The synthesis and characterization of metal-free and metallophthalocyanine polymers by microwave irradiation containing diazadithia macrocyclic moieties

Article abstract of DOI:10.1016/j.dyepig.2009.10.021

A tetranitrile monomer was synthesized by nucleophilic aromatic substitution of N,N′-(2,2′-(propane-1,3-diylbis(sulfanediyl))bis(ethane-2,1-diyl))bis(4-methylbenzenesulfonamide) onto 4-nitrophthalonitrile. A metal-free phthalocyanine polymer was prepared by the reaction of the tetranitrile monomer under N₂ in the presence of 2-(dimethylamino)ethanol at 145?°C for 24?h. Zinc(II), copper(II), cobalt(II), nickel(II), lead(II), phthalocyanine polymers were prepared by reaction of the tetranitrile with the chlorides of zinc (II), copper (II), cobalt (II), nickel (II), lead (II), employing microwave irradiation in the presence 2-(dimethylamino)ethanol at 175?°C, 350?W for 10?min. The thermal stabilities of the phthalocyanine compounds were determined by thermogravimetric analysis. The new compounds were characterized by a combination of IR, ¹H NMR, ¹³C NMR, UV-vis, elemental analysis and MS spectral data.

Full text of DOI:10.1016/j.dyepig.2009.10.021

Dyes and Pigments 85 (2010) 177e182
Contents lists available at ScienceDirect
Dyes and Pigments
journal homepage: www.elsevier.com/locate/dyepig
The synthesis and characterization of metal-free and metallophthalocyanine
polymers by microwave irradiation containing diazadithia macrocyclic moieties
,
Elif Çelenk Kaya a, Hülya Karadeniz b, Halit Kantekin c
*
a Gümüs¸hane Üniversitesi, 29000 Gümüs¸hane, Turkey
b Council of Forensic Medicine, 61080 Trabzon, Turkey
c 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
A tetranitrile monomer was synthesized by nucleophilic aromatic substitution of N,N0-(2,20-(propane-1,3-
diylbis(sulfanediyl))bis(ethane-2,1-diyl))bis(4-methylbenzenesulfonamide) onto 4-nitrophthalonitrile. A
metal-free phthalocyanine polymer was prepared by the reaction of the tetranitrile monomer under N2 in
the presence of 2-(dimethylamino)ethanol at 145 ꢀC for 24 h. Zinc(II), copper(II), cobalt(II), nickel(II), lead
(II), phthalocyanine polymers were prepared by reaction of the tetranitrile with the chlorides of zinc (II),
copper (II), cobalt (II), nickel (II), lead (II), employing microwave irradiation in the presence 2-(dimethy-
lamino)ethanol at 175 ꢀC, 350 W for 10 min. The thermal stabilities of the phthalocyanine compounds were
determined by thermogravimetric analysis. The new compounds were characterized by a combination of
IR, 1H NMR, 13C NMR, UVevis, elemental analysis and MS spectral data.
Article history:
Received 30 June 2009
Received in revised form
23 October 2009
Accepted 26 October 2009
Available online 11 November 2009
Keywords:
Phthalonitrile
Polymeric phthalocyanines
Metallophthalocyanine
Microwave-assisted
Macrocyclic compound
Mixed-donor macrocyclic
Ó 2009 Elsevier Ltd. All rights reserved.
1. Introduction
photo-generated excitons occurs leading to photocurrent in the
external circuit [16e18].
Phthalocyanines are an important class of organic materials
with a very stable electronic configuration which makes them an
important class of functional materials [1]. Metal-free phthalocy-
anine and its metal complexes have been intensively investigated
since the early-1930s. Phthalocyanine chemistry is undergoing
a renaissance because phthalocyanines and many of their deriva-
tives exhibit singular and unconventional physical properties
which are interesting for applications in materials science [2]. They
can be used in jet printing inks [3], catalysts [4], gas sensors [5] and
photonic devices [6,7] and because of the flexibility in tailoring
the electrical and optical properties, phthalocyanines can be used
in many devices like: fuel cells, organic metals, electronic media,
photoelectrical detectors, xerographic media, field effect transis-
tors [8], light-emitting diodes [9e11], optical recording, optical
memories, information displays [12], hole-burning memories,
light-limiters, lasers, non-linear optical elements, etc. [13]. The
photoactive semiconducting properties of phthalocyanine mono-
mers and polymers makes possible the production of low cost,
flexible [14,15]. In organic photovoltaic devices, dissociation of
Recently, phthalocyanines have been used as photosensitizers in
the treatment of cancer [19e21] and intimal hyperplasia [22] for
photodynamic therapy (PDT). Due to the intense absorption in the
visible region, high efficiency to generate reactive oxygen species
(such as singlet oxygen), and low dark toxicity, phthalocyanines
have been used in this avenue for the treatment of various cancers
and photoinactivation of viruses [23e25]. PDT dyes are recognized
as efficient sensitizers of singlet oxygen and the involvement of
singlet oxygen in the PDT process is now widely accepted, thus, the
relative photooxidation rate by singlet oxygen catalyzed by these
dyes has been examined.
In the recent years, it has been recognized that microwave
processing has attracted potential as an alternative to classical
processing because of the inherent advantages of microwave
heating, which is selective, direct, rapid, internal, and controllable
[26]. Microwave processing has therefore been applied in such
varied fields as pulp drying, food cooking, organic synthesis,
ceramic sintering, composite joining, chemical analyses, and waste
treatment [27,28].
Being discovered in 1950s, polymeric phthalocyanine remains an
enigmatic material and many of its intrinsic properties are known
rather insufficiently [29]. Polymeric phthalocyanines were mainly
prepared via polycyclotetramerization reactions of bifunctional
* Corresponding author. Fax: þ90 0462 325 31 96.
E-mail address: halit@ktu.edu.tr (H. Kantekin).
0143-7208/$ e see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.dyepig.2009.10.021

178
E.Ç. Kaya et al. / Dyes and Pigments 85 (2010) 177e182
monomers such as variousnitriles or tetracarboxylic acid derivatives
in the presence of metal salts or metals.
EtOHeMeOH and dried in vacuo. Yield: 0.057 g. (37%), mp:
>300 ꢀC. Anal. Calcd. (for CN end groups) (C148H138N24O16S16)n (%):
C, 58.82; H, 4.60; N, 11.12; S, 16.98. Found: C, 57.73; H, 4.76; N, 11.82;
S, 17.17. IR (KBr pellets): 3436 (NeH), 3058 (AreH), 2921e2851
(Aliph. CeH), 2214 (C^N), 1722, 1640 (C]C), 1593, 1465e1158 (S]
O), 1401 (CH2eSeC), 1245 cmꢁ1 (AreNeC), 1090, 814. 1H NMR
We have previously described the synthesis of novel tetrakis
[N,N0-(2,20-(propane-1,3-diylbis(sulfanediyl))bis(ethane-2,1-diyl))
bis(4-methylbenzenesulfonamide)-phthalocyanine] and its metal
derivatives [30] and new polymeric phthalocyanines substituted
with pyridine through methyleneoxy bridges [31]. In the present
paper, we describe the synthesis and characterization of metal-free
4 and metallophthalocyanine polymers 5, 6, 7, 8 and 9 by micro-
wave irradiation.
(DMSO):
d
¼ 7.74 (m,12H, AreH), 7.71 (m,16H, AreTs), 7.49 (m,16H,
AreTs), 7.23 (m, 12H, AreH), 3.86 (t, 16H, NeCH2), 2.75 (t, 16H,
SeCH2), 2.68 (t, 16H, SeCH2), 2.39 (s, 24H, CH3), 1.75 (m, 8H, CH2).
13C NMR (DMSO):
d
¼ 162.16, 151.43 (AreC), 144.76, 136.54, 134.88
(AreTseC), 130.15, 128.31 (AreTseCH), 125.43, 124.72, 122.66
(AreCH), 59.12, 58.48 (NeCH2), 35.94, 33.16 (SeCH2), 28.56 (CH2).
UVeVis [(in pyridine) lmax/nm10ꢁ53 (molꢁ1 cmꢁ1)]: 710 (5.26), 677
(5.30), 615 (4.86), 343 (5.25) MS; m/z ¼ 3078 [M þ K þ H2O]þ.
2. Experimental
All reactions were carried out under a nitrogen atmosphere
using Standard Schlenk techniques. The IR spectra were recorded
on a Perkin Elmer 1600 FTIR spectrophotometer, using potassium
bromide pellets. 1H and 13C NMR spectra were recorded on a Var-
ian Mercury 200 MHz spectrometer in DMSO-d6 or CDCl3, and
chemical shifts (d) are reported relative to Me4Si as internal
standard. Mass spectra were measured on a Varian 711 and VG
Zapspec spectrometer. Elemental analysis were determined by
a LECO Elemental Analyser (CHNS O932) and Unicam 929 AA
spectrophotometer. UVevis absorption spectra were measured by
a Unicam UVevisible spectrometer. A Seiko II Exstar 6000 thermal
analyzer was used to record DTA curves ꢁu1nder nitrogen atmo-
sphere with a heating rate of 20 ꢀC min in the temperature
range 30e900 ꢀC using platinum crucibles. Melting points were
measured on an electrothermal apparatus. A domestic microwave
oven (Arçelik MD 823) was used for all the syntheses of
phthalocyanines.
2.3. Zinc (II) phthalocyanine (5)
Compound 3 (0.2 g, 0.265 mmol), anhydrous ZnCl2 (0.009 g,
0.0662 mmol) and 2-(dimethylamino)ethanol (2 mL) was irradi-
ated in a microwave oven at 175 ꢀC, 350 W for 10 min. After cooling
to room temperature the reaction mixture refluxed with ethanol
(30 mL) to precipitate the product which was filtered off. The dark
green product was washed with hot EtOHeMeOH and dried in
vacuo. Yield: 75 mg (36%), mp: >300 ꢀC. Anal. Calcd. (for imide end
groups) (C148H140N20O24S16Zn)n (%): C, 56.23; H, 4.46; N, 8.86; S,
16.23. Found: C, 56.77; H, 5.09; N, 9.38; S, 16.00. IR (KBr pellets):
3436 (imide NeH), 3058 (AreH), 2921e2857 (Aliph. CeH), 1774
(sym. C]O), 1717 (asym. C]O), 1651 (C]C), 1596, 1487e1347 (S]
O), 1401 (CH2eSeC). 1256 cmꢁ1 (AreNeC). 1H NMR (CDCl3):
d
¼ 7.94 (m, 12H, AreH), 7.69 (m, 16H, AreTs), 7.43 (m, 16H, AreTs),
7.18 (m, 12H, AreH), 4.14 (t, 16H, NeCH2), 2.88 (t, 16H, SeCH2), 2.72
2.1. N,N0-(2,20-(propane-1,3-diylbis(sulfanediyl))bis(ethane-2,1-
(t, 16H, SeCH2), 2.54 (s, 24H, CH3), 1.62 (m, 8H, CH2). 13C NMR
diyl))bis(N-(3,4-dicyanophenyl)-4-methylbenzenesulfonamide)(3)
(DMSO):
d
¼
154.23, 152.90 (AreC), 134.01, 133.35, 131.61
(AreTseC), 129.81, 128.58 (AreTseCH), 124.61, 124.30, 123.39
(AreCH), 59.63, 59.57 (NeCH2), 36.11, 35.01 (SeCH2), 29.71 (CH2).
UVeVis [(in pyridine) lmax/nm10ꢁ5 3(molꢁ1 cmꢁ1)]: 690 (5.25), 624
(4.65), 358 (4.99). MS; m/z ¼ 3180 [M þ H2O þ 1]þ.
N,N0-(2,20-(propane-1,3-diylbis(sulfanediyl))bis(ethane-
2,1diyl))bis(4-methylbenzenesulfonamide) 1 [30] (1 g, 1.99 mmol)
was dissolved in dry DMF (20 mL) under N2 and 4-nitro-
phthalonitrile 2 (0.688 g., 3.98 mmol) was added to the solution.
After stirring for 10 min, finely ground anhydrous K2CO3 (0.823 g,
5.97 mmol) was added portionwise within 2 h with efficient stirring.
The reaction mixture was stirred under N2 at 50 ꢀC for 5 days. Then
the solution was poured into ice-water (100 g). The precipitate
formed was dried in vacuo over P2O5. The crude product was crys-
tallized from ethanol. Yield: % 82, 1.230 g, mp: 197e199 ꢀC. Anal.
Calcd. For (C37H34N6O4S4) (%): C, 58.86; H, 4.54; N, 11.13; S, 16.99.
2.4. Copper (II) phthalocyanine (6)
Compound 3 (0.2 g, 0.265 mmol), anhydrous CuCl2 (0.0089 g,
0.0662 mmol) and 2-(dimethylamino)ethanol (2 mL) was irradi-
ated in a microwave oven at 175 ꢀC, 350 W for 10 min. After
cooling to room temperature the reaction mixture refluxed with
ethanol (30 mL) to precipitate the product which was filtered off.
The dark green product was washed with hot EtOHeMeOH and
dried in vacuo. Yield: 58 mg (28%), mp: >300 ꢀC. Anal. Calcd. (for
imide end groups) (C148H140N20O24S16Cu)n (%): C, 56.26; H, 4.47;
N, 8.87; S, 16.24. Found: C, 56.65; H, 4.73; N, 9.03; S, 16.78. IR (KBr
pellets): 3306 (imide NeH), 3060 (AreH), 2917e2862 (Aliph.
CeH), 1778 (sym. C]O), 1718 (asym. C]O), 1597, 1469e1345 (S]
O), 1404 (CH2eSeC), 1278 cmꢁ1 (AreNeC). UVeVis [(in pyridine)
Found: C, 58.54; H, 4.24; N,11.46; S,16.46. IR (KBr pellets) nmax/cmꢁ1
:
3070 (AreH), 2925e2856 (Aliph. CeH), 2234 (C^N), 1668 (C]C),
1489e1387 (S]O),1445e1408e1254e706 (CH2eSeC),1353 (CeN).
1H NMR (CDCl3), (
d:ppm): 8.01 (d, 2H, AreH4), 7.74 (s, 2H, AreH1),
7.71 (d, 2H, AreH5), 7.48 (dd, 8H, AreTseH,), 2.95 (t, 4H, NeCH2),
2.87 (s, 6H, CH3), 2.60 (m, 4H, CH2eSeCH2), 2.43 (m, 4H,
CH2eSeCH2), 1.24 (m, 2H, CH2). 13C NMR (CDCl3):
d
¼ 144.14
(AreC14), 134.45(AreC4), 132.47 (AreC13), 130.16 (AreC5), 127.33
(AreC12eTs), 123.90 (AreC2), 114.70 (C^N), 49.77 (NeCH2), 30.55
(SeC9), 29.72 (SeC8), 21.68 (CH2), 21.59 (CH3). MS; m/z ¼ 754 [M]þ.
lmax/nm10ꢁ5 (molꢁ1 cmꢁ1)]: 689 (5.33), 623 (4.91), 329 (5.08).
3
MS; m/z ¼ 3159 [M]þ.
2.5. Cobalt(II) phthalocyanine (7)
2.2. Metal-free phthalocyanine (4)
Compound 3 (0.2 g, 0.265 mmol), anhydrous CoCl2 (0.0086 g,
0.0662 mmol) and 2-(dimethylamino)ethanol (2 mL) was irradi-
ated in a microwave oven at 175 ꢀC, 350 W for 10 min. After cooling
to room temperature the reaction mixture refluxed with ethanol
(30 mL) to precipitate the product which was filtered off. The dark
green product was washed with hot EtOHeMeOH and dried in
vacuo. Yield: 66 mg (32%), mp: >300 ꢀC. Anal. Calcd. (for imide end
groups) (C148H140N20O24S16Co)n (%): C, 56.35; H, 4.47; N, 8.88;
Compound 3 (0.2 g, 0.265 mmol) and 2-(dimethylamino)
ethanol (2 mL) was placed in a Schlenk tube under nitrogen in the
presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) (0.232 g,
1.5 mmol), gently heated, and subsequently heated at 145 ꢀC for
24 h. After cooling to room temperature the reaction mixture
refluxed with ethanol (30 mL) to precipitate the product which was
filtered off. The dark green product was washed with hot

E.Ç. Kaya et al. / Dyes and Pigments 85 (2010) 177e182
179
S, 16.26. Found: C, 56.49; H, 4.43; N, 8.48; S, 16.84. IR (KBr pellets):
3304 (imide NeH), 3062 (AreH), 2921e2862 (Aliph. CeH), 1775
(sym. C]O), 1718 (asym. C]O), 1595, 1470e1348 (S]O), 1404
was poured into excess amount of ice-water mixture. The dark
green crude product was washed with distilled water until the
residue washing water was neutral. Then the final product 4a was
washed with ethanol and dried. Yield: 18 mg (46.2%). M.p: >300 ꢀC.
(CH2eSeC), 1248 cmꢁ1 (AreNeC). 1H NMR (DMSO):
d
¼ 7.86 (m,
12H, AreH), 7.64 (m, 16H, AreTs), 7.54 (m, 16H, AreTs), 7.29 (m,
12H, AreH), 4.37(t, 16H, NeCH2), 2.78 (t, 16H, SeCH2), 2.72 (t, 16H,
SeCH2), 2.43 (s, 24H, CH3), 1.58 (m, 8H, CH2). 13C NMR (DMSO):
Anal. Calc. (for imide end groups) (C148H142N20O24S16)n (%): C,
57.38; H, 4.62; N, 9.04; S, 16.56. Found: C, 57.76; H, 4.84; N, 9.32; S,
16.09. IR (KBr pellets): 3392 (imide NeH), 3057 (AreH), 2923e2846
(Aliph. CeH), 1772 (sym. C]O), 1720 (asym. C]O), 1599,
1443e1399 (S]O),1408 (CH2eSeC), 1240 cmꢁ1 (AreNeC). 1H NMR
d
¼ 157.89, 156.34 (AreC), 132.35, 131.24, 130.02 (AreTseC), 128.58,
126.24 (AreTseCH), 123.97, 123.78, 121.58 (AreCH), 59.54, 59.51
(NeCH2), 36.68, 35.24 (SeCH2), 27.81 (CH2). UVeVis [(in pyridine)
(DMSO):
d
¼ 7.74 (m,12H, AreH), 7.69 (m,16H, AreTs), 7.38 (m,16H,
lmax/nm10ꢁ5
3
(molꢁ1 cmꢁ1)]: 671 (5.44), 608 (5.06), 302 (5.41).
AreTs), 7.22 (m, 12H, AreH), 3.86(t, 16H, NeCH2), 2.92(t, 16H,
SeCH2), 2.86(t, 16H, SeCH2), 2.43 (s, 24H, CH3), 1.68 (m, 8H, CH2).
MS; m/z ¼ 3223 [M þ 3Na þ 1]þ.
13C NMR (DMSO):
d
¼ 150.86, 146.62 (AreC), 144.08, 134.28, 132.58
2.6. Nickel(II) phthalocyanine (8)
(AreTseC), 130.34, 127.86 (AreTseCH), 125.14, 124.76, 121.43
(AreCH), 59.32, 58.35 (NeCH2), 35.28, 33.42 (SeCH2), 25.79 (CH2).
MS; m/z ¼ 3098 [M þ 1]þ.
Compound 3 (0.2 g, 0.265 mmol), anhydrous NiCl2 (0.0086 g,
0.0662 mmol) and 2-(dimethylamino)ethanol (2 mL) was irradi-
ated in a microwave oven at 175 ꢀC, 350 W for 10 min. After cooling
to room temperature the reaction mixture refluxed with ethanol
(30 mL) to precipitate the product which was filtered off. The dark
green product was washed with hot EtOHeMeOH and dried in
vacuo. Yield: 73 mg (35%), mp: >300 ꢀC. Anal. Calcd. (for imide end
groups) (C148H140N20O24S16Ni)n (%): C, 56.35; H, 4.47; N, 8.88;
S, 16.26. Found: C, 56.36; H, 4.54; N, 8.15; S, 16.78. IR (KBr pellets):
3285 (imide NeH), 3060 (AreH), 2919e2857 (Aliph. CeH), 1776
(sym. C]O), 1714 (asym. C]O), 1596, 1470e1347 (S]O), 1407
3. Result and discussion
Metal-free and metallophthalocyanine polymers were synthe-
sized by a polymeric tetramerization reaction (Fig. 1). The first
step in the synthetic procedure was to obtain N,N0-(2,20-(propane-
1,3-diylbis(sulfanediyl))bis(ethane-2,1diyl))bis(N-(3,4-dicya-
nophenyl)-4-methylbenzenesulfonamide) 3. This compound was
prepared from 4-nitrophtalonitrile 2 and N,N0-(2,20-(propane-1,3-
diylbis(sulfanediyl))bis(ethane-2,1-diyl))bis(4-methylbenzenesul-
fonamide) 1 in DMF; K2CO3 was used as the base for this
nucleophilic aromatic displacement. In the IR spectrum of 3, the
disappearance of NO2 and NH stretches, along with the
appearance of new bands at 2234 belonging to the C^N group,
are in agreement with the proposed structure. The 1H NMR
spectrum of a CDCl3 solution of 3 was well resolved and showed
that the formation of this macrocycle was accomplished. The
chemical shifts belonging to the deuterium exchangeable NH
(CH2eSeC), 1254 cmꢁ1 (AreNeC). 1H NMR (DMSO):
12H, AreH), 7.72 (m,16H, AreTs), 7.45 (m,16H, AreTs), 7.13 (m,12H,
AreH), 3.99 (t, 16H, NeCH2), 2.86 (t, 16H, SeCH2), 2.83 (t, 16H,
SeCH2), 2.39 (s, 24H, CH3), 1.74 (m, 8H, CH2). 13C NMR (DMSO):
d
¼ 7.86 (m,
d
¼ 150.95, 148.30 (AreC), 142.05, 137.32, 134.98 (AreTseC), 130.07,
129.76 (AreTseCH), 125.68, 124.43, 122.86 (AreCH), 59.32, 58.35
(NeCH2), 35.38, 32.27 (SeCH2), 29.79 (CH2). UVeVis [(in pyridine)
lmax/nm10ꢁ5 3(molꢁ1 cmꢁ1)]: 683 (5.27), 617 (4.94), 305 (5.40). MS;
m/z ¼ 3154 [M]þ.
groups at
d
¼ 5.36 ppm disappear after the condensation reac-
tion between 1 and 2. In the 1H NMR spectrum of 3, the NH
group of compound 1 disappeared as expected. The 13C NMR
spectrum of 3 indicated the presence of nitrile carbon atoms in
3 at 114.70 (C^N), ppm. FAB mass spectrum and elemental
analysis also confirm the formation of desired compound 3.
The metal-free phthalocyanine 4 derived from the correspond-
ing tetracyano compound 3 was synthesized in 2-(dimethylamino)
ethanol under nitrogen in the presence of 1,8-diazabicyclo[5.4.0]
undec-7-ene (DBU) (0.232 g, 1.5 mmol).
2.7. Lead(II) phthalocyanine (9)
Compound 3 (0.15 g, 0.1989 mmol), anhydrous PbCl2 (0.014 g,
0.0497 mmol) and 2-(dimethylamino)ethanol (2 mL) was irradi-
ated in a microwave oven at 175 ꢀC, 350 W for 10 min. After cooling
to room temperature the reaction mixture refluxed with ethanol
(30 mL) to precipitate the product which was filtered off. The dark
green product was washed with hot EtOHeMeOH and dried in
vacuo. Yield: 41 mg (25%), mp: >300 ꢀC. Anal. Calcd. (for imide end
groups) (C148H140N20O24S16Pb)n (%): C, 53.82; H, 4.27; N, 8.48; S,
15.53. Found: C, 53.32; H, 4.11; N, 8.70; S, 16.29. IR (KBr pellets):
3306 (imide NeH), 3059 (AreH), 2921e2861 (Aliph. CeH), 1778
(sym. C]O), 1725 (asym. C]O), 1596, 1482e1324 (S]O), 1399
Compound 4a was obtained to use its characteristic data for
analysis of the degree of polymerization. For this aim, the metal-
free phthalocyanine was reacted with conc. H2SO4 at room
temperature to give 4a and the cyano end groups of the metal-free
phthalocyanine were converted into imido end groups. In the IR
spectrum of 4 characteristic peaks for phthalocyanines were
observed. The peak at 3436 cmꢁ1 is the characteristic metal-free
phthalocyanine NeH stretching bands. Also, 2214 cmꢁ1 (C^N)
band were present in the spectrum. The mass spectrum of this
compound at m/z ¼ 3078 [M þ K þ H2O]þ support the proposed
formula for this structure. The elemental analysis were confirm
desired compound 4. In the IR spectrum of 4a, the disappearance of
the peak at 2214 cmꢁ1 correspond to the cyano groups of 4 and the
appearance of new peaks at 1772e1720 cmꢁ1 correspond to imido
groups confirm the conversion of the cyano groups into imido
groups. The metallophthalocyanines 5e9 were obtained from tet-
racyano derivative 3 and corresponding anhydrous metal salts
ZnCl2, CuCl2, CoCl2, NiCl2, and PbCl2, respectively, by microwave
irradiation in 2-(dimethylamino)ethanol for 10 min. The metal-free
phthalocyanine was obtained under the same conditions in
the microwave oven but only in low yield (18%) relative to the
(CH2eSeC), 1248 cmꢁ1 (AreNeC). 1H NMR (DMSO):
12H, AreH), 7.59 (m, 16H, AreTs), 7.55 (m, 16H, AreTs), 7.47 (m,
12H, AreH), 4.43 (t, 16H, NeCH2), 2.83 (t, 16H, SeCH2), 2.76 (t, 16H,
SeCH2), 2.51 (s, 24H, CH3), 1.64 (m, 8H, CH2). 13C NMR (DMSO):
d
¼ 8.01 (m,
d
¼ 157.59, 155.76 (AreC), 145.63, 139.98, 132.83 (AreTseC), 130.94,
127.96 (AreTseCH), 127.54, 125.86, 124.21 (AreCH), 54.51, 52.16
(NeCH2), 35.16, 32.19 (SeCH2), 31.23 (CH2). UVeVis [(in pyridine)
lmax/nm10ꢁ5 3(molꢁ1 cmꢁ1)]: 721 (5.36), 681 (5.08), 345 (5.19). MS;
m/z ¼ 3306 [M þ 3]þ.
2.8. The conversion of cyano end groups of the polymeric
metal-free phthalocyanine into imido groups (4a)
A sample of compound 4 (0.15 g, 0.0497 mmol) was dissolved in
a minimum volume of H2SO4 (96 wt.-%) at room temperature. After
3e4 h of stirring, the reaction mixture was filtered. The filtered part

180
E.Ç. Kaya et al. / Dyes and Pigments 85 (2010) 177e182
CH3
14
13
H
N
CN
12
S
S
Ts
Ts
dry DMF
dry K2CO3
11
+
O
O
S
500C
N2
N
H
CN
O2N
4
1
CN
5
3
8
7
2
9
6
CN
CN
N
N
2
S
S
1
10
CN
Ts
3
R
R
Ts
N
Ts
N
S
S
S
S
Ts
N
Ts
N
R
R
N
N
N
N
N
N
M
N
Ts
Ts
Ts
N
Ts
N
N
S
S
N
S
S
N
N
M
N
N
N
N
N
N
N
O
(4a-9)
R:
N H
C
N
R:
(4)
O
Compound
M
4
4a
5
6
7
8
9
2H 2H Zn Cu Co Ni Pb
Fig. 1. Synthesis of new network polymeric phthalocyanine polymers.
3,000
2,500
2,000
1,500
1,000
0,500
0,000
3,000
2,500
2,000
1,500
1,000
0,500
0,000
200
300
400
500
600
700
800
200
300
400
500
600
700
800
(nm)
(nm)
λ
λ
Fig. 2. UVeVis spectra of H2Pc(d), ZnPc(..) and CuPc(-.-.-.) complexes.
Fig. 3. UVeVis spectra of CoPc(d), NiPc(..) and PbPc(-.-.-.) complexes.

E.Ç. Kaya et al. / Dyes and Pigments 85 (2010) 177e182
181
Table 1
metallophthalocyanines. Therefore
4 was obtained using the
Thermal properties of the polymeric phthalocyanines.
conventional heating conditions reported in the experimental
section. The differences between the infrared spectra of the metal-
free phthalocyanine and the metallophthalocyanine polymers 5e9
is clear from the absence of NeH stretching vibrations at 3436 cmꢁ1
and 1090 cmꢁ1 correspond to the inner core [32,33]. The end
groups of the metal-free phthalocyanine polymer were cyano
Compound M Initial decomposition
temperature in ꢀC
Main decomposition
temperature in ꢀC
4
5
6
7
8
9
2H 396
Zn 304
Cu 286
Co 356
Ni 307
Pb 371
481
398
360
451
377
417
groups (2214 cmꢁ1
) while the end groups of the metal-
lophthalocyanine polymers were imido groups (1778e1714 cmꢁ1).
The existence of imido groups in the case of metallophthalocyanine
polymers was attributed to the presence of moisture during work-
up. There was little shift to longer wavelength numbers in most of
the IR bands of the metal complexes with respect to the metal-free
analogues [34]. In the mass spectrum of, Zn, Cu, and Co, Ni, Pb
phthalocyanines, the presence of molecular ion peaks at m/z ¼ 3180
[M þ H2O þ 1]þ, m/z ¼ 3159 [M]þ, 3223 [M þ 3Na þ 1]þ, 3154 [M]þ,
and m/z ¼ 3306 [M þ 3H]þ respectively, confirmed the proposed
structures. The elemental analysis were confirm desired
compounds 5, 6, 7, 8, 9.
Table 2
The spectral IR data of new compounds.
Compound
g
(NeH)
g (AreH) g (Aliph. CeH) g (C^N) g (S]O)
3
4
5
6
7
8
9
e
3070
3058
2925e2856
2921e2851
2921e2857
2917e2862
2921e2862
2919e2857
2921e2861
2234
2214
e
1489_1387
1465e1158
1487e1347
1469e1345
1470e1348
1470e1347
1482e1324
3436
3296 Imide NeH 3062
3306 Imide NeH 3060
3304 Imide NeH 3062
3285 Imide NeH 3060
3306 Imide NeH 3059
e
e
e
Classical molecular weight determinations known in polymer
chemistry are very difficult to conduct. This difficulty is due to the
insolubility or very poor solubility of the polymers in organic
solvents. Additionally, different arrangements of connected
phthalocyanine rings in a polymer must be taken into account.
Several isomers exists for a polymer molecule with a definite
molecular weight. One possible procedure to determine of the
degree of polymerization of polymers is IR spectroscopy [35]. We
determined the degree of polymerization after converting the
cyano end groups of the metal-free phthalocyanine polymer into
imido end groups, due to the relatively good intensity of C]O imide
groups to nitrile groups. After this, the ratios of the absorption
intensities of (AreNeC) of the polymers (w1245 cmꢁ1) to asym.
e
Table 3
Electronic spectra of metal-free phthalocyanine and phthalocyanine complexes in
Pyridin.
Compound lmax/nm10ꢁ5 (molꢁ1 cmꢁ1
3 )
4
5
6
7
8
9
710(5.26)
690(5.25)
689(5.33)
671(5.44)
683(5.27)
721(5.36)
677(5.30)
624(4.65)
623(4.91)
608(5.06)
617(4.94)
681(5.08)
615(4.86)
358(4.99)
329(5.08)
302(5.41)
305(5.40)
345(5.19)
343(5.25)
C]O groups of the imides (w1728 cmꢁ1
[compound/log10 1245/I1718: 4a/0.62, 5/0.92, 6/0.90, 7/0.73, 8/0.86,
) were calculated
I
9/0.88]. The polymerization degrees follow the order:
5 > 6 > 9 > 8 > 7 > 4a. On the other hand, the IR spectrum of 4
shows a low degree of polymerization due to the high intensity of
the nitrile groups [36].
The low solubility of the polymers only enabled spectra to be
recorded in pyridine. The UVeVis absorption spectra of these
polymers exhibit Q and B bands, which are the characteristic bands
for phthalocyanine polymers.
The split Q bands in 4, which are characteristic for metal-free
phthalocyanines, were observed at lmax ¼ 677 and 615 nm (Fig. 2).
These Q band absorptions show the monomeric species with D2h
symmetry and due to the phthalocyanine ring relate to the fully
conjugated 18V electron system [37e39]. In addition, in the UV
region at around 340 nm and called the Soret (or B) band, arising
Table 4
Some analytical data and physical properties of the new compounds.
Compounds Empirical formula
Color
Formula wt M.p. (ꢀC) Yield %
3
4
5
6
7
8
9
C
37H34N6O4S4
Brown
Dark green 3021
754
197e199 82
>300 37
>300 36
>300 28
>300 32
>300 35
>300 25
(C148H138N24O16S16
)
n
(C148H140N20O24S16Zn)n Dark green 3161
(C148H140N20O24S16Cu)n Dark green 3159
(C148H140N20O24S16Co)n Dark green 3154
(C148H140N20O24S16Ni)n Dark green 3154
(C148H140N20O24S16Pb)n Dark green 3303
phthalocyanines are well known, the phthalocyanines compounds
are not stable above 286 ꢀC. The initial and main decomposition
temperatures are given in Tables 1e4. The initial decomposition
temperature decreased in the order: 4 > 9 > 7 > 8 > 5 > 6.
from the deeper
p levels / LUMO transition between an a2u and
the same orbitals and extending to the blue of the visible spectrum,
is generally much less intense. The presence of absorption band in 4
in the near UV region at lmax ¼ 343 nm shows Soret region B bands
which have been ascribed to the deeper VeV* levels of LUMO
transitions [40].
4. Conclusions
The UVevis absorption spectra of metallophthalocyanines 5, 6
(Fig. 2), 7, 8, and 9 (Fig. 3) in pyridine show intense Q absorption at
lmax ¼ 690, 689, 671, 683 and 721 nm, respectively with a weaker
absorptions at 624, 623, 608, 617 and 681 nm, respectively. The
single Q bands in metallo derivatives 5, 6, 7, 8, and 9 are charac-
teristic. This result is typical of metal complexes of substituted and
unsubstituted metallophthalocyanines with D4h symmetry [41]. B
band absorptions of 5, 6, 7, 8, and 9 were observed at lmax ¼ 358,
329, 302, 305 and 345 nm, respectively, as expected.
A tetranitrile monomer 3 was synthesized by nucleophilic
aromatic substitution of N,N0-(2,20-(propane-1,3-diylbis(sulfane-
diyl))bis(ethane-2,1-diyl))bis(4-methylbenzenesulfonamide) 1 onto
4-nitrophthalonitrile 2. The metal-free phthalocyanine polymer 4
was prepared by the reaction of the tetranitrile monomer 3 in the
presence of 2-(dimethylamino)ethanol. Metallophthalocyanine
polymers were prepared by reaction of the tetranitrile 3 with the
chlorides of zinc (II), copper (II), cobalt (II), nickel (II), lead (II), by
microwave irradiation in the presence 2-(dimethylamino)ethanol
at 175 ꢀC, 350 W for 10 min. The thermal stabilities of the phtha-
locyanine compounds were determined by thermogravimetric
The thermal behaviour of the metallophthalocyanines were
investigated by TG/DTA. Although the thermal stabilities of

182
E.Ç. Kaya et al. / Dyes and Pigments 85 (2010) 177e182
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