A novel metal-free and metallophthalocyanines containing four 19-membered dithiadiazadioxa macrocycles by microwave irradiation: Synthesis and characterization

Article abstract of DOI:10.1016/j.jorganchem.2007.11.022

The novel tetrasubstituted metal-free phthalocyanine (5) and metallophtalocyanines (6, 7 and 8) bearing four 19-membered dithiadiazadioxa macrocyclic moieties on peripheral positions have been synthesized by cyclotetramerization reaction of phthalonitrile

Full text of DOI:10.1016/j.jorganchem.2007.11.022

Available online at www.sciencedirect.com
Journal of Organometallic Chemistry 693 (2008) 505–509
www.elsevier.com/locate/jorganchem
A novel metal-free and metallophthalocyanines containing four
19-membered dithiadiazadioxa macrocycles by microwave
irradiation: Synthesis and characterization
Zekeriya Bıyıklıog˘lu, Halit Kantekin *
Department of Chemistry, Faculty of Arts and Sciences, Karadeniz Technical University, 61080 Trabzon, Turkey
Received 21 September 2007; received in revised form 8 November 2007; accepted 12 November 2007
Available online 21 November 2007
Abstract
The novel tetrasubstituted metal-free phthalocyanine (5) and metallophtalocyanines (6, 7 and 8) bearing four 19-membered
dithiadiazadioxa macrocyclic moieties on peripheral positions have been synthesized by cyclotetramerization reaction of phthalonitrile
1
derivative (4) in a multi-step reaction sequence. The new compounds were characterized by a combination of IR, H NMR, 13C NMR,
UV–Vis, elemental analysis and MS spectral data.
Ó 2007 Elsevier B.V. All rights reserved.
Keywords: Phthalocyanine; Dithiadiazamacrocycle; Phthalonitrile; Macrocyclization; Tosylation
1. Introduction
and also non-metal ions can be incorporated. A number
of modifications can be made in the macrocycle either by
introduction of different central ions or by substitution of
functional groups at the peripheral sites of the ring [6].
Microwaves have been previously used for the synthesis
of phthalocyanines and include a wider range of references
on the topic [7–15].
We have previously synthesized phyhalocyanines con-
taining 14-membered tetraaza macrocyclic [13], four pyri-
dyl groups [14] polymeric group [15] by microwave
irradiation. In this paper, we have rapidly prepared
metal-free and metallophthalocyanines by microwave irra-
diation and we have described characterization of the new
metal-free and metallophthalocyanines, bearing dithiadiaz-
adioxa macrocyclic moieties (Fig. 1).
Phthalocyanines and metallophthalocyanines have been
investigated for many years owing to their range applica-
tions in many fields, including use and investigation in
chemical sensors, liquid crystals, Langmuir–Blodgett films,
non-linear optics, optical data storage and as carrier gener-
ation materials in near-IR devices. Substituted derivatives
can be used for photodynamic cancer therapy and other
processes driven by visible light. A disadvantage of phthal-
ocyanines and metal phthalocyanines is their low solubility
in organic solvents or water [1,2].
Phthalocyanines have become noted recently for their
special optical and electrical properties such as electrical
conductivity, photovoltaic effects, and electrochromism
[3,4]. Also, their use as efficient is becoming important in
photodynamic therapy, as well [5].
2. Results and discussion
Phthalocyanines have a two dimensional 18-p electron
conjugated system, in which more than 70 different metal
The preparation of the target metal-free 5 and metall-
ophthalocyanines (6, 7 and 8) is shown in Scheme 1. The
structures of novel compounds were characterized by
the combination of 1H NMR, 13C NMR, IR, UV–Vis,
*
Corresponding author. Tel.: +90 462 377 2589; fax: +90 462 325 3196.
E-mail address: halit@ktu.edu.tr (H. Kantekin).
0022-328X/$ - see front matter Ó 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2007.11.022

506
Z. Bıyıklıog˘lu, H. Kantekin / Journal of Organometallic Chemistry 693 (2008) 505–509
2
Metal-free phthalocyanine 5 was synthesized by micro-
wave irradiation [13–15] of the corresponding dicyano
compound 4 in dry quinoline for 15 min. The IR spectrum
of metal-free phthalocyanine 5 shows the 3288 (NH), 3054
(Ar–H) vibrations. In the 1H NMR spectrum of 5, the typ-
ical shielding of inner core protons could not be observed
due to the probable strong aggregation of the molecules
[19]. The signals related to aromatic protons and aliphatic
protons in the macrocyclic moieties and phthalocyanine
skeleton gave significant absorbance characteristic of the
proposed structure. The disappearance of the C„N
stretching vibration on the IR spectra of 4 suggested the
formation of compound 5. The MS mass spectra of com-
pound 5, which shows a peak at m/z = 3246 [M]+ support
the proposed formula for this compound.
1.5
1
0.5
0
200
300
400
500
600
λ (nm)
700
800
900
Fig. 1. UV–Vis spectra of compounds 5 (ꢁ ꢁ ꢁ), 6 (–ꢁ–ꢁ) and 7 (—-) in
chloroform.
The metallophthalocyanines 6, 7 and 8 were synthesized
in moderate yield 40%, 44% and 39%, respectively. The
metallophthalocyanines (6, 7 and 8) were obtained from
dicyano derivative 4 and corresponding anhydrous metal
salts NiCl2, CoCl2 and CuCl2 respectively, by microwave
irradiation in dry quinoline for 15 min. The IR spectra of
metallophthalocyanines (6, 7 and 8) the disappearance of
strong C„N stretching vibration of 4 is an evidence for
the formation of metallophthalocyanines 6, 7 and 8. The
rest of the IR spectra of metallophthalocyanines are very
similar to those of the metal-free phthalocyanine 5. In the
1H NMR spectra of these compounds are almost identical
to those of metal-free phthalocyanine 5. Also, it should be
elemental analysis and MS spectral data. N-[2-({3-[(2-ami-
nophenyl)thio]propyl}thio)phenyl]-4,40-di(toluene-p-sulfo-
nylamino)
1
[16], 1,2-dibromo-4,5-bis(2-iyodoethoxy)
benzene 2 [17] were prepared according to the literatures.
Compound 1 [16] was reacted with 1,2-dibromo-4,5-
bis(2-iyodoethoxy)benzene 2 [17] in dry CH3CN containing
finely ground anhydrous Cs2CO3 as a template agent in a
Schlenk system under an argon atmosphere to give the
new dithiadiazadioxa macrocycle 3 in 58% yield. Tosyla-
tion of aza groups, which are used as protective groups
of aza functions in the cyclotetramerization, is effective in
the cyclization. Analytical and spectroscopic data of 3
clearly confirm the success of the cyclization reaction. In
the 1H NMR spectrum of 3 the chemical shifts of NH pro-
tons in precursor compound 1 disappear after the macro-
1
mentioned that the other differences in the H NMR spec-
tra of metal-free phthalocyanine and metallophthalocya-
nines were the broad signals encountered in the case of
compounds 6, 7 and 8, owing to the aggregation of planar
phthalocyanine molecules at the considerably high concen-
tration used for NMR measurements. They are in agree-
ment with the structural information. In the mass
spectrum of compounds 6, 7 and 8, the presence of molec-
ular ion peaks at m/z = 3302 [M]+, 3303 [M]+ and 3307
[M]+, respectively, confirmed the proposed structures.
In general, phthalocyanines show typical electronic
spectra with two strong absorption regions, one in the
UV region at about 300–500 nm related to the B band
and the other in the visible region at 600–700 nm related
to the Q band [20]. The split Q bands in 5, which are char-
acteristic for metal-free phthalocyanines were observed at
1
cyclization reaction. In the H NMR. spectrum of 3, the
chemical shifts due to Ar–H, CH2–O, CH2–N protons were
observed at d = 7.17, 3.66, 3.50 ppm, respectively. 13C
NMR spectral data were also in good agreement with the
formation of 3. The chemical shifts for aromatic carbon
atoms, CH2–O and CH2–N were observed at d = 147.44,
119.36, 114.67, 64.66 and 49.85 ppm, respectively. The dif-
ference between in infrared spectra of the precursor com-
pounds and the macrocycle is clear from the presence of
characteristic vibrations belonging to the starting materi-
als, such as Ar–H (3054 cmꢀ1), SO2 (1348–1161 cmꢀ1),
Ar–O–C (1089 cmꢀ1) and the absence of N–H stretching
vibrations. The MS mass spectrum of 3, which shows a
peak at m/z = 918 [M]+ support the proposed formula
for this compound.
4,50-Dicyano substituted macrocycle was synthesized by
treating the dibromo compound 3 with three equivalents of
CuCN according to Rosenmund von Braun reaction [18] in
a moderately high-boiling solvent such as DMF at 145 °C
under argon atmosphere. The 1H NMR spectrum of 4 clo-
sely resembles that of the precursor compound 3 as
expected. The 13C NMR spectrum of 4 shows the presence
of nitrile carbon atoms at d = 113.61 ppm which indicates
the completion of conversion of 3–4. The MS mass spec-
trum of compound 4, which shows a peak at m/z = 812
[M+1]+ support the proposed formula for this compound.
k
max = 707 and 689 nm. These Q band absorptions show
the monomeric species with D2h symmetry and due to the
phthalocyanine ring related to the fully conjugated 18-p
electron system [21–23]. The presence of strong absorption
bands in 5 in the near UV region at kmax = 334 and 281 nm
also shows Soret region B bands which have been ascribed
to the deeper p–p* levels of LUMO transitions.
The UV–Vis absorption spectra of metallophthalocya-
nines (6, 7 and 8) in chloroform show intense Q absorption
at kmax = 680, 686 and 691 nm, with weaker absorptions at
611, 617 and 622 nm, respectively. The single Q bands in
metallo derivatives 6, 7 and 8 are characteristic. This result
is typical for metal complexes of substituted and unsubsti-

Z. Bıyıklıog˘lu, H. Kantekin / Journal of Organometallic Chemistry 693 (2008) 505–509
507
Ts
I
I
O
O
Br
Br
S
S
NH Ts
NH Ts
Br
Br
S
S
N
N
O
O
dry CH3CN
Cs2CO3
2
3
Ts
1
dry
DMF
CuCN
Ts
Ts
CN
S
S
N
N
O
O
CN
4
dry
Quinoline
MW, 350 W
S
S
Ts
O
Ts
O
S
S
N
N
N
N
Ts
Ts
O
O
N
N
N
N
N
M
N
N
N
O
O
Ts
Ts
O
O
N
N
N
N
S
S
Ts
Ts
S
S
Compound
M
8
5
6
7
2H Ni Co
Cu
Scheme 1. The synthesis of the metal-free phthalocyanine and metallophthalocyanines (Ts = p-toluenesulphonyl).
tuted metallophthalocyanines with D4h symmetry [24] B
band absorptions of compound 6, 7 and 8 were observed
at kmax = (342 and 270), (351 and 276), (354 and 282) nm
as expected, respectively.
suppliers. All solvents were dried and purified as described
by Perrin and Armarego [25]. The IR spectra were recorded
on a Perkin–Elmer 1600 FT-IR Spectrophotometer, using
1
KBr pellets or NaCl disc. H and 13C NMR spectra were
recorded on a Varian Mercury 200 MHz spectrometer in
CDCl3, DMSO, and chemical shifts were reported (d) rela-
tive to Me4Si as internal standard. Mass spectra were mea-
sured on a Micromass Quatro LC/ULTIMA LC-MS/MS
spectrometer. Elemental analyses were determined by a
LECO Elemental Analyser (CHNS O932) and Unicam
929 AA spectrophotometer, respectively. Melting points
were measured on an electrothermal apparatus and are
3. Experimental
N-[2-({3-[(2-aminophenyl)thio]propyl}thio)phenyl]-4,40-
di(toluene-p-sulfonylamino) (1) [16] and 1,2-dibromo-4,5-
bis(2-iyodoethoxy)benzene (2) [17] were prepared accord-
ing to the literatures. All reagents and solvents were of
reagent grade quality and were obtained from commercial

508
Z. Bıyıklıog˘lu, H. Kantekin / Journal of Organometallic Chemistry 693 (2008) 505–509
uncorrected. Optical spectra in the UV–Vis region were
recorded with a Unicam UV2-100 spectrophotometer,
using 1 cm pathlength cuvettes at room temperature.
water, dried over anhydrous magnesium sulfate and then
evaporated to dryness. Methanol 10 ml was added to this
section and then stirred at room temperature for 6 h. At
the end of this period, the precipitation occured. The
resulting brown precipitate was filtered off, washed with
cold methanol and diethyl ether and dried in vacuo. Yield:
1.38 g (68%), m.p.: 175–177 °C. Anal. Calc. for
C41H38N4O6S4(811.02): C, 60.71; H, 4.72; N, 6.90. Found:
3.1. 10,11-Dibromo-5,16-bis[(4-methylphenyl)sulfonyl]-
6,7,15,16,23,24-hexahydro-5H,14H,-22H-tribenzo[b,h,o]-
[1,4,10,14,7, 17]dioxadithiadiazacyclononadecine (3)
N-[2-({3-[(2-aminophenyl)thio]propyl}thio)phenyl]-4,40-
di(toluene-p-sulfonylamino) (1) (3 g, 5.01 mmol) and in dry
acetonitrile (120 ml) containing finely ground anhydrous
Cs2CO3 (4.07 g, 12.52 mmol) and purged under argon in
a Schlenk system connected to a vacuum-line was heated
and stirred under argon until 1 was dissolved. This solution
was stirred at 110 °C and a solution of 1,2-dibromo-4,5-
bis(2-iyodoethoxy)benzene 2 (2.88 g, 5.01 mmol) in dry
acetonitrile (40 ml) was added dropwise over a period of
4 h. The reaction was monitored by TLC using chloro-
form/petroleum ether/methanol (7:2:1) and was completed
in 120 h at the same temperature. At the end of this period,
the reaction mixture was filtered and washed with dry ace-
tonitrile and then the combined solution was evaporated to
dryness under reduced pressure. The oily product was
mixed with water (50 ml) and then extracted with chloro-
form (3 ꢂ 70 ml). The combined extract was washed with
water, dried over MgSO4 and then filtered and evaporated
to dryness to give crude product. The crude product was
chromatographed on silica gel with chloroform as eluents.
Yield: 2.66 g (58%), m.p.: 85–87 °C. Anal. Calc. for
C39H38N2O6S4Br2(918.80): C, 50.98; H, 4.17; N, 3.04.
Found: C, 50.40; H, 4.10; N, 3.31%. IR (KBr tablet)
C, 60.78; H, 4.89; N, 6.71%. IR (KBr tablet) mmax/cmꢀ1
:
3059 (Ar–H), 2922–2851 (Aliph. C–H), 2229 (C„N),
1594, 1515, 1468, 1347–1161 (SO2), 1088, 914, 815, 756,
1
723. H NMR. (200 MHz, CDCl3), (d: ppm): 7.52 (s, 2H,
Ar–H), 7.48 (m, 4H, tosyl Ar–H), 7.23 (m, 4H, tosyl
Ar–H), 7.19 (t, 2H, Ar–H), 7.16 (d, 2H, Ar–H), 7.12
(t, 2H, Ar–H), 7.01 (d, 2H, Ar–H), 3.74 (m, 4H, CH2–O),
3.66 (t, 4H, CH2–N), 2.81 (t, 4H, CH2–S), 2.36 (s, 6H,
CH3), 1.80 (m, 2H, CH2–CH2–CH2). 13C NMR.
(200 MHz, CDCl3), (d: ppm): 151.73, 144.28, 139.45,
134.27, 130.82, 129.84, 128.26, 125.71, 123.55, 117.73,
115.29, 113.61, 111.48, 68.05, 49.93, 32.11, 29.94, 21.89.
MS (FAB), (m/z): 812 [M+1]+.
3.3. Metal-free phthalocyanine (5)
A
mixture of 5,16-bis[(4-methylphenyl)sulfonyl]-
6,7,15,16,23,24-hexahydro-5H,14H,22H-tribenzo[b,h,o] [1,4,
10,14,7,17]dioxadithiadiazacyclononadecine-10,11-dicarbo-
nitrile (4) (0.3 g, 0.37 mmol) and dry quinoline (2.5 ml) was
irradiated in a microwave oven at 220 °C, 350 W for
15 min. After cooling to room temperature the reaction
mixture refluxed with ethanol to precipitate the product
which was filtered off. The green solid product was washed
with hot ethanol (40 ml) and dried in vacuo. The solid
product was chromatographed on silica gel with chloro-
form:methanol (9.5:0.5) as eluents. Yield: 151 mg (41%),
m
max/cmꢀ1: 3054 (Ar–H), 2924–2853 (Aliph. C–H), 1597,
1468, 1348–1161 (SO2), 1089, 907, 814, 759, 673, 650,
575. 1H NMR. (200 MHz, CDCl3), (d: ppm): 7.48 (m,
4H, tosyl Ar–H), 7.32 (m, 4H, tosyl Ar–H), 7.25 (t, 2H,
Ar–H), 7.21 (d, 2H, Ar–H), 7.15 (t, 2H, Ar–H), 7.09 (d,
2H, Ar–H), 7.17 (s, 2H, Ar–H), 3.66 (m, 4H, CH2–O),
3.50 (t, 4H, CH2–N), 2.87 (t, 4H, CH2–S), 2.38 (s, 6H,
CH3), 1.53 (m, 2H, CH2–CH2–CH2). 13C NMR.
(200 MHz, CDCl3), (d: ppm): 147.44, 143.77, 138.14,
135.58, 130.00, 129.70, 129.28, 127.89, 124.63, 119.36,
114.67, 64.66, 49.85, 34.44, 29.69, 21.64. MS (FAB),
(m/z): 918 [M]+.
m.p.: >300 °C. Anal. Calc. for
C164H154N16O24S16
(3246.08): C, 60.68; H, 4.78; N, 6.90. Found: C, 60.34; H,
4.59; N, 6.73%. IR (KBr tablet) mmax/cmꢀ1: 3288 (N–H),
3054 (Ar–H), 2923–2857 (Aliph. C–H), 1618, 1594, 1500,
1467, 1346–1161 (SO2), 1088, 1050, 810, 724, 673, 575.
UV–Vis (CHCl3):
k
max/nm: [(10ꢀ5 e dm3 molꢀ1 cmꢀ1)]:
1
281 (4.83), 334 (4.68), 689 (5.08), 707 (5.11). H NMR.
(200 MHz, DMSO-d6), (d: ppm) 8.42 (s, 8H, Ar–H),
7.68–7.32 (m, 32H, tosyl Ar–H), 7.57–6.95 (m, 16H,
Ar–H), 7.51–7.23 (t, 16H, Ar–H), 3.90 (m, 16H, CH2–O),
2.99 (t, 16H, CH2–S), 2.95 (m, 16H, CH2–N), 2.40 (s,
24H, CH3), 2.19 (m, 8H, CH2–CH2): MS (FAB), (m/z):
3246 [M]+.
3.2. 5,16-Bis[(4-methylphenyl)sulfonyl]-6,7,15,16,23,24-
hexahydro-5H,14H,22H- tribenzo[b,h,o] [1,4,10,14,7,17]-
dioxadithiadiazacyclononadecine-10,11-dicarbonitrile (4)
A
mixture of 10,11-dibromo-5,16-bis[(4-methyl-
phenyl)sulfonyl]-6,7,15,16,23,24-hexahydro-5H,14H,22H-
tribenzo[b,h,o][1,4,10,14,7,17]dioxadithiadiazacyclononade-
cine (3) (2.30 g, 2.50 mmol), CuCN (0.67 g, 7.5 mmol), and
dry pyridine (0.12 ml) in dry DMF (25 ml) was refluxed
under nitrogen for 48 h. The mixture was cooled to room
temperature and then poured into aqueous ammonia. After
stirring for 24 h, the mixture was extracted with chloro-
form. The combined organic layers were washed with
3.4. Nickel(II) phthalocyanine (6)
A
mixture of 5,16-bis[(4-methylphenyl)sulfonyl]-
6,7,15,16,23,24-hexahydro-5H,14H,22H-tribenzo[b,h,o][1,4,
10,14,7,17]dioxadithiadiazacyclononadecine-10,11-dicarbo-
nitrile (4) (0.3 g, 0.37 mmol) anhydrous NiCl2 (11.92 mg,
0.09 mmol) and dry quinoline (2.5 ml) was irradiated in a
microwave oven at 220 °C, 350 W for 15 min. After cooling

Z. Bıyıklıog˘lu, H. Kantekin / Journal of Organometallic Chemistry 693 (2008) 505–509
509
to room temperature the reaction mixture refluxed with
ethanol to precipitate the product which was filtered off.
The green solid product was washed with hot ethanol
(30 ml) and dried in vacuo. The green solid product was
chromatographed on silica gel with chloroform:methanol
(9.5:0.5) as eluents. Yield: 150 mg (40%), m.p.: >300 °C.
Anal. Calc. for C164H152N16O24S16Ni (3302.75): C, 59.64;
H, 4.63; N, 6.78; Ni, 1.77. Found: C, 59.07; H, 4.88; N,
6.82; Ni, 2.02%. IR (KBr tablet) mmax/cmꢀ1: 3054 (Ar–H),
2923–2851 (Aliph. C–H), 1632, 1595, 1500, 1468, 1346-
1162 (SO2), 1089, 1045, 815, 724, 675, 575. UV–Vis
(CHCl3): kmax/nm: [(10ꢀ5 e dm3 molꢀ1 cmꢀ1)]: 270 (4.88),
hot ethanol (45 ml) and dried in vacuo. The green solid
product was chromatographed on silica gel with chloro-
form:methanol (9.5:0.5) as eluents. Yield: 145 mg (39%),
m.p.: >300 °C. Anal. Calc. for C164H152N16O24S16Cu
(3307.61): C, 59.55; H, 4.63; N, 6.77; Cu, 1.92. Found: C,
59.48; H, 4.45; N, 6.89; Cu, 2.10%. IR (KBr tablet) mmax
/
cmꢀ1: 3054 (Ar–H), 2923–2854 (Aliph. C–H), 1629, 1593,
1497, 1465, 1341–1161 (SO2), 1083, 1048, 806, 721, 573.
UV–Vis (CHCl3):
k
max/nm: [(10ꢀ5 e dm3 molꢀ1 cmꢀ1)]:
282 (4.71), 354 (4.60), 622 (4.40), 691 (4.96). MS (FAB),
(m/z): 3307 [M]+.
1
342 (4.76), 611 (4.58), 680 (5.16). H NMR. (200 MHz,
Acknowledgement
DMSO-d6), (d: ppm) 8.58 (s, 8H, Ar–H), 7.74–7.44 (m,
32H, tosyl Ar–H), 7.65–7.03 (m, 16H, Ar–H), 7.59–7.32
(t, 16H, Ar–H), 3.94 (m, 16H, CH2–O), 3.06 (m, 16H,
CH2–S), 2.98 (t, 16H, CH2–N), 2.49 (s, 24H, CH3), 2.23
(m, 8H, CH2–CH2). MS (FAB), (m/z): 3302 [M]+.
This study was supported by the Research Fund of
Karadeniz Technical University, Trabzon-Turkey.
References
3.5. Cobalt(II) phthalocyanine (7)
[1] C.C. Leznoff, C.C. Lever, A.B.P. Lever (Eds.), Phthalocyanines,
Properties and Applications, vols. 1–4. VCH, New York, 1989, 1993,
1996.
A mixture of 5,16-bis[(4-methylphenyl)sulfonyl]-6,7,
15,16,23,24-hexahydro-5H,14H,22H-tribenzo[b,h,o][1,4,10,
14,7,17]dioxadithiadiazacyclononadecine-10,11-dicarboni-
trile (4) (0.3 g, 0.37 mmol) anhydrous cobalt(II) chloride
(11.94 mg, 0.09 mmol) and dry quinoline (2.5 ml) was irra-
diated in a microwave oven at 220 °C, 350 W for 15 min.
After cooling to room temperature the reaction mixture
refluxed with ethanol to precipitate the product which
was filtered off. The green product was washed with hot
ethanol (35 ml) and dried in vacuo. The solid product
was chromatographed on silica gel with chloroform:meth-
anol (9.5:0.5) as eluents. Yield: 164 mg (44%), m.p.:
>300 °C. Anal. Calc. for C164H152N16O24S16Co (3303.00):
C, 59.63; H, 4.63; N, 6.78; Co, 1.78. Found: C, 59.36; H,
[2] M. Hanack, M. Lang, Adv. Mater. 6 (1994) 819.
[3] C.C. Leznoff, C.C. Lever, A.B.P. Lever (Eds.), Phthalocyanines,
Properties and Applications, VCH, Weinheim, 1989.
[4] C.C. Leznoff, C.C. Lever, A.B.P. Lever (Eds.), Phthalocyanines,
Properties and Applications, VCH, Weinheim, 1993.
[5] I. Rosenthal, Photochem. Photobiol. 53 (1991) 859.
[6] F.M. Moser, A.L. Tomas, The Phthalocyanines, CRC Press, Bocar-
aton, FL, 1983.
[7] H.I. Beltran, R. Esquivel, A. Sosa-Sanchez, J.L. Sosa-Sanchez, H.
Hopfl, V. Barba, N. Farfan, M.G. Garcia, O. Olivares-Xometl, L.S.
Zamodio-Rivera, Inorg. Chem. 43 (2004) 3555.
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Mater. Sci. 39 (2) (2004) 723.
[9] A. Burczyk, A. Loupy, D. Bogdal, A. Petit, Tetrahedron 61 (1)
(2005) 179.
[10] H.I. Beltran, R. Esquivel, M. Lozada-Cassou, M.A. Dominguez-
Aguilar, A. Sosa-Sanchez, J.L. Sosa-Sanchez, H. Hopfl, V. Barba,
R. Luna-Garcia, N. Farfan, L.S. Zamodio-Rivera, Chem. – A Eur.
J. 11 (9) (2005) 2705.
4.41; N, 6.88; Co, 2.06%. IR (KBr tablet) mmax/cmꢀ1
:
3035 (Ar–H), 2945–2851 (Aliph. C–H), 1619, 1595, 1501,
1469, 1370–1140 (SO2), 1117, 938, 804, 736, 627. UV–Vis
(CHCl3): kmax/nm: [(10ꢀ5 e dm3 molꢀ1 cmꢀ1)]: 276 (4.75),
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1
351 (4.64), 617 (4.52), 686 (5.04). H NMR. (200 MHz,
¨
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DMSO-d6), (d: ppm) 8.55 (s, 8H, Ar–H), 7.70–7.41 (m,
32H, tosyl Ar–H), 7.61–7.00 (m, 16H, Ar–H), 7.54–7.27
(t, 16H, Ar–H), 3.92 (m, 16H, CH2–O), 3.04 (m, 16H,
CH2–S), 2.99 (m, 16H, CH2–N), 2.47 (s, 24H, CH3), 2.21
(m, 8H, CH2–CH2). MS (FAB), (m/z): 3303 [M]+.
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3.6. Copper(II) phthalocyanine (8)
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A mixture of 5,16-bis[(4-methylphenyl)sulfonyl]-6,7,
15,16,23,24-hexahydro-5H,14H,22H-tribenzo[b,h,o][1,4,10,
14,7,17]dioxadithiadiazacyclononadecine-10,11-dicarboni-
trile (4) (0.3 g, 0.37 mmol) anhydrous copper(II) chloride
(12.10 mg, 0.09 mmol) and dry quinoline (2.5 ml) was irra-
diated in a microwave oven at 220 °C, 350 W for 15 min.
After cooling to room temperature the reaction mixture
refluxed with ethanol to precipitate the product which
was filtered off. The light green product was washed with