1226, 1174, 1096, 1053, 869, 779.
UV–Vis (CHCl3): kmax/nm: [(10À5
e
dm3 molÀ1 cmÀ1)]: 690 (5.27),
O
618 (4.69), 291 (4.98), 264 (5.09). MS (FAB), (m/z): 1287[M+K]+.
2.5. Nickel(II) phthalocyanine (7)
4-(1,2-Dihydroacenaphthylen-1-yloxy)phthalonitrile
3 (0.2 g,
0.675 mmol) was dissolved in 2-(dimethylamino)ethanol (2 ml)
and dry NiCl2 (21.84 mg, 0.168 mmol) was added to this solution.
The reaction mixture was irradiated in a microwave oven at
175 °C, 350 W, for 7 min. After the reaction mixture was cooled
to room temperature, 30 ml of ethanol was added to the mixture
and stirred overnight. At the end of this period, this mixture was
filtered off. The green crude product was refluxed with ethanol
for 5 h. Then it was filtered off again. Obtained dark green product
was dried in vacuo over P2O5. Finally, it was purified by preparative
thin layer chromatography (TLC) using solely chloroform solvent
system. This product is soluble in CHCl3, CH2Cl2, THF, DMF, DMSO
and pyridine. Yield: 88 mg (42%), m.p.: 260–296 °C. Anal. Calc. for
Compound
M
5
6
7
8
Zn+2
Cu+2
Ni+2
Co+2
Scheme 2. The synthesis of the metallophthalocyanines (5–8) by using microwave
process.
(d: ppm): 7.86–7.74 (d, 4H, Ar-H), 7.62–7.53 (d, 20H, Ar-H), 7.39–
7.36 (m, 12H, Ar-H), 6.32 (t, 4H, CH), 3.65 (d, 8H, CH2). 13C NMR
(CDCl3) (d: ppm): 174.20, 166.71, 163.54, 163.27, 141.24, 140.62,
134.73, 130.72, 126.57, 126.29, 125.15, 124.11, 123.04, 122.44,
121.27, 120.97, 109.33, 80.78, 40.01, 35.52. UV–Vis (CHCl3): kmax
/
C80H48N8O4Ni: C, 77.24; H, 3.89; N, 9.01. Found: C, 77.22; H,
nm: [(10À5
e
dm3 molÀ1 cmÀ1)]: 712 (5.15), 679 (5.12), 650
3.86; N, 9.04%. IR (KBr tablet) vmax/cmÀ1: 3038 (Ar-H), 2925–
2854 (Aliph. C–H), 1732, 1601, 1465, 1377, 1274, 1122, 1067,
778. 1H NMR (CDCl3) (d: ppm): 7.80–7.71 (d, 4H, Ar-H), 7.57–
7.53 (d, 20H, Ar-H), 7.37–7.34 (m, 12H, Ar-H), 6.34 (t, 4H, CH),
3.55 (d, 8H, CH2). 13C NMR (CDCl3) (d: ppm): 170.96, 148.24,
142.69, 141.43, 138.26, 137.48, 131.28, 130.43, 128.37, 127.63,
126.38, 123.14, 122.13, 121.54, 120.30, 119.84, 105.00, 92.14,
(4.93), 618 (4.88), 305 (5.15). MS (FAB), (m/z): 1185 [MÀ2]+.
2.3. Zinc(II) phthalocyanine (5)
4-(1,2-Dihydroacenaphthylen-1-yloxy)phthalonitrile
3 (0.2 g,
0.675 mmol) was dissolved in 2-(dimethylamino)ethanol (2 ml)
and dry Zn(CH3COO)2 (30.74 mg, 0.168 mmol) was added to this
solution. The reaction mixture was irradiated in a microwave oven
at 175 °C, 350 W, for 7 min. After the reaction mixture was cooled
to room temperature, 30 ml of ethanol was added to the mixture
and stirred overnight. At the end of this period, this mixture was fil-
tered off. The green crude product was refluxed with ethanol for
5 h. Then it was filtered off again. Obtained dark green product
was dried in vacuo over P2O5. Finally it was purified by preparative
thin layer chromatography (TLC) using solely chloroform solvent
system. This product is soluble in CHCl3, CH2Cl2, THF, DMF, DMSO
and pyridine. Yield: 67 mg (32%), m.p.: 269–297 °C. Anal. Calc. for
55.42, 29.95. UV–Vis (CHCl3): kmax/nm: [(10À5
e
dm3 molÀ1 cmÀ1)]:
681 (5.23), 622 (5.11), 290 (5.04). MS (FAB), (m/z): 1243[M]+.
2.6. Cobalt(II) phthalocyanine (8)
4-(1,2-Dihydroacenaphthylen-1-yloxy)phthalonitrile
3 (0.2 g,
0.675 mmol) was dissolved in 2-(dimethylamino)ethanol (2 ml)
and dry CoCl2 (21.84 mg, 0.168 mmol) was added to this solution.
The reaction mixture was irradiated in a microwave oven at 175 °C,
350 W, for 10 min. After the reaction mixture was cooled to room
temperature, 30 ml of ethanol was added to the mixture and stir-
red overnight. At the end of this period, this mixture was filtered
off. The green crude product was refluxed with ethanol for 5 h.
Then it was filtered off again. Obtained dark green product was
C
80H48N8O4Zn: C, 76.83; H, 3.87; N, 8.96. Found: C, 76.86; H, 3.82;
N, 8.94%. IR (KBr tablet) vmax/cmÀ1: 3038 (Ar-H), 2917–2857 (Aliph.
C–H), 1606, 1483, 1396, 1339, 1275, 1224, 1097, 1049, 943, 779,

1088
A. Nas, H. Kantekin / Polyhedron 30 (2011) 1085–1090
Fig. 1. 13C NMR spectrum of 4-(1,2-dihydroacenaphthylen-1-yloxy)phthalonitrile (3) in CDCl3.
Fig. 2. Mass spectrum of 4-(1,2-dihydroacenaphthylen-1-yloxy)phthalonitrile (3).
dried in vacuo over P2O5. Finally, it was purified by preparative thin
layer chromatography (TLC) using solely chloroform solvent sys-
tem. This product is soluble in CHCl3, CH2Cl2, THF, DMF, DMSO
and pyridine. Yield: 76 mg (36%), m.p.: 264–291 °C. Anal. Calc. for
C80H48N8O4Co: C, 77.23; H, 3.89; N, 9.01; Co, 4.74. Found: C,
77.27; H, 3.91; N, 9.05, Co, 4.76%. IR (KBr tablet) vmax/cmÀ1: 3032

A. Nas, H. Kantekin / Polyhedron 30 (2011) 1085–1090
1089
(Ar-H), 2923–2853 (Aliph. C–H), 1606, 1517, 1475, 1413, 1342,
tal analysis results of the dicyano compound and phthalocyanines
demonstrated a good agreement with the calculated values.
In the IR spectrum of 3, the disappearance of broad –OH peaks
and the presence of Ar–O–C at 1253 cmÀ1 and the presence of
sharp C„N functional group at 2227 cmÀ1 supported the forma-
tion of desired compound 3. The 1H NMR spectrum of 3 indicated
that the proton of –OH group of compound 1 disappeared, as ex-
pected. In addition, new signals belonging to aromatic protons ap-
peared in the range of d = 7.85–7.34 ppm, and aliphatic protons at
6.31 and 3.70 ppm. The 13C NMR spectrum of 3 in deuterated CDCl3
gave new signals at d = 115.9 and 115.51 ppm belonging to dicyano
carbon atoms (Fig. 1). In the MS (FAB) spectrum of 3, we also ob-
served the molecular ion peak at (m/z): 296[M]+, which confirmed
the proposed structure (Fig. 2).
When the IR spectra of compound 3 compared with compound
4, the stretching vibrations at 2227 cmÀ1 belonging to C„N func-
tional group of 3 disappeared after formation of metal-free phtha-
locyanine (4). The weak vibration at 3285 cmÀ1 indicated the
presence of N–H stretching vibrations of the inner phthalocyanine
core in metal-free phthalocyanine (4). On the other hand, this
vibration band disappeared in the IR spectra of metallophthalocy-
anines. In the 1H NMR spectrum of 4, the NH protons could not be
observed because of the strong aggregation of the molecules [35].
In the MS (FAB) spectrum of 4, we observed the molecular ion peak
at (m/z): 1185 [MÀ2]+, which confirmed the proposed structure.
The IR spectra of metallophthalocyanines, which were very sim-
ilar to metal-free phthalocyanine (4), clearly indicated the forma-
tion of compounds 5–8 with the disappearance of the C„N
functional group of 3. Because of their paramagnetic nature, 1H
NMR and 13C NMR of the copper(II) phthalocyanine 6 and cobalt
(II) phthalocyanine 8 were precluded. In the MS (FAB) spectra of
5–8, we observed the molecular ion peaks at (m/z): 1251[M+1]+,
(m/z): 1287[M+K]+, (m/z): 1243[M]+, (m/z): 1244[M+1]+, respec-
tively, which confirmed the proposed structure.
1227, 1123, 1095, 778, 752. UV–Vis (CHCl3): kmax/nm: [(10À5
e
dm3 molÀ1 cmÀ1)]: 684 (5.18), 621 (4.81), 366 (4.80). MS (FAB),
(m/z): 1244[M+1]+.
3. Results and discussion
The synthesis of substituted target metal-free phthalocyanine
(4) and metallophthalocyanines (5–8) were outlined in Schemes
1 and 2. Initially, the synthesis of 4-(1,2-dihydroacenaphthylen-
1-yloxy)phthalonitrile (3) was obtained by base-catalyzed nucleo-
philic aromatic nitro displacement of 4-nitrophthalonitrile (2) with
the –OH function of 1,2-dihydroacenaphthylen-1-ol (1). This reac-
tion was carried out in anhydrous DMF containing finely ground
dry K2CO3 as a base in a Schlenk system under a nitrogen atmo-
sphere at 50 °C for 3 days. Compound (3) was obtained in 69%
yield. A new metal-free phthalocyanine (4) was accomplished by
cyclotetramerization reaction of dicyano compound (3) in n-pent-
anol with the presence of a few drops of 1,8-diazabicyclo[5.4.0] un-
dec-7-ene (DBU) as a strong base at 160 °C under a nitrogen
atmosphere. The conversion of this new dicyano compound (3)
into the metallophthalocyanines (5–8) was accomplished by cyclo-
tetramerization in 2-(dimethylamino)ethanol (DMAE) in the pres-
ence of metal salts (Zn(CH3COO)2, CuCl2, NiCl2, CoCl2) at 175 °C,
350 W by microwave irradiation in the range of 7–10 min. In con-
trast to the analogous compounds with bulky moieties, phthalocy-
anines generally have low solubility. However, the novel
phthalocyanines (4–8) that synthesized are soluble in CHCl3,
CH2Cl2, THF, DMF, DMSO and pyridine.
The characterization of all new products were performed by a
combination of methods involving elemental analysis, IR, 1H
NMR, 13C NMR, UV–Vis spectroscopy, mass spectrometry. Elemen-
It is known that the best confirming indicator for the phthalocy-
anines is their UV–Vis spectra. The spectra of metallophthalocya-
nine complexes consist of an intense absorption band in the
visible region traditionally near 670 nm called the Q band and a
generally weaker band near 340 nm called the Soret or B band both
being
attributed to the
p
–
p⁄ transitions [36]. The Q band of all the compounds was
p–
p⁄ transition from the highest occupied molec-
ular orbital to the lowest unoccupied molecular orbital of the
phthalocyanine (À2) ring [37,38].
In the electronic spectrum of the metal-free phthalocyanine (4)
(Fig. 3) in chloroform at the room temperature, the characteristic
split Q absorption band was observed with absorptions at kmax
:
679 and 712 nm with shoulders at 650 and 618 nm as expected.
In the UV–Vis absorption spectra of zinc(II) 5, copper(II) 6, nicke-
l(II) 7, cobalt(II) 8 phthalocyanines (Figs. 3 and 4) in chloroform
at the room temperature, the absorptions were observed as ex-
Fig. 3. UV–Vis spectra of compounds 4 (—), 5 (- - -) and 6 (. . .) in chloroform.
pected. It was observed that the intense Q absorption at kmax
:
691, 690, 681 and 684 nm with weaker absorptions at 620, 618,
622 and 621 nm, respectively (Figs. 3 and 4). Besides, the UV–Vis
spectra of 5, 6, 7 and 8 in chloroform were observed the intense
B absorption at kmax: 360, (264 and 291), 290 and 366 nm as
expected.
Table 1
Thermal properties of the novel phthalocyanines.
Compound
M
Initial decomposition
Main decomposition
temperature in °C
temperature in °C
4
5
6
7
8
2H
Zn
Cu
Ni
269.9
269.6
364.4
260.5
264.9
292.2
297.7
414.3
296.9
291.9
Co
Fig. 4. UV–Vis spectra of compounds 7 (—) and 8 (- - -) in chloroform.

1090
A. Nas, H. Kantekin / Polyhedron 30 (2011) 1085–1090
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of the metal-free (4) and metallophthalocyanines (5–8) were
investigated by TG/DTA. Though the potential thermal stabilities
of phthalocyanines are well known, the obtained novel phthalocy-
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tial and main decomposition temperatures were given in Table 1.
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6 > 4 > 5 > 8 > 7.
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4. Conclusion
We have synthesized and characterized a new symmetrically
substituted metal-free phthalocyanine and its transition metal
complexes (5–8) which were prepared by a condensation of 1,2-
dihydroacenaphthylen-1-ol 1 and 4-nitro phthalonitrile 2 with
Co(II), Ni(II), Cu(II), or Zn(II) salts in DMAE, respectively. Phthalo-
nitrile compound 3 was synthesized by reaction of 1,2-dihydroace-
naphthylen-1-ol (1) with 4-nitro phthalonitrile (2). The structures
of the new compounds were both characterized and illuminated by
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Acknowledgement
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This study was supported by the Research Fund of Karadeniz
Technical University, Project no: 2006.111.02.1 (Trabzon-Turkey).
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