Microwave-assisted synthesis and characterization of a new soluble metal-free and metallophthalocyanines peripherally fused to four 18-membered tetrathiadiaza macrocycles

Article abstract of DOI:10.1016/j.jorganchem.2010.01.030

Preparation of some novel symmetrically tetrasubstituted metal-free phthalocyanine (6) and metallophthalocyanines (7-10) containing four 18-membered tetrathiadiaza macrocycles moieties on peripheral positions has been achieved by cyclotetramerization reaction of phthalonitrile derivative (5) in a multi-step reaction sequence. Metal-free phthalocyanine (6) was synthesized by microwave irradiation of 13,24-bis[(4-methylphenyl)sulfonyl]-6,7,14,15,23,24-hexahydro-13H,22H-tribenzo[b,h,n][1,4,10,13,7,16]tetrathiadiazacyclo-octadecine-18,19-dicarbonitrile (5) in 2-(dimethylamino)ethanol. The metallophthalocyanines (7-10) were prepared by the reaction of the phthalonitrile compound (5) with NiCl₂, Zn(CH₃COO)₂, CoCl₂, CuCl₂ salts, respectively, by microwave irradiation in 2-(dimethylamino)ethanol for at 175 °C, 350 W. The new compounds were characterized by IR, ¹H NMR, ¹³C NMR, UV-Vis, elemental analysis and MS spectra data.

Full text of DOI:10.1016/j.jorganchem.2010.01.030

Journal of Organometallic Chemistry 695 (2010) 1210–1214
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Microwave-assisted synthesis and characterization of a new soluble metal-free and
metallophthalocyanines peripherally fused to four 18-membered tetrathiadiaza
macrocycles
*
Halit Kantekin , Gülsev Dilber, Asiye Nas
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:
Preparation of some novel symmetrically tetrasubstituted metal-free phthalocyanine (6) and metallopht-
halocyanines (7–10) containing four 18-membered tetrathiadiaza macrocycles moieties on peripheral
positions has been achieved by cyclotetramerization reaction of phthalonitrile derivative (5) in a
multi-step reaction sequence. Metal-free phthalocyanine (6) was synthesized by microwave irradiation
of 13,24-bis[(4-methylphenyl)sulfonyl]-6,7,14,15,23,24-hexahydro-13H,22H-tribenzo[b,h,n][1,4,10,13,7,
16]tetrathiadiazacyclo-octadecine-18,19-dicarbonitrile (5) in 2-(dimethylamino)ethanol. The metall-
ophthalocyanines (7–10) were prepared by the reaction of the phthalonitrile compound (5) with NiCl2,
Zn(CH3COO)2, CoCl2, CuCl2 salts, respectively, by microwave irradiation in 2-(dimethylamino)ethanol
for at 175 °C, 350 W. The new compounds were characterized by IR, 1H NMR, 13C NMR, UV–Vis, elemental
analysis and MS spectra data.
Received 18 November 2009
Received in revised form 7 January 2010
Accepted 24 January 2010
Available online 1 February 2010
Keywords:
Phthalocyanine
Metallophthalocyanine
Metal-free
Macrocyclic compound
Transition metal
Tosylation
Ó 2010 Elsevier B.V. All rights reserved.
1. Introduction
clothing [8]. Phthalocyanines, on the other hand, can also photo-
catalytically reduce methyl viologen [1].
Just like many other scientists all over the world, we have clo-
sely been dealing with phthalocyanines and their derivatives be-
cause of their fascinating and fairly useful chemical features for
various scientific areas. The aforementioned word of phthalocya-
nine, which is derived from the Greek term for naphtha (rock oil)
and cyanine (dark blue), was first used by Professor Reginald P. Lin-
stead of the Imperial College of Science and Technology in 1933 to
describe a class of organic compounds which consists of metal-free
or di hydrogen phthalocyanines or metallophthalocyanines and
their derivatives [1].
Phthalocyanines, which are of enormous technological impor-
tance for the manufacture of green and blue pigments [2] and
are of considerable interest owing to their fascinating electronic
and optical properties [3], do not occur in nature [4]. In many
fields, phthalocyanines have been remarkably used because of
their magnificently versatile properties to illustrate photodynamic
reagents for cancer therapy [5,6], and other medical applications
[7], for optical read–write discs [8], in chemical sensors, in photo-
copying machines [9,10], Langmuir–Blodgett films [11], solar cells,
electrochromism, high energy batteries [1,12], fibrous assemblies
[13], coloring for plastics and metal surfaces and dyestuffs for
Peripherally unsubstituted phthalocyanines and metallopht-
halocyanines are slightly soluble in common organic solvents. Gen-
erally, the low solubility circumstance in various organic solvents
or water is a major problem for phthalocyanine and metallopht-
halocyanine derivatives. However, some groups such as bulky
groups [7,14–16], or paraffinic alkyl, polyoxyethylene [13], alkoxy,
alkylthio chains [11,17,18], placed into the peripheral and nonpe-
ripheral positions, can increase the solubility of phthalocyanines
or metallophthalocyanines. Furthermore; amino, sulfo or carboxyl
groups provide water-soluble products [15,16,19–21]. In addition,
phthalocyanines are soluble in concentrated phosphoric and
sulfuric acids, and in chlorosulfonic, anhydrous hydrofluoric, ethyl-
sulfuric and trichloroacetic acids [22]. The solubility of the phtha-
locyanine increases when substituents are placed on the
phthalocyanine ring. At this circumstance, supramolecular organi-
sation may be achieved [4].
Recently, microwave processing techniques have been received
a great deal of attention due to its various advantages such as
selectivity, rapid, direct, controllable, internal, etc. [23–25].
We have already described the synthesis of metal phthalocya-
nines tetrathia macrocyclic moieties on the periphery [26]. In this
study, we described the microwave-assisted synthesis and
characterization of a new soluble metal-free (6) and metallopht-
halocyanines (7–10) peripherally fused to four 18-membered
* Corresponding author. Tel.: +90 462 377 25 89; fax: +90 462 325 31 96.
E-mail address: halit@ktu.edu.tr (H. Kantekin).
0022-328X/$ - see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2010.01.030

H. Kantekin et al. / Journal of Organometallic Chemistry 695 (2010) 1210–1214
1211
tetrathiadiaza macrocycles. We have prepared 1,2-di(o-aminophe-
nylthio)ethane (1) according to the literature [27].
ature was gradually increased up to 85 °C. A solution of 1,2-bis(2-
iodoethylmercapto)-4,5-dicyanobenzene 4 (1.71 g, 3.42 mmol) in
dry acetonitrile (200 ml) was added dropwise over 3 h. The reac-
tion mixture was continuously stirred under nitrogen atmosphere
at reflux temperature for 5 days. The reaction mixture was through
monitored by thin layer chromatography (TLC) chloroform/metha-
nol (3:1) solvent system. At the end of this period, the reaction
mixture was filtered off and the solvent was evaporated under re-
duced pressure, resulting in a light-brown precipitate. The ob-
tained product was washed with EtOH, diethylether and then
dried in vacuo (P2O5). Yield: 1.53 g (54%), mp: 172–174 °C. Anal.
Calc. for C40H36O4N4S6: C, 57.94; H, 4.38; N, 6.66. Found: C,
2. Experimental
All reactions were carried out under a dry nitrogen atmosphere
using Standard Schlenk techniques. 1,2-bis(2-iodoethylmercapto)-
4,5-dicyanobenzene 4 was prepared according to the literature
[28]. All chemicals, solvents, and reagents were of reagent grade
quality and were used as purchased from commercial sources. All
solvents were dried and purified as described by reported proce-
dure [29]. Acetonitrile was dried by distillation over P2O5. And
prior to use, K2CO3 was dried at 130 °C.
57.61; H, 4.83; N, 6.21%. IR (KBr tablet) m
max/cmꢀ1: 3065 (Ar–H),
2924–2853 (Aliph. C–H), 2230 (CN), 1567, 1461, 1347–1159
(SO2), 1090, 964, 894, 757, 671, 574. 1H NMR (CDCl3) (d: ppm):
7.70 (s, 2H, Ar–H), 7.69 (d, 4H, tosyl, Ar–H), 7.65 (d, 2H, Ar–H),
7.59 (t, 2H, Ar–H), 7.37 (d, 2H, Ar–H), 7.34 (d, 4H, tosyl, Ar–H),
7.19 (d, 2H, Ar–H), 3.62 (t, 4H, N–CH2), 3.55 (s, 4H, CH2–S), 2.98
(t, 4H, S–CH2), 2.38 (s, 6H, CH3–tosyl). 13C NMR (CDCl3) (d: ppm):
144.32, 143.61, 140.23, 138.07, 136.67, 131.41, 130.27, 128.31,
126.67, 125.92, 123.61, 119.23, 115.12, 114.57, 51.72, 38.62,
31.65, 20.43. MS (FAB), (m/z): 830 [M+1]+.
Elemental analyses of the complexes were performed on a LECO
Elemental Analyser (CHNS O932) and Unicam 929 AA spectropho-
tometer, respectively. FT-IR spectra were obtained on a Perkin El-
mer 1600 FT-IR spectrophotometer with the samples prepared as
KBr pellets. UV–Visible spectra were recorded using a Unicam
UV–Visible spectrometer operating in the range 200–850 nm with
quartz cells. NMR spectra were recorded on a Varian Mercury
200 MHz spectrometer in CDCl3, and chemical shifts were reported
(d) relative to TMS as an internal standard. Mass spectra were re-
corded on a Micromass Quatro LC/ULTIMA LC–MS/MS spectrome-
ter. Melting points were measured on an electrothermal
apparatus. Domestic microwave oven was used for all synthesis
of phthalocyanines.
2.3. Metal-free phthalocyanine (6)
A mixture of 5 (0.2 g, 0.24 mol) and 2-(dimethylamino)ethanol
(2 ml) was irradiated at 175 °C, 350 W for eight minutes by using
microwave. After the mixture being cooled to room temperature,
EtOH (25 ml) was added, stirred for over night and filtered off. This
product was refluxed by EtOH (40 ml) for 4 h. The dark-green prod-
uct obtained was filtered off, washed with hot EtOH–MeOH and
then dried in vacuo (P2O5). This obtained product was purified by
preparative thin layer chromatography (TLC) by means of chloro-
form/methanol (9:1) solvent system. The dark-green solid product
is soluble in CHCl3, CH2Cl2, DMSO, DMF, THF and pyridine. Yield:
0.272 g (34%), mp >300 °C. Anal. Calc. for C160H146N16O16S24: C,
57.91; H, 4.43; N, 6.75. Found: C, 57.59; H, 4.81; N, 6.87%. IR
2.1. N,N0-[ethane-1,2-diylbis(thio-2,1-phenylene)]bis(4
methylbenzene sulfonamide) (3)
1,2-Di(o-aminophenylthio)ethane 1 (1.50 g, 5.43 mmol) was
dissolved in pyridine (40 ml) under nitrogen atmosphere. Tosyl
chloride 2 (2.58 g, 13.58 mmol), which was dissolved in pyridine
(20 ml), was added dropwise to first solution with stirring over
2 h at ꢀ5 °C. After complete addition, the reaction mixture was
continuously stirred at ꢀ5 °C for 3 h and then overnight at the
room temperature. At the end of this elapsed period, the orange
solution was poured slowly on a mixture which contained HCl
(187 ml conc.) and ice (70 g) and diluted with water (100 ml).
The reaction mixture was extracted with chloroform (50 ml ꢁ 3)
and the organic layer was dried over anhydrous magnesium sul-
fate. After removal of the solvent under reduced pressure, ethanol
(30 ml) was added to residue and filtered off. The brown solid
product was crystallized from ethanol to give pure product and
then dried in vacuo (P2O5). Yield: 2.32 g (73%), mp: 180–182 °C.
Anal. Calc. for C28H28S4O4N2: C, 57.51; H, 4.83; N, 4.79. Found: C,
(KBr tablet)
m
max/cmꢀ1: 3262 (N–H), 3075 (Ar–H), 2923–2853
(Aliph. C–H), 1727, 1647, 1466, 1324–1158 (SO2), 1090, 910, 830,
742. 1H NMR (CDCl3) (d: ppm): 7.79 (s, 8H, Ar–H), 7.73 (m, 32H, to-
syl, Ar–H), 7.61 (d, 8H, Ar–H), 7.57 (m, 8H, Ar–H), 7.34 (d, 8H, Ar–
H), 7.27 (d, 8H, Ar–H), 4.13 (t, 16H, N–CH2), 3.63 (t, 16H, CH2–S),
2.97 (t, 16H, S–CH2), 2.35 (s, 24H, CH3). 13C NMR (CDCl3) (d:
ppm): 144.32, 142.83, 141.44, 138.61, 136.53, 131.15, 130.90,
128.96, 128.03, 125.43, 123.71, 118.17, 115.39, 113.25, 56.64,
37.81, 31.03, 22.29. UV–Vis (CHCl3): kmax/nm: [(10ꢀ5 dm3
e
molꢀ1 cmꢀ1)]: 237 (5.26), 259 (5.19), 292 (4.92), 644 (4.56), 671
57.01; H, 4.61; N, 4.83%. IR (KBr tablet) m
max/cmꢀ1: 3265 (N–H),
(4.71), 707 (5.07), 740 (5.11).MS (FAB), (m/z): 3357 [M+K]+.
3069 (Ar–H), 2922–2854 (Aliph. C–H), 1597 (N–H bending),
1473, 1338–1167 (SO2), 1089, 909, 803, 760, 668, 561. 1H NMR
(CDCl3) (d: ppm): 8.63 (s, 2H, N–H), 7.67 (d, 4H, tosyl, Ar–H),
7.63 (d, 2H, Ar–H), 7.61 (t, 2H, Ar–H), 7.31 (d, 2H, Ar–H), 7.28 (d,
4H, tosyl, Ar–H), 7.24 (t, 2H, Ar–H), 2.45 (t, 4H, CH2–S), 2.36 (s,
6H, CH3). 13C NMR (CDCl3) (d: ppm): 144.29, 138.87, 136.11,
135.39, 130.23, 129.78, 127.22, 124.89, 122.77, 119.81, 35.13,
21.60. MS (FAB), (m/z): 585[M+1]+.
2.4. Nickel(II) phthalocyanine (7)
A mixture of 5 (0.2 g, 0.24 mol), NiCl2 (0.0078 g, 0.06 mmol) and
2-(dimethylamino)ethanol (2 ml) was irradiated at 175 °C, 350 W
for ten minutes by using microwave. After the mixture being
cooled to room temperature, EtOH (25 ml) was added, stirred for
over night and filtered off. This product was refluxed by EtOH
(40 ml) for 4 h. The dark-green product obtained was filtered off,
washed with hot EtOH–MeOH and then dried in vacuo (P2O5).
The product obtained was purified by preparative thin layer chro-
matography (TLC) by means of chloroform/methanol (8:2) solvent
system. The dark-green solid product is soluble in CHCl3, CH2Cl2,
DMSO, DMF and pyridine. Yield: 0.293 g (36%), mp >300 °C. Anal.
Calc. for C160H144N16O16S24Ni: C, 56.94; H, 4.30; N, 6.64; Ni, 1.74.
2.2. 13,24-Bis[(4-methylphenyl)sulfonyl]-6,7,14,15,23,24-hexahydro-
13H,22H-tribenzo [b,h,n][1,4,10,13,7,16]tetrathiadiazacyclo-
octadecine-18,19-dicarbonitrile (5)
N,N0-[ethane-1,2-diylbis(thio-2,1-phenylene)]bis(4 methylben-
zene sulfonamide) 3 (2.0 g, 3.42 mmol) was dissolved in dry aceto-
nitrile (200 ml) under nitrogen atmosphere. Finely ground
anhydrous potassium carbonate (1.42 g, 10.26 mmol) was added
to the solution. After stirring for 2 h at 50 °C, the reaction temper-
Found: C, 56.71; H, 4.60; N, 6.93; Ni, 1.41%. IR (KBr tablet) mmax
/
cmꢀ1: 3049 (Ar–H), 2912–2851 (Aliph. C–H), 1632, 1585, 1465,
1344–1157 (SO2), 1088, 965, 891, 721. 1H NMR (CDCl3) (d: ppm):

1212
H. Kantekin et al. / Journal of Organometallic Chemistry 695 (2010) 1210–1214
7.99 (s, 8H, Ar–H), 7.71 (m, 32H, tosyl, Ar–H), 7.67 (d, 8H, Ar–H),
7.47 (m, 8H, Ar–H), 7.29 (d, 8H, Ar–H), 7.26 (d, 8H, Ar–H), 3.71
(t, 16H, N–CH2), 3.27 (t, 16H, CH2–S), 3.14 (t, 16H, S–CH2), 2.44
C
160H144N16O16S24Cu: C, 56.85; H, 4.29; N, 6.63; Cu, 1.88. Found: C,
56.45; H, 4.67; N, 6.83; Cu, 1.67%. IR (KBr tablet)
max/cmꢀ1: 3049
(Ar–H), 2923–2851 (Aliph. C–H), 1729, 1594, 1465, 1340–1157
m
(s, 24H, CH3. UV–Vis (CHCl3): kmax/nm: [(10ꢀ5
e
dm3 molꢀ1 cmꢀ1)]:
(SO2), 1088, 892, 721. UV–Vis (CHCl3): kmax/nm: [(10ꢀ5 dm3
e
278 (6.22), 322 (5.07), 653 (4.83), 710 (5.18). MS (FAB), (m/z): 3392
molꢀ1 cmꢀ1)]: 254 (5.23), 289 (5.06), 655 (4.83), 720 (5.25). MS
[M+H2O]+.
(FAB), (m/z): 3402 [M+Na]+.
2.5. Zinc(II) phthalocyanine (8)
3. Results and discussion
A
mixture of 5 (0.2 g, 0.24 mol), Zn(CH3COO)2 (0.0109 g,
0.06 mmol) and 2-(dimethylamino)ethanol (2 ml) was irradiated
at 175 °C, 350 W for nine minutes by using microwave. After the
mixture being cooled to room temperature, EtOH (25 ml) was
added, stirred for over night and filtered off. The product was re-
fluxed by EtOH (40 ml) for 4 h. The green product obtained was fil-
tered off, washed with hot EtOH–MeOH and then dried in vacuo
(P2O5). The product obtained was purified by preparative thin layer
chromatography (TLC) by means of chloroform/methanol (9:1) sol-
vent system. The green solid product is soluble in CHCl3, CH2Cl2,
DMSO, DMF, THF and pyridine. Yield: 0.285 g (35%), mp >300 °C.
Anal. Calc. for C160H144N16O16S24Zn: C, 56.82; H, 4.29; N, 6.63; Zn,
1.93. Found: C, 56.52; H, 4.67; N, 6.97; Zn, 1.58%. IR (KBr tablet)
The synthetic procedure, as shown in Scheme 1, started with
the synthesis of the 1,2-di(o-aminophenylthio)ethane 1 as de-
scribed according to the reported procedure [27]. The compound
3 was synthesized reaction of 1,2-di(o-aminophenylthio)ethane 1
with p-toluenesulfonylchloride 2. The synthesis of the phthalonit-
rile derivative, namely 13,24-bis[(4-methylphenyl)sulfonyl]-6,7,
14,15,23,24-hexahydro-13H,22H-tribenzo [b,h,n][1,4,10,13,7,16]
tetrathiadiazacyclo-octadecine-18,19-dicarbonitrile
5 was ob-
tained 4,5-bis[(2-iodoethyl)sulfanyl]benzene-1,2-dicarbonitrile 4
in dry acetonitrile containing anhydrous potassium carbonate as
base [30,31]. This base catalyzed macrocyclization reaction was
carried out in dry acetonitrile at 50 °C for 5 days and giving mod-
erate yield (54%). The cyclotetramerization of phthalonitrile deriv-
ative 5 in to the metal-free phthalocyanine 6 was accomplished in
2-(dimethylamino)ethanol for 8 min. During the formation of me-
m
max/cmꢀ1: 3054 (Ar–H), 2961–2840 (Aliph. C–H), 1726, 1588,
1466, 1344–1158 (SO2), 1086, 888, 718. 1H NMR (CDCl3) (d:
ppm): 7.82 (s, 8H, Ar–H), 7.76 (m, 32H, tosyl, Ar–H), 7.68 (d, 8H,
Ar–H), 7.60 (m, 8H, Ar–H), 7.38 (d, 8H, Ar–H), 7.25 (d, 8H, Ar–H),
4.11 (t, 16H, N–CH2), 3.60 (t, 16H, CH2–S), 3.20 (t, 16H, S–CH2),
2.50 (s, 24H, CH3). 13C NMR (CDCl3) (d: ppm): 147.32, 145.61,
141.23, 139.07, 135.67, 132.42, 130.93, 129.74, 128.82, 126.93,
124.13, 119.21, 115.60, 114.57, 68.17, 38.71, 30.35, 23.74. UV–Vis
tal-free phthalocyanines, 2-(dimethylamino)ethanol acts as
a
nucleophilic reagent and it reducts phthalocyanine ring by two
electrons, and also acts as donor of protons [32]. The metallopht-
halocyanines 7–10 were prepared from the corresponding dicyano
derivative and the corresponding metal salts (Ni, Zn, Co, Cu) in high
boiling solvent (e.g. DMAE) at 175 °C 350 W for 10, 9, 9, 12 min,
resulting in moderate yields 36, 35, 37, 33(%), respectively.
(CHCl3): kmax/nm: [(10ꢀ5 dm3 molꢀ1 cmꢀ1)]: 244 (5.14), 366
e
(5.06), 646 (4.64), 718 (5.19).MS (FAB), (m/z): 3399 [M+1+H2O]+.
All novel compounds were identified through various spectro-
scopic techniques such as IR, 1H NMR, 13C NMR, UV–Vis, MS spec-
tral data and elemental analysis. The IR spectrum of 3 clearly
indicated the presence of the NH group by intense stretching bands
at 3265 cmꢀ1. In the 1H NMR spectrum of 3 in deuterated chloro-
form, the tosylated amino groups were shown by the presence of
sulfonamide bands at d = 8.63 ppm. The aromatic protons belong-
ing to 1,2-di(o-aminophenylthio)ethane 1 appear as doublet at
d = 7.63, 7.31 ppm and as triplet at d = 7.61, 7.28 ppm. The doublet
at d = 7.67, 7.28 ppm belong to aromatic protons of tosyl benzene.
The triplet at d = 2.45 ppm for CH2–S and singlet at d = 2.36 ppm for
CH3 protons confirms the proposed structure. 13C NMR spectrum of
this compound exhibits characteristic signals at 144.29, 138.87,
136.11, 135.39, 130.23, 129.78, 127.22, 124.89, 122.77, 119.81,
35.13, 21.60. The MS spectrum of 3 shows a peak at m/z: 585
[M+1]+ and the elemental analyses support the proposed structure.
In the IR spectrum of 5, the presence of intense CN stretching
band at 2230 cmꢀ1 and the disappearance of the strong NH stretch-
ing vibrations at 3265 cmꢀ1 confirm the formation of this com-
pound. The 1H NMR spectrum of 5 in deuterated chloroform
showed a new signal due to an aromatic proton at d = 7.70 ppm,
as expected. The 13C NMR spectrum of 5 also indicated the pres-
ence of nitrile carbon at d = 114.57 ppm. In the MS spectrum of
compound 5, the presence of characteristic molecular ion peak at
m/z: 830 [M+1]+ confirmed the proposed structure.
2.6. Cobalt(II) phthalocyanine (9)
A mixture of 5 (0.2 g, 0.24 mol), CoCl2 (0.0078 g, 0.06 mmol) and
2-(dimethylamino)ethanol (2 ml) was irradiated at 175 °C, 350 W
for nine minutes by using microwave. After the mixture being
cooled to room temperature, EtOH (25 ml) was added, stirred for
over night and filtered off. The product was refluxed by EtOH
(40 ml) for 4 h. The dark-green product obtained was filtered off,
washed with hot EtOH–MeOH and then dried in vacuo (P2O5). This
product obtained was purified by preparative thin layer chroma-
tography (TLC) by means of chloroform/methanol (9:1) solvent
system. The dark-green solid product is soluble in CHCl3, CH2Cl2,
DMSO, DMF, THF and pyridine. Yield: 0.301 g (37%), mp >300 °C.
Anal. Calc. for C160H144N16O16S24Co: C, 56.93; H, 4.30; N, 6.64; Co,
1.75. Found: C, 56.53; H, 4.57; N, 6.82; Co, 1.89%. IR (KBr tablet)
m
max/cmꢀ1: 3054 (Ar–H), 2922–2851 (Aliph. C–H), 1726, 1585,
1466, 1345–1157 (SO2), 1088, 962, 893, 722. UV–Vis (CHCl3):
kmax/nm: [(10ꢀ5 dm3 molꢀ1 cmꢀ1)]: 250 (5.16), 293 (5.12), 643
e
(4.73), 712 (5.21).MS (FAB), (m/z): 3376 [M+1]+.
2.7. Copper(II) phthalocyanine (10)
A mixture of 5 (0.2 g, 0.24 mol), CuCl2 (0.0081 g, 0.06 mmol)
and 2-(dimethylamino)ethanol (2 ml) was irradiated at 175 °C,
350 W for twelve minutes by using microwave. After the mixture
being cooled to room temperature, EtOH (25 ml) was added, stirred
for over night and filtered off. The product was refluxed by EtOH
(40 ml) for 4 h. The green product obtained was filtered off,
washed with hot EtOH–MeOH and then dried in vacuo (P2O5). This
product obtained was purified by preparative thin layer chroma-
tography (TLC) by means of chloroform/methanol (9:1) solvent
system. The green solid product is soluble in CHCl3, CH2Cl2, DMSO,
DMF and pyridine. Yield: 0.269 g (33%), mp >300 °C. Anal. Calc. for
IR spectrum of 6, the disappearance of CN stretching vibration
of 5 is an evidence for the formation of the metal-free phthalocya-
nine 6. In addition to this circumstance, the strong NH stretching
vibrations and Ar–H vibrations are observed at 3262, 3075 cmꢀ1
,
respectively. In the 1H NMR spectrum of 6, the typical shielding
of inner core protons could not be observed due to the probable
strong aggregation of the molecules [33]. The signals related to
aromatic protons and aliphatic protons in the macrocyclic moieties
and phthalocyanine skeleton were characteristic of the purposed

H. Kantekin et al. / Journal of Organometallic Chemistry 695 (2010) 1210–1214
1213
Scheme 1. The synthesis of the metal-free phthalocyanine 6 and metallophthalocyanines 7, 8, 9, 10.
structure. In the MS spectrum of 6, the presence of characteristic
molecular ion peak at m/z: 3357 [M+K]+ confirmed the proposed
structure.
ocyanines 6–10 were reasonably soluble in CHCl3, CH2Cl2, DMSO,
DMF, pyridine.
Electronic spectra are especially useful to identify the structure
of the phthalocyanines. Generally, UV–Vis spectra of phthalocya-
nines show typical electronic spectra with two strong absorbtion
bands known as Q and B-bands. The Q-band in the visible region
In the IR spectra, the disappearance of strong CN stretching
vibration of 5 is also an evidence for the formation metallophthalo-
cyanines 7–10. The IR spectra of metallophthalocyanines 7–10 are
very similar to metal-free phthalocyanine 6, with the exception of
NH stretching vibration appeared at 3262 cmꢀ1 due to inner core
protons of metal-free phthalocyanine 6. The 1H NMR spectra of
these compounds in deuterated chloroform were almost identical
to those of 6. In the mass spectra of compounds 7–10, the presence
of molecular ion peaks at m/z: 3392 [M+H2O]+, 3399 [M+1+H2O]+,
3376 [M+1]+, and 3402 [M+Na]+ confirmed the proposed struc-
tures, respectively. In addition to these data, the elemental analysis
of these compounds was also determined. Besides, the new phthal-
at ca. 600–750 nm (Q-band) is attributed to the
p–
p* transition
from HOMO (highest occupied molecular orbital) to the LUMO
(lowest unoccupied molecular orbital) of the Pc (ꢀ2) ring and the
B-band in the UV region at ca. 300–400 nm (B-band) arises from
the deeper p–
p* transitions [34].
The electronic spectra are given for compound 6, 7, 8 (Fig. 1)
and 9, 10 (Fig. 2). In the UV–Vis spectrum of metal-free phthalocy-
anine 6 in chloroform, the characteristic split Q-band was observed
with absorptions at kmax: 707 and 740 nm. The UV–Vis absorption

1214
H. Kantekin et al. / Journal of Organometallic Chemistry 695 (2010) 1210–1214
tions show that the obtained metal-free phthalocyanine and its
transition metal complexes can dissolve various solvents such as
CHCl3, CH2Cl2, DMSO, DMF, THF and pyridine.
1.5
1
Acknowledgement
This study was supported by the Research Fund of Karadeniz
Technical University, Project No: 2004.111.002.6 (Trabzon-
Turkey).
0.5
0
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200
300
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We have presented the synthesis of a new soluble phthalocya-
nine 6 and four metallophthalocyanines (7–10) from the new mac-
rocyclic
ligand
5
by
microwave
irradiation
in
2-
(dimethylamino)ethanol for at 175 °C, 350 W. It is seen that struc-
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