Novel metal (II) phthalocyanines with 3,4,5-trimethoxybenzyloxy- substituents: Synthesis, characterization, aggregation behaviour and antioxidant activity

Article abstract of DOI:10.1016/j.dyepig.2012.07.023

A new substituted phthalonitrile derivative was prepared by a nucleophilic displacement reaction of 3,4,5-trimethoxybenzyl alcohol with 4-nitrophthalonitrile. Novel metallophthalocyanines [M: Zn (II), Co (II), Ni (II)] with four peripheral 3,4,5-trimethoxybenzyloxy groups were synthesized by cyclotetramerization of phthalonitrile derivative. These compounds were purified by crystallization and column chromatography. They were characterized by elemental analysis, FTIR, ¹H NMR, ¹³C NMR and UV-VIS spectral data. The aggregation investigations carried out in different concentrations indicate that 3,4,5-trimethoxybenzyloxy-substituted phthalocyanine compounds do not have any aggregation behaviour in concentration range of 10^-2-10^-8 M. The antioxidant activities of phthalocyanines were investigated by in vitro antioxidant assays such as free radical scavenging ability of 1,1-diphenyl-2-picrylhydrazyl (DPPH) and ferrous ion chelating ability. The highest DPPH activity and ferrous ion chelating activity were obtained from Tetrakis [(3,4,5-trimethoxybenzyloxy) phthalocyaninato] cobalt and 4-(3,4,5-trimethoxybenzyloxy) phthalonitrile, respectively. 4-(3,4,5-trimethoxybenzyloxy) phthalonitrile was shown to have a fairly ferrous ion chelating activity.

Full text of DOI:10.1016/j.dyepig.2012.07.023

Dyes and Pigments 96 (2013) 152e157
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Dyes and Pigments
journal homepage: www.elsevier.com/locate/dyepig
Novel metal (II) phthalocyanines with 3,4,5-trimethoxybenzyloxy-substituents:
Synthesis, characterization, aggregation behaviour and antioxidant activity
a
,
a
b
*
ꢀ
M. Salih Agırtas¸ , Beyza Cabir , Sadin Özdemir
a Department of Chemistry, Faculty of Science, Yüzüncü Yıl University, 65080 Van, Turkey
b Department of Biology, Faculty of Arts and Science, Siirt University, 56100 Siirt, Turkey
a r t i c l e i n f o
a b s t r a c t
Article history:
A new substituted phthalonitrile derivative was prepared by a nucleophilic displacement reaction of
3,4,5-trimethoxybenzyl alcohol with 4-nitrophthalonitrile. Novel metallophthalocyanines [M: Zn (II), Co
(II), Ni (II)] with four peripheral 3,4,5-trimethoxybenzyloxy groups were synthesized by cyclo-
tetramerization of phthalonitrile derivative. These compounds were purified by crystallization
and column chromatography. They were characterized by elemental analysis, FTIR, 1H NMR, 13C NMR and
UVeVIS spectral data. The aggregation investigations carried out in different concentrations indicate that
3,4,5-trimethoxybenzyloxy-substituted phthalocyanine compounds do not have any aggregation
behaviour in concentration range of 10ꢀ2e10ꢀ8 M. The antioxidant activities of phthalocyanines were
investigated by in vitro antioxidant assays such as free radical scavenging ability of 1,1-diphenyl-2-
picrylhydrazyl (DPPH) and ferrous ion chelating ability. The highest DPPH activity and ferrous ion
chelating activity were obtained from Tetrakis [(3,4,5-trimethoxybenzyloxy) phthalocyaninato] cobalt
and 4-(3,4,5-trimethoxybenzyloxy) phthalonitrile, respectively. 4-(3,4,5-trimethoxybenzyloxy) phtha-
lonitrile was shown to have a fairly ferrous ion chelating activity.
Received 26 April 2012
Received in revised form
16 July 2012
Accepted 30 July 2012
Available online 11 August 2012
Keywords:
Metallophthalocyanines
Synthesis
3,4,5-Trimethoxybenzyloxy groups
Aggregation
Antioxidant
Chelating activity
Ó 2012 Elsevier Ltd. All rights reserved.
1. Introduction
We and other research groups have greatly extended this series of
derivatives over the last few years [30,31]. As a part of these
Recently, metallophthalocyanines have found a great number
of important technological applications such as chemical sensors
[1e4], medical application [5e7], non-linear optic devices [8], dyes
and pigments [9e11], catalyst [12e14], electrochromic devices, as
liquid crystals [15], as LangmuireBlodgett films [16,17], photo-
chromic materials [18,19],and as photosensitizers for photody-
namic therapy [20e23]. The planar aromatic phthalocyanine
molecule can be substituted with a wide variety of functional
groups [24e27]. Methoxy groups have been extensively investi-
gated for structureeactivity relationships (SAR) since the antioxi-
dant effect of methoxy groups is well known [28]. It is biologically
important for cytotoxic agents and microtubule-binding agents
(MBAs) used in cancer chemotherapy [29]. When phthalocyanines
are combined with methoxy groups, these groups may show
a strong antioxidant effect. There is a considerable interest in the
development of the structureeactivity relationships for new
phthalocyanine derivatives. In order to prevent aggregation,
inclusion of large bulky groups on the periphery has been proposed.
endeavours, here we report the synthesis of a new series of
phthalocyanines carrying four 3,4,5-trimethoxybenzyloxy substit-
uents groups.
2. Experimental
2.1. General
All chemical used were of reagent grade quality. 1,1-Diphenyl-
2-picryl-hydrazyl (DPPH), ferrous chloride, 3-(2-pyridyl)-5,6-bis
(4-phenyl-sulfonic acid)-1,2,4-triazine (Ferrozine), butylated
hydroxyanisole (BHA), butylated hydroxytoluene (BHT) and N,N-
dimethylformamide (DMF) were purchased from Sigma (Sigmae
Aldrich GmbH, Sternheim, Germany). ZnCl2, CoCl2, NiCl2, K2CO3,
CHCl3, THF, DMSO and DBU were purchased from Merck. The
solvents were purified according to standard procedure [32] and
ꢁ
stored over molecular sieves (4 A). All reactions were carried out
under dry nitrogen atmosphere. Melting points were measured on
an electrothermal apparatus. Electronic spectra were recorded on
a Hitachi U-2900 Spectrophotometer. Routine IR spectra were
recorded on a Thermo Scientific FTIR (ATR sampling accessory)
spectrophotometer. 1H NMR spectra were recorded on a Bruker
* Corresponding author. Tel.: þ90 432 225 10 25x2232; fax: þ90 432 225 11 88.
ꢀ
E-mail address: salihagirtas@hotmail.com (M. Salih Agırtas¸ ).
0143-7208/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.dyepig.2012.07.023

ꢀ
M. Salih Agırtas¸ et al. / Dyes and Pigments 96 (2013) 152e157
153
CN
CN
OH
O
O2N
CN
CN
OCH3
H3CO
OCH3
H3CO
3
OCH3
1
OCH3
2
OCH3
OCH3
H3CO
H3CO
H3CO
O
O
H3CO
N
M
N
N
N
N
N
N
N
OCH3
O
O
OCH3
OCH3
OCH3
H3CO
OCH3
4
5
6
M= Zn Co Ni
Scheme 1. The route for the synthesis of compounds 3e6.
300 MHz spectrometer with tetramethylsilane as internal
standard.
atmosphere. After stirring for 15 min, K2CO3 (5.2 g, 36 mmol) was
added into the mixture over a period of 2 h. After stirring the
reaction mixture for a further 24 h, the reaction mixture was
poured into water (200 mL) and stirred. The precipitate was
filtered, washed with water, and dried in vacuum. Yield; 2.50 g
(77%). Compound is soluble in CHCl3, acetonitrile, DMF, acetone,
THF, dimethyl sulfoxide. Mp: 168e169 ꢁC. 1H NMR (300 MHz,
2.2. 4-(3,4,5-Trimethoxybenzyloxy)phthalonitrile (3)
A mixture of 3,4,5-trimethoxybenzyl alcohol 2 (1.65 cm3) and 4-
nitrophthalonitrile 1 (1.73 g, 16 mmol) in 30 mL dimethylforma-
mide (DMF) was stirred at room temperature under nitrogen
CDCl3)
d ppm: 8,1 (d); 7,9 (d); 7,5 (d,d); 6,8 (s); 5,2 (s); 3,8e3,7 (s);

ꢀ
154
M. Salih Agırtas¸ et al. / Dyes and Pigments 96 (2013) 152e157
Fig. 1. Electronic spectra of 4e6 in THF.
4.73; N, 8.22%. Found: C, 63.41; H, 4.70; N, 8.20%. 1H NMR (DMSO-
d6) ppm: 8, 3e6, 4 (AreH); 4.6 (OCH2); 3, 8e3, 7 (OCH3). UVeVis
(THF)
Table 1
Solubility of phthalocyanines in various solvents.
d
l
max/nm (log ): 682 (5.33), 614 (4.81) and 348 (5.23). IR
3
Solvent
4
5
6
spectrum (cmꢀ1): 2936, 2836, 1590, 1505, 1487, 1455, 1420, 1231,
1119, 1000, 745.
Tetrahydrofuran
Dimethylformamide
Dimethyl sulfoxide
Chloroform
Dichloroethane
Acetone
þþþþ
þþþþ
þþþþ
þþþþ
þþþꢀ
þþþþ
þþþꢀ
ꢀꢀꢀꢀ
þþþþ
þþþþ
þþþþ
þþþþ
þþþþ
þꢀꢀꢀ
þꢀꢀꢀ
ꢀꢀꢀꢀ
þþþþ
þþþþ
þþþþ
þþþþ
þꢀꢀꢀ
þþꢀꢀ
ꢀꢀꢀꢀ
ꢀꢀꢀꢀ
2.4. [Tetrakis (3,4,5-trimethoxybenzyloxy)phthalocyaninato] cobalt
(II) (5)
Acetonitrile
Methanol
Prepared similarly to 4 from 3, using CoCl2. The yield was 0.080 g
(5, 90%). Calc. for C72H64 Co N8O16: C, 63.76; H, 4.76; N, 8.26%.
þþþþSolubility in range of 0.150e0.240 mol/L at room temperature.
þþþꢀSolubility in range of 0.100e0.190 mol/L at room temperature.
þþꢀꢀSolubility in range of 0.075e0.080 mol/L at room temperature.
þꢀꢀꢀSolubility in range of 0.032e0.050 mol/L at room temperature and.
ꢀꢀꢀꢀinsoluble at room temperature.
Found: C, 63.71; H, 4.72; N, 8.28%. UVeVis (THF)
l
max/nm (log ):
3
665 (5.31), 605 (4.87), 328 (5.25). IR spectrum (cmꢀ1): 2938, 2835,
1591, 1506, 1456, 1418, 1331, 1231, 1121, 1094, 1002, 750.
2.5. [Tetrakis (3,4,5-trimethoxybenzyloxy)phthalocyaninato] nickel
(II) (6)
3,3 (s); 2,5 (s). 13C NMR (DMSOd6); 162.1, 153.4, 137.9, 131.3, 121.0,
116.7 (CN), 116.2, 106.6, 106.2, 71.3, 60.4, 56.4 (OCH3). IR spectrum
(cmꢀ1): 3084, 2978, 2942, 2228, 1592, 1565, 1506, 1493, 1460, 1383,
1287, 1247, 1119,1092, 980. Anal calculated for C18H16N2O4: C 66.66;
H 4.97; N 8.64%. Found C 65.78; H 4.87; N 8.41%.
Prepared similarly to 4 from 3, using NiCl2. The yield was
0.1369 g (10.10%). Calc. for C72H64 Ni N8O16: C, 63.77; H, 4.76; N,
8.26%. Found: C, 63.76; H, 4.72; N, 8.24%. 1H NMR (DMSO-d6)
d
ppm: 8, 3e6, 4 (AreH); 4.8 (OCH2); 3, 8 (OCH3). UVeVis (THF)
2.3. [Tetrakis (3,4,5-trimethoxybenzyloxy)phthalocyaninato] zinc
(II) (4)
l
max/nm (log
3
): 675 (5.26). IR spectrum (cmꢀ1): 2929, 2835, 1592,
1505, 1483, 1455, 1418, 1230, 1120, 1063, 749.
4-(3,4,5-trimethoxybenzyloxy) phthalonitrile
3
(0.162 g,
0.0005 mol) and (ZnCl2 0.017 g, 0.127 mmol) were dissolved in N,N-
dimethylformamide (1.5e2 cm3) under nitrogen in the presence of
DBU. Then, the mixture was refluxed for 8 h under nitrogen
atmosphere. After cooled down to room temperature, the crude
product was precipitated by adding water. The precipitate was
filtered, and then washed with hot water several times. After
purification, the product was dried. The product is soluble in DMF,
THF, CHCl3, acetone, dichloroethane and dimethyl sulfoxide. The
yield was 0.0915 g (6.72%). Calc. for C72H64N8O16Zn: C, 63.46; H,
2.6. Free radical scavenging activity
In this test [33], the method was used for determining DPPH
scavenging activity by a spectrophotometric method based on the
reduction of a DMF solution of DPPH radicals. Each compound (5,
25, 50, 75 and 100 mg/L) in DMF (0.5 mL) was mixed with 2 mL of
methanol solution containing DPPH radical. The mixture was
shaken vigorously and left for 30 min in the dark medium. The
absorbance was measured at 517 nm against a blank which consists
Fig. 2. Electronic spectra of 4 in DMF a concentration range of a 1: (1$10ꢀ2), 2: (2$10ꢀ3 M), 3: (7$10ꢀ4 M), 4: (4$10ꢀ5 M), 5: (2$10ꢀ6 M), 6: (1$10ꢀ7 M), 7: (3$10ꢀ8 M).

ꢀ
M. Salih Agırtas¸ et al. / Dyes and Pigments 96 (2013) 152e157
155
Fig. 3. Electronic spectra of 5 in DMF a concentration range of a 1: (1$10ꢀ2), 2: (2$10ꢀ3 M), 3: (7$10ꢀ4 M), 4: (4$10ꢀ5 M), 5: (2$10ꢀ6 M), 6: (1$10ꢀ7 M), 7: (3$10ꢀ8 M).
of 2.5 mL DMF with a spectrophotometer. Inhibition of free radical,
4-nitrophthalonitrile 1 in dry DMF in the presence of dry K2CO3.
DPPH, as percent (I%) was calculated according to formula:
The complexes 4e6 were synthesized by the reaction of 3 with
ZnCl2, CoCl2, NiCl2 under N2 atmosphere. The route for the
synthesis of compounds 3e6 is shown in Scheme 1. The charac-
terization of the compounds was carried out by the combination of
several methods, including elemental analysis, IR, 1H NMR, 13C NMR
and UVevis spectra. The proposed structures of the compounds
were confirmed by the results of these analyses.
ꢀ
ꢁ.
I% ¼ Acontrol ꢀ Asample Acontrol ꢂ 100;
where Acontrol is the absorbance of the control reaction (containing
all reagents except the test compound), and Asample is the absor-
bance of the test compound. Tests were carried out in triplicate.
BHA and BHT were used as positive control.
The structures of compounds 3, 4, and 6 were proved by 1H NMR
for both the phthalonitrile derivative and phthalocyanine through
aromatic ring protons in their respective regions. In the 1H NMR
spectrum of compound 3 in CDCl3, aromatic protons appear at 8.1e
7.9 (d) ppm, 7.6 (d,d), 6.8 (s) (AreH) and aliphatic protons as
a singlet at 5.2 (CH2) 3, 8e3, 7 (OCH3) ppm. The 13C NMR of
compound 3 in DMSO-d6 gave signals at 116 ppm (CN) and 56.4
(OCH3). In the 1H NMR spectrum of compound 4 within DMSO-d6,
aromatic protons appear at 8.3e6.4 ppm as broad, the CH2 aliphatic
protons appear at 4.6 (OCH2) ppm, and the OCH3 aliphatic protons
appear at 3.8e3.7 ppm. Integration of the signals in the aromatic
region allowed the structure of 4 to be determined. 1H NMR
measurement of compound 5 was excluded due to its paramagnetic
properties. In the 1H NMR spectrum of compound 6 within DMSO-
d6, aromatic protons appear at 7.9e6.6 ppm as broad, the CH2
aliphatic protons appear at 4.8 (OCH2) ppm, and the OCH3 aliphatic
protons appear at 3.8 ppm.
Comparison of the IR spectral data clearly indicated the
formation of compound 3 by the appearance of new absorption
bands at 3084 cmꢀ1 (Ar), 2978, 2942 (OCH3), 2228 cmꢀ1 (CN),
1592e1565 cmꢀ1 (C]C), and 1247 cmꢀ1 (AreOeAr). After
conversion of the dinitrile derivative 3 into Pcs 4e6, the sharp peak
for the (CN) vibrations disappeared. The CeH stretching vibration
of aliphatic methylene groups and AreOeAr vibrations were
observed at 2936e2836, 1231 cmꢀ1 for phthalocyanine 4, 2938e
2835, 1231 cmꢀ1 for phthalocyanine 5, and 2929e2835,
1230 cmꢀ1 for phthalocyanine 6, respectively.
2.7. Ferrous ion chelating activity
Ferrous ions chelating activity of free and bounded compounds
were determined according to the method of Dinis et al. [34].
Briefly, 0.5 mL various concentrations (5e100 mg/L) of DMF solu-
tion containing compounds were incubated with 25 mL of 2 mM
FeCl2 solution. The reaction was started by adding of 0.1 mL of
ferrozine (5 mM). The mixture was left for standing 10 min at room
temperature then the absorbance was measured at 562 nm against
blank. The results were expressed as percentage of inhibition of the
ferrozineeFe2þ complex formation. EDTA was used as a positive
control. The percentage of inhibition of the ferrozineeFe2þ complex
formation was calculated using the formula given;
ꢀ
ꢁ.
Chelating activityð%Þ ¼ Acontrol ꢀ Asample Acontrol ꢂ 100;
where Acontrol is the absorbance of the control reaction, and Asample
represents the absorbance obtained in the presence of extracts or
EDTA.
3. Results and discussion
3.1. Synthesis and characterization
The UVevis spectra of the phthalocyanines 4e6 in THF showed
characteristic Q band absorptions at 682, 665, and 675 nm which
Our key starting compound 3 was obtained through the
reaction between 3,4,5-trimethoxybenzyl alcohol
2
and
Fig. 4. Electronic spectra of 6 in DMF a concentration range of a 1: (1$10ꢀ2), 2: (2$10ꢀ3 M), 3: (7$10ꢀ4 M), 4: (4$10ꢀ5 M), 5: (2$10ꢀ6 M), 6: (1$10ꢀ7 M), 7: (3$10ꢀ8 M).

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M. Salih Agırtas¸ et al. / Dyes and Pigments 96 (2013) 152e157
156
were attributed to the
pep* transition from the highest occupied
molecular orbital (HOMO) to the lowest unoccupied molecular
orbital (LUMO) of the Pcs ring. The other bands (B) in UV region for
4, 5 were observed at 348e328 nm due to transition from the
deeper
p levels to the LUMO. The absorption spectra of 4e6 in THF
were shown in Fig. 1.
Phthalocyanines 4e6 became highly soluble in various organic
solvents, including tetrahydrofuran, dimethylformamide, dimethyl
sulfoxide and chloroform, due to the incorporation of four 3,4,5-
trimethoxybenzyloxy groups into the phthalocyanine rings. The
solubility of phthalocyanines in various solvents was shown in
Table 1.
The aggregation behaviour of phthalocyanines was investigated
in different concentrations. None of the phthalocyanines 4e6
exhibited any aggregation in DMF in the concentration range
1.10ꢀ2 Me3.10ꢀ8 M (Figs. 2e4). As frequently encountered in most
phthalocyanines, weaker absorption on the higher energy side of Q
bands indicates the presence of aggregated species which are
generally observed together with the main Q bands essentially
responsible for the intense absorption occurring due to the
monomeric species. The graph of molar absorptivity versus
concentration gave a constant value for the concentration range of
1.10ꢀ2e3.10ꢀ8 M. The spectra showed monomeric behaviour evi-
denced by a single Q band, typical of metallophthalocyanines
compounds for 4e6 in DMF, which depict the monomeric nature of
the these complexes in this solvent [35].
Fig. 6. Chelating effect of 3, 4, 5, 6 compounds on ferrous ion.
ferrous ion-chelating activity, different compounds such as 3, 4, 5
and 6 were tested. As shown in Fig. 6 maximum chelating activity
(96.7%) was obtained at concentration of 100 mg/L. The order of
chelating activity of compounds was found to be 3 > 6 > 5 > 4
(Fig. 6). EDTA showed 98.8% chelating activity. As a result,
compound 3 can be used as a positive control for metal chelating.
4. Conclusion
A
novel series of phthalocyanines carrying four 3,4,5-
trimethoxybenzyloxy functionalities were synthesized and charac-
terized. Phthalocyanines without any substituent have poor solu-
bility in organic solvents and have limited application area [38]. The
phthalocyanine derivatives including 3,4,5-trimethoxybenzyloxy
groups may exhibit important applications because of high solu-
bility in organic solvents. In this study we have shown that the 3,4,5-
trimethoxybenzyloxy groups can be efficient substituents to keep
phthalocyanine macrocycles away from aggregation. Free radical
scavenging activity (DPPH) and ferrous ion-chelating activity of all
compounds were studied. It was determined that only 3 and 5
possess chelating activity and DPPH activity. Additionally,
compound 3 can be used instead of EDTA for chelating activity.
3.2. Scavenging effect on DPPH free radical
Free radicals are known to be a major factor in biological
damage. DPPH, a free radical compound that is stable at room
temperature, has been widely used to determine the free radical-
scavenging activity of different samples such as organic and inor-
ganic compounds [36]. In Fig. 5, experimental results of the free and
metal bounded compounds on 1,1-diphenyl-2-picrylhydrazyl
(DPPH) radical-scavenging activity are shown. When the concen-
tration was increased from 5 mg/L to 100 mg/L, DPPH activity
increased from 12.7% to 51.6% mg/L and 53.9% to 67.9 mg/L for 6 and
5, respectively. It was found that 5 had the highest DDPH activity,
while 3 had the lowest. BHA and BHT showed more DPPH activity
than studied compounds.
Acknowledgements
This study was supported by the Research Fund of Yüzüncü Yıl
University.
3.3. Ferrous ion-chelating activity
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