Microwave-assisted synthesis and characterization of novel symmetrical substituted 19-membered tetrathiadiaza metal-free and metallophthalocyanines and investigation of their biological activities

Article abstract of DOI:10.1016/j.jorganchem.2011.01.035

This work reports on a new symmetrically substituted metal-free phthalocyanine and its transition metal complexes which were prepared by a condensation of N,N′-[propan-1,3-diilbis(tiyoetan-2,1-diil)]bis(4- methylbenzenesulfonamid) (1) and 1,2-bis (2-iodom

Full text of DOI:10.1016/j.jorganchem.2011.01.035

Journal of Organometallic Chemistry 696 (2011) 1659e1663
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Microwave-assisted synthesis and characterization of novel symmetrical
substituted 19-membered tetrathiadiaza metal-free and metallophthalocyanines
and investigation of their biological activities
,
c
a
Asiye Nas a, Elif Çelenk Kaya b, Halit Kantekin a , Atalay Sökmen , Volkan Çakır
*
a Department of Chemistry, Karadeniz Technical University, 61080 Trabzon, Turkey
b Gümüs¸hane University, 29000 Gümüs¸hane, Turkey
c Department of Biology, 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 work reports on a new symmetrically substituted metal-free phthalocyanine and its transition metal
complexes which were prepared by a condensation of N,N0-[propan-1,3-diilbis(tiyoetan-2,1-diil)]bis(4-
methylbenzenesulfonamid) (1) and 1,2-bis (2-iodomercaptoethyl)-4,5-dicyanobenzene (2) with NiCl2, ZnCl2,
CoCl2, CuCl2,and PbO salts in 2-(dimethylamino)ethanol, respectively. The phthalocyanines bearing thia
and aza donor atoms at the peripheral position were characterized by IR, UVeVis, 1H NMR, 13C NMR,
Mass spectra, and elemental analysis data. The thermal behaviors of 4e9 were investigated by TG/DTA.
Novel phthalocyanines were also investigated for enlightening their possible biological activities by
employing antimicrobial (antibacterial and antifungal), antineoplastic and antioxidative assays. Of all
tested, four samples exhibited antimicrobial activity against test microorganisms, among which, Bran-
hamella catarrhalis was the most sensitive one with a MIC value around 0.312 mg/mL followed by a yeast,
Candida albicans (MIC. 0.625 mg/mL). Due to their colored nature, the samples were found not to be
applicable for antioxidative and antineoplastic assays.
Received 17 November 2010
Received in revised form
26 January 2011
Accepted 30 January 2011
Keywords:
1,2-bis(2-iodomercaptoethyl)-4,5-
dicyanobenzene
Metallophthalocyanine
Microwave-assisted
Thermogravimetry
Metal-free phthalocyanine
Biological activity
Ó 2011 Elsevier B.V. All rights reserved.
1. Introduction
Recently, microwave processing techniques have attracted consid-
erable interest as potential alternatives to classical template pro-
Phthalocyanine which is a class of organic compounds was first
used by Reginald P. Linstead in 1933 [1]. On account of their tech-
nological and scientific significance in various fields, phthalocya-
nines have attracted considerable attention over many decades.
They have been employed in several ‘hi-tech’ applications such as
photo conducting material in laser printers and light absorbing
layers in recordable CDs [2], and used in optical limiting devices
[3e5], liquid crystals (LCs) [6e8], solar cells [9,10], batteries [11]. Due
to the fact that diamagnetic central metal ions (such as Zn or Mg)
enhance the photo toxicity of the phthalocyanines, the substituted
phthalocyanine derivatives can also be used for photodynamic
cancer therapy and other processes driven by visible light [12e15].
Generally, phthalocyanines can be obtained by the template
reactions of diverse precursors such as phthalonitrile, cyano-ben-
zamide, phthalic acid and phthalamide with metal salts in high-
boiling nonaqeous solvents at elevated temperatures [16,17].
cessing in view of the advantages of microwave heating which is
direct, rapid, controllable and selective [18e20].
Up to this point, a great variety of symmetrical phthalocyanines
have been fairly numerously synthesized [21e23]. We have also
synthesized novel phthalocyanines bearing macrocyclic substitu-
ents (e.g. diazaheptathia [24], tetraoxamonoaza [25], and dithia-
diazadioxa [26]).
In this study, we report that the preparation and characteriza-
tion by spectral features of metal-free and metallophthalocyanines
bearing four 19-membered tetrathiadiaza moieties at the periph-
eral positions. Besides, we have carried out the thermogravimetric
study of tetrasubstituted metal-free phthalocyanine (4) and met-
allophthalocyanines (5e9) in order to compare their thermal
stabilities. We believe that these novel compounds which have
a relatively high thermal stability will be fundamental substances
for potential applications in the future. Furthermore, in this work
we investigate that the four of these novel phthalocyanines exhibit
moderate antimicrobial activity against test microorganisms except
for Branhamella catarrhalis.
* Corresponding author. Tel.: þ90 462 377 25 89; fax: þ90 462 325 31 96.
E-mail address: halit@ktu.edu.tr (H. Kantekin).
0022-328X/$ e see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2011.01.035

1660
A. Nas et al. / Journal of Organometallic Chemistry 696 (2011) 1659e1663
2. Experimental
was purified by column chromatography with silica gel, using chlo-
roform: methanol (4:6) as the solvent system. Yield: 0.035 g (35%),
m.p: 206e270 ꢀC. Anal. Calcd. for (C132H154N16O16S24) (%): C, 53.02; H,
5.19; N, 7.49; S, 25.74. Found: C, 52.83; H, 5.37; N, 7.61; S, 25.62%. IR
(KBr pellet) nmax/cmꢁ1: 3065 (AreH), 2921e2851 (Aliph. CeH), 1585,
1506, 1454, 1377, 1322, 1250, 1152, 1124, 1073, 962, 746. 1H NMR
N,N0-[propan-1,3-diilbis(tiyoetan-2,1-diil)]bis(4-methylbenzenesul-
fonamid) (1) and 1,2-bis(2-iodomercaptoethyl)-4,5-dicyanobenzene (2)
were prepared according to the reported procedures [27,28]. All
chemicals, solvents, and reagents were of reagent grade quality and
were used as purchased from commercial sources. All reactions were
carried under a dry nitrogen atmosphere using Standard Schlenk
techniques. All reagents and solvents were dried and purified before
use as described by reported procedure [29]. FT-IR spectra were
obtained on a Perkin Elmer 1600 FTIR Spectrophotometer with the
samples prepared as KBr pellets.NMR spectra were recorded on
aVarianMercury200MHzSpectrometerinCDCl3, andchemicalshifts
(CDCl3): (
SeCH2), 3.34 (t, 16H, NeCH2), 3.25 (t, 16H, NeCH2), 2.78 (t, 16H,
SeCH2), 2.36 (t, 16H, SeCH2), 2.17 (s, 24H, CH3),1.5 (m, 24H, CH2). 13
NMR (CDCl3), ( : ppm): 153.77,146.23,140.93,135.23,132.95,122.03,
115.55, 114.61, 48.36, 45.23, 40.81, 38.84, 36.31, 34.46, 31.94, 29.16,
d: ppm): 7.69 (m,16H, AreH), 7.30 (s, 8H, AreH), 5.07 (t,16H,
C
d
25.13. UVeVis [(pyridine) [(10ꢁ5 dm3 molꢁ1cmꢁ1)]: 707 (5.08), 665
3
(5.04), 338 (5.23). MS (FAB), (m/z): 2987 [M þ 1]þ.
were reported (d) relative to Me4Si as an internal standard. Mass
spectra were recorded on a Micromass Quatro LC/ULTIMA LC-MS/MS
Spectrometer. Elemental analyses and metal contents of these
compounds were performed on a Costech ECS 4010 Spectropho-
tometer. Melting points were measured on an electrothermal appa-
ratus. UVeVisible spectra were recorded using a Unicam UV2-100
2.1.3. Nickel (II) phthalocyanine (5)
A mixture of 4,14-bis[(4-methylphenyl)sulfonyl]-3,4,5,6,9,10,13,14,
15,16-dekahydro-2H,8H,12H-1,17,7,11,4,14-benzotetrathiadiazacyclono-
nadecin-19,20-dicarbonitrile (3) (0.10 g, 0.13 mmol), anhydrous NiCl2
(0.0043 g, 0.033 mmol), and 2-(dimethylamino)ethanol (2 mL) were
irradiated in a microwave oven at 175 ꢀC, 350 W for 7 min. After
cooling to the room temperature, this reaction mixture was refluxed
withethanol. Thedark greenproduct was filtered off, washed with hot
ethanol and methanol, and then dried in vacuo over P2O5. Thisproduct
obtained was purified by column chromatography with silica gel,
using chloroform: ethanol (4:6) as the solvent system. Yield: 0.045 g
(44%), m.p: 226e257 ꢀC. Anal. Calcd. for (C132H152N16NiO16S24) (%): C,
52.03; H, 5.03; N, 7.36; S, 25.26. Found: C, 52.20; H, 5.21; N, 7.47; S,
25.34%. IR (KBr pellet) nmax/cmꢁ1: 3069 (AreH), 2922e2846 (Aliph.
Spectrophotometer, using
1 cm pathlength cuvettes at room
temperature. Domestic microwave oven was used for carrying out all
synthesis of phthalocyanines. A Seiko II Exstar 6000 thermal analyzer
was used to record the DTAꢁc1urves under a nitrogen atmosphere with
a heating rate of 20 ꢀC min in the temperature range of 30e900 ꢀC
using platinum crucibles.
2.1. Synthesis
2.1.1. Synthesis of 4,14-bis[(4-methylphenyl)sulfonyl]-
CeH), 1586, 1414, 1344, 1157, 1122, 960, 880, 812. 1H NMR (CDCl3): (
d:
3,4,5,6,9,10,13,14,15,16-dekahydro-2H,8H,12H-1,17,7,11,4,14-
benzotetrathiadiazacyclononadecin-19,20- dicarbonitrile (3)
ppm): 7.62 (m, 16H, AreH), 7.48 (s, 8H, AreH), 5.70 (t, 16H, SeCH2),
3.33 (t,16H, NeCH2), 3.21 (t,16H, NeCH2), 2.78 (t,16H, SeCH2), 2.46 (t,
N,N0-(2,20-(propane-1,3-diylbis(sulfanediyl))bis(ethane-2,1 diyl))
bis(4-methylbenzene sulfonamide) (1) (0.95 g, 1.9 mmol) was dis-
solved in dry DMF (20 mL) under a nitrogen atmosphere and finely
ground anhydrous K2CO3 (0.79 g, 5.7 mmol) was added and the
mixture stirred at 50 ꢀC for 2 h. A solution of 1, 2-bis(2-iodo-
mercaptoethyl)-4,5-dicyanobenzene (2) (0.95 g, 1.9 mmol) in dry
DMF (90 mL) was added dropwise over 3 h. After stirring at 50 ꢀC
for 6 days, the reaction mixture was poured into ice (100 g) and
stirred for 2 h. The residue was extracted with chloroform
(2 ꢂ 100 mL). The organic layer was dried over anhydrous sodium
sulfate and the solvent was evaporated under reduced pressure to
give a yellow crude product. The product was precipitated from
ethanol. The solid product was chromatographed on silica gel with
hexane/ethyl acetate (6:4) as eluents. Yield: 0.75 g (53%) m.p:
127e130 ꢀC. Anal. Calcd. for (C33H38N4O4S6) (%): C, 53.05; H, 5.13; N,
7.50; S, 25.75. Found: C, 53.24; H, 5.26; N, 7.62; S, 25.88%. IR (KBr
pellet) nmax/cmꢁ1: 3077 (AreH), 2922e2851 (Aliph. CeH), 2231
(C^N), 1588, 1564, 1462, 1345, 1259, 1156, 1120, 970, 904, 833. 1H
16H, SeCH2), 2.15(s, 24H, CH3),1.27 (m, 24H, CH2).13CNMR(CDCl3), (
d:
ppm): 150.31, 144.67, 140.14, 130.76, 125.49, 123.52, 115.24, 115.02,
46.05, 44.78, 41.50, 38.66, 32.95, 32.07, 30.18, 29.72, 25.95. UVeVis
[(pyridine) [(10ꢁ5
3
dm3 molꢁ1 cmꢁ1)]: 716 (5.18), 647 (4.80), 368
(5.11). MS (FAB), (m/z): 3043 [M þ 1]þ.
2.1.4. Zinc (II) phthalocyanine (6)
A
mixture of 4,14-bis[(4-methylphenyl)sulfonyl]-3,4,5,6,9,10,
13,14,15,16-dekahydro- 2H,8H,12H-1,17,7,11,4,14-benzotetrathiadiaza-
cyclononadecin-19,20-dicarbonitrile (3)(0.10g, 0.13 mmol), anhydrous
ZnCl2 (0.0045 g, 0.033 mmol), and 2-(dimethylamino)ethanol (2 mL)
were irradiated in a microwave oven at 175 ꢀC, 350 W for 9 min. After
cooling to the room temperature, this reaction mixture was refluxed
with ethanol. The dark green product was filtered off, washed with
hot ethanol and methanol, and then dried in vacuo over P2O5. This
product obtained was purified bycolumn chromatography with silica
gel, using chloroform: ethanol (4:6) as the solvent system. Yield:
0.028
g
(36%), m.p: 202e240 ꢀC. Anal. Calcd. for
NMR(CDCl3), (
d
: ppm): 7.77 (d, 4H, AreH),7.55 (d, 4H, AreH), 7.26
(C132H152N16ZnO16S24) (%): C, 51.92; H, 5.02; N, 7.34; S, 25.20. Found:
C, 51.80; H, 5.24; N, 7.42; S, 25.38%. IR (KBr pellet) nmax/cmꢁ1: 3069
(AreH), 2922e2846 (Aliph. CeH), 1586, 1404, 1333, 1158, 1088, 959,
(s, 2H, AreH), 5.86 (t, 4H, SeCH2), 3.36 (t, 4H, NeCH2), 3.12 (t, 4H,
NeCH2), 2.63 (t, 4H, SeCH2), 2.49 (t, 4H, SeCH2), 2.42 (s, 6H, CH3),
1.24 (m, 2H, CH2). 13C NMR (CDCl3), (
d: ppm): 149.72, 145.12, 142.63,
888, 742. 1H NMR (CDCl3): (
d: ppm): 7.90 (m, 16H, AreH), 7.53 (s, 8H,
134.12, 126.04, 125.77, 115.17, 114.83, 47.15, 44.69, 41.54, 40.04,
AreH), 5.67(t,16H, SeCH2),3.81(t,16H, NeCH2), 3.62(t,16H, NeCH2),
2.69 (t, 16H, SeCH2), 2.42 (t, 16H, SeCH2), 2.22 (s, 24H, CH3), 1.25 (m,
35.23, 32.00, 30.48, 29.74, 25.07. MS (FAB), (m/z): 743 [M ꢁ 3]þ.
24H, CH2). 13C NMR (CDCl3), (
d: ppm): 150.13, 146.74, 143.29, 135.60,
2.1.2. Metal-free phthalocyanine (4)
127.12, 120.43, 115.92, 115.34, 50.32, 45.44, 42.83, 40.28, 39.27, 33.47,
A
mixture of 4,14-bis[(4-methylphenyl)sulfonyl]-3,4,5,6,9,10,13,
30.75, 29.64, 24.78. UVeVis [(pyridine) [(10ꢁ5 dm3 molꢁ1 cmꢁ1)]:
3
14,15,16-dekahydro-2H,8H,12H-1,17,7,11,4,14-benzotetrathiadiazacycl-
ononadecin-19,20-dicarbonitrile (3) (0.10 g, 0.13 mmol), 2-(dimethy-
lamino)ethanol (2 mL) and DBU (2 drops) were irradiated in
a microwave oven at 175 ꢀC, 350 W for 10 min. After cooling to the
room temperature, this reaction mixture was refluxed with ethanol.
The dark green product was filtered off, washed with hot ethanol and
methanol, and then dried in vacuo over P2O5. This product obtained
713 (5.25), 644 (4.75), 365 (5.08). MS (FAB), (m/z): 3049 [M]þ.
2.1.5. Cobalt (II) phthalocyanine (7)
A mixture of 4,14-bis[(4-methylphenyl)sulfonyl]-3,4,5,6,9,10,13,14,
15,16-dekahydro-2H,8H,12H-1,17,7,11,4,14-benzotetrathiadiazacyclo-
nonadecin-19,20-dicarbonitrile (3) (0.10 g, 0.13 mmol), anhydrous
CoCl2 (0.0043 g, 0.033 mmol), and 2-(dimethylamino)ethanol

A. Nas et al. / Journal of Organometallic Chemistry 696 (2011) 1659e1663
1661
(2 mL) were irradiated in a microwave oven at 175 ꢀC, 350 W for
Table 1
Antimicrobial activity of the samples against selected microorganisms.a
8 min. After cooling to the room temperature, this reaction mixture
was refluxed with ethanol. The dark green product was filtered off,
washed with hot ethanol and methanol, and then dried in vacuo
over P2O5. This product obtained was purified by column chroma-
tography with silica gel, using chloroform: ethanol (4:6) as the
solvent system. Yield: 0.045 g (44%), m.p: 208e245 ꢀC. Anal. Calcd.
for (C132H152N16CoO16S24) (%): C, 52.03; H, 5.03; N, 7.35; S, 25.25.
Compound E. coli
St. aureus
B. subtilis
B. catarrhalis C. albicans
5
6
7
8
1.25 (10)b 2.5 (8)
1.25 (9)
1.25 (10)
1.25 (9)
1.25 (9)
0.312 (14)
0.156 (15)
0.156 (14)
0.312 (14)
0.625 (11)
1.25 (8)
1.25 (8)
1.25 (8)
2.5 (7)
2.5 (8)
2.5 (8)
0.625 (10)
0.625 (11)
0.625 (10)
Ampicillinc 1.562 (21) 0.781 (23) 1.562 (20) 0.781 (23)
N.A.
31.25 (21)
Amp Bd
N.A.
N.A.
N.A.
N.A.
Found: C, 52.18; H, 5.18; N, 7.49; S, 25.41%. IR (KBr pellet) nmax
/
a
Only the samples exhibiting positive activity were given in the Table.
Inhibition zone in diameter (mm) around the discs impregnated with 300
cmꢁ1: 3074 (AreH), 2912e2851 (Aliph. CeH), 1585, 1411, 1377, 1157,
b
m
g/
1119, 963, 891. UVeVis [(pyridine) [(10ꢁ5 dm3 molꢁ1 cmꢁ1)]: 692
3
disc of individual sample dissolved in DMSO. All inhibition zones are given in
(5.28), 617 (4.82), 479 (4.65). MS (FAB), (m/z): 3069 [M þ Na þ 3]þ.
parenthesis.
c
Ampicillin (mg/mL) was used as reference antibiotic in micro-well dilution assay
(Sigma) for antibacterial activity assay.
2.1.6. Copper (II) phthalocyanine (8)
d
AmpB ¼ Amphotericin B (
mg/mL) was used as reference antibiotic in micro-well
dilution assay (Sigma) for antifungal activity assay. N.A. Not applicable.
A mixture of 4,14-bis[(4-methylphenyl)sulfonyl]-3,4,5,6,9,10,13,14,
15,16-dekahydro-2H,8H,12H-1,17,7,11,4,14-benzotetrathiadiazacyclo-
nonadecin-19,20-dicarbonitrile (3) (0.10 g, 0.13 mmol), anhydrous
CuCl2 (0.0044 g, 0.033 mmol), and 2-(dimethylamino)ethanol
(2 mL) were irradiated in a microwave oven at 175 ꢀC, 350 W for
7 min. After cooling to the room temperature, this reaction mixture
was refluxed with ethanol. The dark green product was filtered off,
washed with hot ethanol and methanol, and then dried in vacuo
over P2O5. This product obtained was purified by column chroma-
tography with silica gel, using chloroform: methanol (8:2) as the
solvent system.. Yield: 0.038 g (37%), m.p: 221e263 ꢀC. Anal. Calcd.
for (C132H152N16CuO16S24) (%):C, 51.95; H, 5.02; N, 7.34; S, 25.22.
66032. Disc-diffusion, micro-well dilution, and MIC agar dilution
assays were performed following the methodology given in the
previous study [30]. For these, all samples were dissolved in
dimethylsulfoxide (DMSO) and prepared as 10 mg/mL concentra-
tion prior to the respective assays. Standard antibiotics employed as
controls are also given in Table 1.
3.2. Antioxidant activity assays
Found: C, 52.03; H, 5.07; N, 7.39; S, 25.31%. IR (KBr pellet) vmax
cmꢁ1: 3070 (AreH), 2923e2857 (Aliph. CeH), 1722, 1596, 1410,
1326e1157 (SO2), 1092, 954, 814, 661. UVeVis (chloroform): lmax
/
The antioxidative capacity of the samples was evaluated by
using DPPH and
b-carotene/linoleic acid assays [31,32]. In both
/
assays, butylated hydroxytoluene (BHT) was used as positive
control.
nm: [(10ꢁ5
3
dm3 molꢁ1 cmꢁ1)]: 710 (5.21), 662 (5.11), 377 (5.20).
MS (FAB), (m/z): 3046 [M ꢁ 1]þ.
2.1.7. Lead (II) phthalocyanine (9)
4. Results and discussion
A mixture of 4,14-bis[(4-methylphenyl)sulfonyl]-3,4,5,6,9,10,13,14,
15,16-dekahydro-2H,8H,12H-1,17,7,11,4,14-benzotetrathiadiazacyclo-
nonadecin-19,20-dicarbonitrile (3) (0.10 g, 0.13 mmol), anhydrous
PbO (0.0074 g, 0.033 mmol), and 2-(dimethylamino)ethanol (2 mL)
were irradiated in a microwave oven at 175 ꢀC, 350 W for 6 min.
After cooling to the room temperature, this reaction mixture was
refluxed with ethanol. The dark green product was filtered off,
washed with hot ethanol and methanol, and then dried in vacuo
over P2O5. This product obtained was purified by column chroma-
tography with silica gel, using chloroform: methanol (9:1) as the
solvent system. Yield: 0.064 g (59%) m.p: 225e260 ꢀC. Anal. Calcd.
for (C132H152N16PbO16S24) (%):C, 49.61; H, 4.79; N, 7.01; S, 24.08.
The preparation of the target metal-free (4) and Ni (II) (5), Zn
(II) (6), Co (II) (7), Cu (II) (8), Pb (II) (9) phthalocyanines was
shown in Scheme 1. Compound 3 was synthesized by the reaction
of N,N0-(2,20-(propane-1,3-diylbis(sulfanediyl))bis(ethane-2,1diyl))bis
(4-methylbenzenesulfonamide) (1) [27] with 1,2-bis (2-iodo-
mercaptoethyl)-4,5-dicyanobenzene (2) [28] in dry DMF containing
finely ground anhydrous K2CO3 as a template agent at 50 ꢀC
under a nitrogen atmosphere. Compound 3 was obtained with
a percent yield of 53%. (Scheme 1). The characteristic vibration
changes which were observed in the IR spectrum were clearly
evident for the formation of the compound 3. The absence of
NeH and the presence of C^N stretching vibration at 2231 cmꢁ1
in the IR spectrum confirmed the formation of 3 (Table 2). In the
1H NMR spectrum of this compound, the chemical shifts of NH
protons in precursor compound 1 disappeared after the macro-
cyclization reaction. 13C NMR spectrum of this compound clearly
indicated the presence of nitrile carbon atoms with peak at
Found: C, 49.65; H, 4.80; N, 7.05; S, 24.24%. IR (KBr pellet) vmax
cmꢁ1: 3042 (AreH), 2928e2844 (Aliph. CeH), 1709, 1584, 1477,
1364e1155 (SO2), 1064, 940, 883, 767. 1H NMR (CDCl3), (
: ppm):
/
d
7.73 (m, 16H, AreH), 7.56 (m, 16H, AreH), 7.20 (s, 8H, AreH), 4.86
(t, 32H, CH2eN), 4.10 (t, 16H, CH2eS), 3.48 (t, 32H, CH2eS), 2.02
(m, 8H, CH2ꢁ),1.25 (s, 24H, CH3). 13C NMR (CDCl3), (
d: ppm): 158.24,
154.52, 153.26, 147.39, 140.68, 138.36, 136.80, 130.44, 122.10, 105.00,
d
¼
115.17 and 114.83 ppm. This compound displayed the
50.54, 44.15, 43.47, 41.25, 38.17, 33.32, 26.94. UVeVis (chloroform):
expected molecular ion peak at (m/z) ¼ 743 indicating formation
of [M ꢁ 3]þ. The elemental analysis results of compound 3 were
in accordance with its calculated results.
lmax/nm: [(10ꢁ5
3
dm3 molꢁ1 cmꢁ1)]: 751 (5.29), 677 (4.82), 425
(5.00). MS (FAB), (m/z): 3189 [M ꢁ 2]þ.
Metal-free phthalocyanine (4) was synthesized by microwave
irradiation of the corresponding dicyano compound 3 in 2-
(dimethyl-amino) ethanol in the presence a few drops of DBU for 10
min. The disappearance of the ChN stretching vibration in the IR
spectrum of compound 3 supported the formation of compound 4
(Table 2). In the 1H NMR spectrum of this compound, the chemical
shifts which belong to the inner core protons of compound 4 could
not be observed due to the strong aggregation of this molecule [33].
In the mass spectrum of this compound, the molecular ion peak
which was appeared at (m/z) ¼ 2987 [M þ 1]þ supported the
3. Biological activity assays
3.1. Antibacterial and antifungal assays
The samples were individually tested against a panel of seven
microorganisms including five bacteria; Escherichia coli ATCC
25922, Staphylococcus aureus ATCC 25923, Bacillus subtilis ATCC
6633, B. catarrhalis ATCC 25238, Pseudomonas aeruginosa and two
yeasts; Candida albicans ATCC 60193 and Candida glabrata ATCC

1662
A. Nas et al. / Journal of Organometallic Chemistry 696 (2011) 1659e1663
Ts
CN
CN
S
S
S
S
I
CN
CN
S
S
N
N
S
S
HN
HN
Ts
Ts
K2CO3
dry DM
F
50 o
C
I
Ts
2
1
3
S
S
Ts
Ts
S
S
N
S
N
S
N
S
N
S
Ts
Ts
N
N
N
N
N
M
N
N
N
S
N
S
N
Ts
Ts
S
N
S
N
S
S
Ts
Ts
S
S
Scheme 1. The synthesis of the metal-free phthalocyanine 4 and metallophthalocyanines 5e9.
proposed formula for this structure. The elemental analysis results
were confirmed the desired structure of the compound 4.
3046 [M ꢁ 1]þ, (m/z): 3189 [M ꢁ 2]þ respectively, which confirmed
the proposed structure.
Metallophthalocyanines (5e9) were obtained with a percent yield
of 44, 36, 44, 37, 59% respectively. Metallophthalocyanines (5e9)
were obtained from dicyano derivative (3) and the corresponding
anhydrous metal salts NiCl2, ZnCl2, CoCl2, CuCl2, and PbO respectively,
by microwave irradiation in 2-(dimethylamino)ethanol in the range
of 6 to 10 min. In the IR spectra of metallophthalocyanines (5e9), the
disappearance of strong ChN stretching vibration of 3 was a clearly
evidence for the formation of metallophthalocyanines (5e9) (Table
2). The 1H NMR spectrum of metallophthalocyanines and metal-
free phthalocyanine were almost identical as expected. In the MS
(FAB) spectra of 5e9, we observed the molecular ion peaks at (m/z):
3043 [M þ 1]þ, (m/z): 3049 [M]þ, (m/z): 3069 [M þ Na þ 3]þ, (m/z):
The spectra of phthalocyanine 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
pep
* transitions [34]. The metal-
free phthalocyanine (4) displayed a typical electronic spectrum
with two significant absorption bands [35], were of them in the
visible region at lmax¼707 nm and 665 nm corresponding to the Q
2
1.5
1
Table 2
The spectral IR data of new compounds.
0.5
Compound
g
(AreH)
g
(Aliph. CeH)
g (C^N)
3
4
5
6
7
8
9
3077
3065
3069
3069
3074
3070
3042
2922e2851
2921e2851
2922e2846
2922e2846
2912e2851
2923e2857
2928e2844
2231
_
_
_
_
_
_
0
200
300
400
500
600
λ ( nm )
700
800
900
Fig. 1. UVeVis spectra of compounds 4 (dd), 5 (.) and 6 (e e e) in pyridine.

A. Nas et al. / Journal of Organometallic Chemistry 696 (2011) 1659e1663
1663
2
(II), Cu (II), and Pb (II) salts in DMAE, respectively. The novel
phthalocyanines were characterized by IR, UVeVis, 1H NMR, 13C
NMR, Mass spectra, and elemental analysis data. The thermal
behaviors of the metal-free phthalocyanine (4) and metal-
lophthalocyanines (5e9) were investigated by TG/DTA and it was
seen that our novel compounds were not stable above 202 ꢀC. Their
possible biological activities were also investigated and four
samples exhibited antimicrobial activity against test microorgan-
isms. However, due to their colored nature, the samples were found
not to be applicable for antioxidative and antineoplastic assays.
1.5
1
0.5
0
200
300
400
500
600
λ ( nm )
700
800
900
Acknowledgment
Fig. 2. UVeVis spectra of compounds 7 (e e e) in pyridine, 8 (dd) and 9 (.) in
chloroform.
This study was supported by The Scientific Technological
Research Council of Turkey (TUBITAK Project no: 107T429).
Table 3
References
Thermal properties of the new phthalocyanines.
Compound
M
Initial decomposition
temperature in ◦C
Main decomposition
temperature in ◦C
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symmetry of the metal-free phthalocyanine is D2h
.
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against test microorganisms except for B. catarrhalis (Table 1). After
all, stronger activity was observed by exhibiting MIC values around
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to their colored nature, the samples were found not to be applicable
for antioxidative and antineoplastic assays where spectrophoto-
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5. Conclusion
We have synthesized and characterized new symmetrically
substituted metal-free(4) and metallophthalocyanines (5e9) which
were prepared by a condensation of N,N0-[propan-1,3-diilbis(tiyoe-
tan-2,1-diil)]bis(4-methylbenzenesulfonamid) (1) and 1,2-bis (2-
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