Synthesis and electrochemistry of metallophthalocyanines bearing {4-[(2E)-3-(3,4,5-trimethoxyphenyl)prop-2-enoyl]phenoxy} groups

Article abstract of DOI:10.1016/j.jorganchem.2013.11.021

In this study, metallophthalocyanines 4, 5, 6 was carried out by the cyclotetramerization of 4-{3-[(2E)-3-(3,4,5-trimethoxyphenyl)prop-2-enoyl] phenoxy}phthalonitrile 3. The synthesis of metallo derivatives [Zn(II), Co(II), Cu(II)] of phthalocyanines obtained from corresponding phthalonitrile derivative and in the presence of the anhydrous divalent metal salts (Zn(CH ₃COO)₂, CoCl₂ and CuCl₂) was described. These phthalocyanines showed good solubility in organic solvents such as chloroform, tetrahydrofuran, DMSO and DMF. The newly synthesized Pcs were verified by IR, ¹H NMR, ¹³C NMR, UV-vis and MS spectral data. The electrochemical properties of the zinc(II), copper(II) and cobalt(II) phthalocyanines were investigated by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) methods. The cobalt complex showed a metal based reduction process, while zinc phthalocyanines were giving ligand based electron transfer processes.

Full text of DOI:10.1016/j.jorganchem.2013.11.021

Journal of Organometallic Chemistry 752 (2014) 25e29
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Synthesis and electrochemistry of metallophthalocyanines bearing
{4-[(2E)-3-(3,4,5-trimethoxyphenyl)prop-2-enoyl]phenoxy} groups
a,
b
b
c
d
e
_
*
Irfan Acar , Tayfun Arslan , Saim Topçu , Ays¸e Aktas¸ , Serkan S¸ en , Hüseyin Serencam
a Department of Energy Systems Engineering, Faculty of Technology, Karadeniz Technical University, 61830 Trabzon, Turkey
b Department of Chemistry, Faculty of Arts and Sciences, Giresun University, Giresun, Turkey
c Department of Chemistry, Faculty of Sciences, Karadeniz Technical University, 61080 Trabzon, Turkey
d Department of Chemistry, Faculty of Arts and Sciences, Ordu University, Ordu, Turkey
e Department of Food Engineering, Faculty of Engineering, Bayburt University, 69000, Bayburt, Turkey
a r t i c l e i n f o
a b s t r a c t
Article history:
In this study, metallophthalocyanines 4, 5, 6 was carried out by the cyclotetramerization of 4-{3-[(2E)-3-
(3,4,5-trimethoxyphenyl)prop-2-enoyl]phenoxy}phthalonitrile 3. The synthesis of metallo derivatives
[Zn(II), Co(II), Cu(II)] of phthalocyanines obtained from corresponding phthalonitrile derivative and in
the presence of the anhydrous divalent metal salts (Zn(CH3COO)2, CoCl2 and CuCl2) was described. These
phthalocyanines showed good solubility in organic solvents such as chloroform, tetrahydrofuran, DMSO
and DMF. The newly synthesized Pcs were verified by IR, 1H NMR, 13C NMR, UVevis and MS spectral data.
The electrochemical properties of the zinc(II), copper(II) and cobalt(II) phthalocyanines were investigated
by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) methods. The cobalt complex
showed a metal based reduction process, while zinc phthalocyanines were giving ligand based electron
transfer processes.
Received 17 May 2013
Received in revised form
7 November 2013
Accepted 19 November 2013
Keywords:
Phthalocyanine
Zinc
Microwave
Metallophthalocyanine
Cyclic voltammetry
Differential pulse voltammetry
Ó 2013 Elsevier B.V. All rights reserved.
1. Introduction
metallophthalocyanines which linked long chain aliphatic groups,
amide groups and carboxylic acid groups [13,14] or crown ether
Phthalocyanines (Pcs) have 18-
p
electron system, known as
groups [15e19], etc. at the peripheral and non-peripheral positions
of phthalocyanine ring. On the other hand, tetra-substituted Pcs are
more soluble than octa-substituted Pcs due to the high dipole
moment which derives from the unsymmetrical arrangement of
the substituents at the periphery [20,21].
The chalcone moieties are of great interest and significance
since this sub-unit is found in numerous natural compounds
[22,23]. Therefore, intense efforts have been dedicated to the
development of efficient methods for the synthesis of functional-
ized chalcones. They have attracted prominent current interest for
several years because of their broad range of biological properties
such as anticancer, antiinflammatory, antioxidant, cytotoxic, anti-
microbial, analgesic and antipyretic [24]. Furthermore, chalcones
are useful in various applications such as non-linear optics (NLO),
electrochemical sensing, optical limiting, Langmuir films and
photoinitiated polymerization [25e28].
aromatic macrocyclic compounds, which don’t occur in nature.
They have attracted great interest for the first time since their
accidental discovery in Scotland in 1928. Their considerable prop-
erties that include flexibility, thermal and chemical properties,
photoconductivity and semiconductivity [1] have been of huge
attention in research. In many fields, phthalocyanines have been
remarkably used because of their magnificently industrial and
technological properties such as for optical read-write discs [2],
medical applications [3], chemical sensors in photocopying ma-
chines [4,5], solar cells for high energy batteries [6] and photo-
catalysis [7]. In recent years, especially metallophthalocyanines
have been remarkably used photodynamic reagents for cancer
therapy [8e11] because of their good singlet oxygen generation
ability.
Low solubility of phthalocyanines in organic solvents and water
restricts for the investigations of their chemical and physical be-
haviours in many fields [12]. It is synthesized soluble metal-free or
Microwave assisted synthesis of phthalocyanines not only re-
duces chemical reactions times from hours to minutes but also
improves reactions yield and their reproducibility [29e34]. The
redox properties of phthalocyanines are critically related to most of
their industrial applications. Redox process depend on various
factors such as the type of metal, solvent, axial ligands and
* Corresponding author. Tel.: þ90 462 377 84 54; fax: þ90 462 771 72 51.
_
E-mail address: acar_irfan_2000@yahoo.com (I. Acar).
0022-328X/$ e see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jorganchem.2013.11.021

_
26
I. Acar et al. / Journal of Organometallic Chemistry 752 (2014) 25e29
substituents. Cyclic voltammetry is the most widely used method
to determine electrochemical properties in solution. Electro-
chemical properties of metallophthalocyanines have been inten-
sively studied [35,36]. Electrochemical analyses of the newly
synthesized metallophthalocyanine complexes are necessary to
determine their possible applications in different electrochemical
technologies such as chemical sensors, electrocatalysts and elec-
trochromic materials. Therefore, we have synthesized, character-
ized and investigated the electrochemical properties of these novel
metallophthalocyanine complexes substituted with (2E)-1-(3-
Hydroxyphenyl)-3-(3,4,5-trimethoxyphenyl)prop-2-en-1-one
groups on peripherally position.
1241, 1126, 1098, 1001, 828, 752. UVevis (chloroform): lmax, nm
(log ε): 334 (5.13), 611 (4.32), 672 (4.69). MALDI-TOF-MS m/z: 1819
[M þ H]þ.
2.1.4. Synthesis of copper(II) phthalocyanine (6)
The reaction was carried out by the compound 4 procedure
using compound 3 (0.2 g, 0.45 ꢀ 10ꢁ3 mol) anhydrous CuCl2
(30 ꢀ 10ꢁ3 g, 0.23 ꢀ 10ꢁ3 mol) and 2-(dimethylamino)ethanol
(0.002 L). The obtained green solid product was chromatographed
on preparative silicagel plate with chloroform:methanol (100:5) as
eluents. Yield: 0.105 g (51%). IR (KBr tablet) nmax/cmꢁ1: 3065 (Are
H), 2928e2836 (Aliph. CeH), 1661, 1579, 1503, 1432, 1419, 1313,
1275, 1242, 1185, 1124, 1051, 952, 828, 796, 747. UVevis (chloro-
form): lmax, nm (log ε): 338 (5.16), 622 (4.21), 682 (4.61). MALDI-
TOF-MS m/z: 1824 [M þ H]þ.
2. Experimental
2.1. Synthesis
2.1.1. Synthesis of 4-{4-[(2E)-3-(3,4,5-trimethoxyphenyl)prop-2-
enoyl]phenoxy}phthalonitrile (3)
3. Results and discussion
(2E)-1-(4-Hydroxyphenyl)-3-(3,4,5-trimethoxyphenyl)prop-2-en-
1-one (1) (1 g, 3.18 ꢀ 10ꢁ3 mol) was dissolved in dry DMF (0.010 L) and
4-nitrophthalonitrile (0.55 g, 3.18 ꢀ 10ꢁ3 mol) was added under
nitrogen atmosphere. To this reaction mixture finely ground anhy-
drous potassium carbonate (1.31 g, 9.54 ꢀ 10ꢁ3 mol) was added in 8
portions every 15 min. The reaction mixture was stirred under N2 at
50 ꢂC for 4 days. Then the solution was poured into ice-water (100 g).
Solid product was filtered, washed water and dried in vacuo over P2O5.
The crude product 3 was crystallized from ethanol. Yield: 0.70 g (50%),
mp: 151e153 ꢂC. IR (KBr pellet), nmax/cmꢁ1: 3071 (AreH), 2939e2840
(Aliph. CeH), 2232 (C^N), 1663, 1580, 1504, 1420, 1319, 1280, 1249,
1127, 1001, 957, 832, 754, 666, 608, 524. 1H NMR (400 MHz, CDCl3):
3.1. Syntheses and characterization
Starting from (2E)-1-(3-Hydroxyphenyl)-3-(3,4,5-trimethoxy
phenyl)prop-2-en-1-one 1 and 4-nitrophthalonitrile 2, the general
synthetic route for the synthesis of new metallophthalocyanines are
given in Scheme 1. The synthesis of peripheral substituted phthalo-
nitrile derivative
3 is based on the reaction of (2E)-1-(3-
Hydroxyphenyl)-3-(3,4,5-trimethoxyphenyl)prop-2-en-1-one with
4-nitrophthalonitrile (in dry DMF and in the presence of dry K2CO3 as
base, at 50 ꢂC in 96 h). The metallophthalocyanines 4e6 were ob-
tained by the anhydrous metal salts [Zn(CH3COO)2, CoCl2 and CuCl2]
in 2-(dimethylamino)ethanol by microwave irradiation. The struc-
d
7.97 (d, J ¼ 8 Hz, 2H, AreH), 7.78 (d, J ¼ 8 Hz, 2H, AreH), 7.75 (s, 1H,
AreH), 7.64 (t, J ¼ 8 Hz,1H, AreH), 7.40 (d, J ¼ 16 Hz, 1H, -H), 7.34 (bt,
1H, AreH), 7.28 (d, J¼16 Hz,1H, -H), 6.88 (s,2H, AreH),3.92(s,6H,Oe
CH3), 3.90 (s, 3H, OeCH3); 13C NMR (100 MHz, CDCl3):
188.87,161.26,
tures of the target compounds were confirmed using IR, 1H NMR, 13
C
a
NMR and MS spectral data. The characterization data of the new
compounds are consistent with the assigned formula.
b
d
The IR spectra of the phthalonitrile compound 3 clearly indicate
the presence of C^N group by the intense stretching bands at
2232 cmꢁ1. The 1H NMR spectra of phthalonitrile compound 3 were
recorded in CDCl3. In the 1H NMR spectrum of compound 3, OH
group of (2E)-1-(3-Hydroxyphenyl)-3-(3,4,5-trimethoxyphenyl)
prop-2-en-1-one disappeared as expected. In the 1H NMR spectrum
of 3 the aromatic protons appear at 7.97 (d), 7.78 (d), 7.75 (s), 7.64
(t), 7.34 (bt), 6.88 (s) ppm. In the 13C NMR spectrum of compound 3
154.17, 153.54, 146.16, 140.97, 135.57, 130.98, 129.96, 126.08, 124.68,
121.79, 121.71, 120.58, 120.35, 117.79, 115.26, 114.85, 109.41, 106.01,
61.00, 56.30, 56.24 MS (ESþ), (m/z): 459 [M þ H2O þ H]þ.
2.1.2. Synthesis of zinc(II) phthalocyanine (4)
Amixtureof4-{3-[(2E)-3-(3,4,5-trimethoxyphenyl)prop-2-enoyl]
phenoxy}phthalonitrile 3 (0.25 g, 0.57 ꢀ 10ꢁ3 mol), anhydrous
Zn(CH3COO)2 (53 ꢀ 10ꢁ3 g, 0.29 ꢀ 10ꢁ3 mol) and 2-(dimethylamino)
ethanol (0.0025 L) was irradiated in a microwave oven at 175 ꢂC,
350 W for 8 min. After cooling to room temperature the reaction
mixture was refluxed with ethanol to precipitate the product which
was filtered off and dried in vacuo over P2O5. The obtained green solid
product was purified from the column chromatography which is
placed aluminium oxide using only chloroform:methanol (100:3) as
solvent system. Yield: 0.115 g (44%). IR (KBr tablet) nmax/cmꢁ1: 3068
(AreH), 2933e2835 (Aliph. CeH), 1660, 1578, 1465, 1432, 1317, 1275,
1234, 1124, 1088, 1043, 1000, 826, 795, 746. 1H NMR (400 MHz,
indicated the presence of nitrile carbon atom at
d
¼ 115.26,
120.58 ppm. In the mass spectra of phthalonitrile compound 3, the
molecular ion peak was observed at m/z 459 [M þ H2O þ H]þ.
The IR spectrum of the zinc phthalocyanine 4, cobalt phthalo-
cyanine 5 and copper phthalocyanine 6 clearly indicates the
cyclotetramerization of the phthalonitrile derivatives 3 with the
disappearance of the C^N peaks at 2232 cmꢁ1. The IR spectra of
ZnPc, CoPc and CuPc are also very similar. 1H NMR spectrum of
compound 4 the aromatic protons appeared at 7.77e7.71, 7.62e
7.53, 7.36e7.31, 6.86 ppm, aliphatic CH3 protons at 3.92, 3.79 ppm.
1H NMR measurement of the cobalt and copper phthalocyanines
5e6 were precluded owing to its paramagnetic nature. The mass
spectra of tetra-substituted phthalocyanines 4, 5 and 6 confirmed
the proposed structure, with the molecular ion being easily iden-
tified at 1826 [M þ H]þ, 1819 [M þ H]þ and 1824 [M þ H]þ
respectively.
CDCl3)(d: ppm): 7.77e7.71 (m,16H, AreH), 7.62e7.53 (m,12H, AreH),
7.36e7.31 (m, 8H, AreH), 6.86 (m, 8H, AreH), 3.92 (m, 24H, OeCH3),
3.79 (m, 12H, OeCH3). UVevis (chloroform): lmax, nm (log ε): 349
(4.90), 615 (4.16), 680 (4.83). MALDI-TOF-MS m/z: 1826 [M þ H]þ.
2.1.3. Synthesis of cobalt(II) phthalocyanine (5)
The reaction was carried out by the compound 4 procedure
using compound 3 (0.2 g, 0.45 ꢀ 10ꢁ3 mol) anhydrous CoCl2
(30 ꢀ 10ꢁ3 g, 0.23 ꢀ 10ꢁ3 mol) and 2-(dimethylamino)ethanol
(0.002 L). The obtained green solid product was chromatographed
on preparative silicagel plate with chloroform:methanol (100:5) as
eluents. Yield: 0.1 g (49%). IR (KBr tablet) nmaxs/cmꢁ1: 3065 (AreH),
2924e2852 (Aliph. CeH), 1661, 1579, 1503, 1462, 1377, 1320, 1275,
The metal-free and metallophthalocyanine complexes exhibit
distinctive electronic spectra with two strong absorption regions,
one of them in the UV region at about 300e350 nm (B band) and
the other one in the visible region at 600e700 nm (Q band) [37].
UVeVis spectra of metallophthalocyanines 4e6 in chloroform
displayed an intense single Q band absorption of
around 672e682 nm. The maximum absorption band of ZnPc
p /
p* transitions

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I. Acar et al. / Journal of Organometallic Chemistry 752 (2014) 25e29
27
Scheme 1. The synthesis of metallophthalocyanines 4, 5 and 6.
derivative 4 appeared at 680 nm, while the Q bands of CoPc 5 and
CuPc 6 centred at 672 and 682 nm (Fig. 1).
3.2. Electrochemical measurements
The solution redox properties of the phthalocyanines were
studied by CV and DPV on a platinum working electrode in DCB
containing 0.1
M Tetrabutylammonium hexafluorophosphate
(TBAHFP). Table 1 lists the assignments of the couples recorded and
the estimated electrochemical parameters, which includes the half-
wave potentials (E1/2), the ratio of anodic to cathodic peak currents
(Ipa/Ipc), peak to peak potential separations (
between the first reduction and oxidation processes (
potentials are given versus Ag/AgCl reference electrode.
D
Ep) and the difference
DE1/2). The
Reduction of an electroactive species is associated to energy
level of its LUMO and whereas oxidation of an electroactive species
depends on the energy level of HOMO. Redox processes of phtha-
locyanines occur via successive one-electron transfer between
working electrode and
p-conjugated system of the phthalocyanine
ring system. A typical redox reaction yields a long lived anion or
Fig. 1. UVevis spectrum of 4, 5 and 6 in CHCl3.

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I. Acar et al. / Journal of Organometallic Chemistry 752 (2014) 25e29
Table 1
Cyclic voltammogram and differential pulse voltammogram of
The electrochemical data of the phthalocyanines.
copper(II) phthalocyanine 6 are illustrated in Fig. 3. The copper(II)
phthalocyanine gave very similar voltammograms with zinc(II)
derivative except potential shifts. The reduction peak potential of
the zinc derivative was more negative (ꢁ1.125 V) than the copper(II)
phthalocyanine (ꢁ0.813 V) corresponding to electropositivity of
central metal ion. The separation between the first and second ring
reductions was found 0.21 V for zinc(II) and 0.38 V for copper(II)
phthalocyanine in accord with literature values obtained for the
complexes which have redox inactive metal centre. The introduc-
tion of zinc ion into phthalocyanine ring can be considered as a
perturbation of the frontier MOs of the phthalocyanine molecule.
The introduction of metal ion results an increase in negative charge
of the ring system thus the system become harder to reduction.
The cyclic voltammogram of the cobalt(II) phthalocyanine 5
exhibited five redox processes (Fig. 4). Scanning the potential to the
negative side, three reversible reduction processes at ꢁ0.294 V,
ꢁ1.280 and ꢁ1.460 V and upon scanning anodically, two oxidation
processes at 0.734 V and 1.140 V were recorded. The peak ratios and
Compound
Redox
step
Ep (V)
E1/2
D
mV
Ep
Ip,a/Ip,c
DE1/2
(V)
ZnPc
R1
R2
R3
O1
O2
O3
R1
R2
R3
O1
O2
R1
R2
R3
O1
ꢁ1.230 (ꢁ1.020)
ꢁ1.440 (ꢁ1.340)
ꢁ1.680 (ꢁ1.610)
0.655 (0.532)
1.050 (0.869)
1.400 (1.290)
ꢁ1.125
ꢁ1.390
ꢁ1.645
0.593
0.960
1.345
ꢁ0.284
ꢁ1.230
ꢁ1.350
210
100
70
132
181
110
20
0.44
1.00
1.02
0.58
0.57
0.39
0.93
0.55
0.94
e
1.718
CoPc
CuPc
ꢁ0.294 (ꢁ0.274)
ꢁ1.280 (ꢁ1.180)
ꢁ1.460 (ꢁ1.240)
0.734 (ꢁ)
1.018
2.139
100
220
e
1.410 (ꢁ)
e
e
ꢁ0.813 (ꢁ0.735)
ꢁ1.190 (ꢁ1.140)
ꢁ1.460 (ꢁ1.360)
1.410 (1.320)
ꢁ0.774
ꢁ1.165
ꢁ1.410
1.365
78
50
100
90
0.93
0.73
0.49
0.48
Scan rate 100 mV/s.
D
Ep values of cathodic peaks indicate one-electron transfer reactions.
cation radical in non-aqueous solutions. The redox processes in
metallophthalocyanines depend on the central metal ion, whether
possessing an energy level between HOMO and LUMO of the
phthalocyanine. The complexes with Co, Fe and Mn possessing this
type orbitals, in general, exhibit redox processes via central metal
ion. In contrast to Co and Fe complexes Zn, Cu or Ni complexes
undergo reduction and oxidation to yield cation and anion radicals,
respectively [38e42]. The first reduction of cobalt(II) phthalocya-
nine is always on the Co(II) centre and the first oxidation is
dependent on the solvent used.
The cyclic voltammogram and differential pulse voltammogram
of ZnPc 4 exhibited six redox processes in the ꢁ1.75 to þ1.65 V
range as shown in Fig. 2. It gives three reduction processes, which
are appeared at ꢁ1.230 V, ꢁ1.440 V and ꢁ1.680 V. Three oxidation
peaks resulted at 0.655 V, 1.050 V and 1.400 V. The anodic to
cathodic peak separations of the electrochemical couples varied
from 70 to 210 mV showed that reversible and quasi-reversible
nature of the electrode processes. The anodic to cathodic peak
current ratio of reduction peaks and cathodic to anodic peak cur-
rent ratio of the oxidation peaks varied from 0.39 to 1.02 support
reversible and quasi-reversible nature of the processes.
Thefirstandsecondreductionof theCoPchadapotentialdifferenceof
an approximately 0.946 V, which was in agreement with other CoPc
complexes. The lower DE1/2 gap suggested that the first reduction of
the CoPc originated from the redox couple [Co(II)Pc(-2)]/[Co(I)Pc(-2)]
in DCB [43].
4. Conclusion
The novel phthalonitrile derivative 3 substituted with (2E)-1-(3-
Hydroxyphenyl)-3-(3,4,5-trimethoxyphenyl)prop-2-en-1-one group
and their peripherally zinc(II), cobalt(II) and copper(II) phthalocya-
nine complexes 4e6 have been synthesized for the first time
in this study. The new phthalonitrile compound and metal-
lophthalocyanines have been characterized by UVevis, IR, 1H NMR,
13C NMR, ES-MS mass spectroscopies and LT MALDI-TOF mass spec-
trometer. All these new phthalocyanine complexes showed excellent
solubility in many organic solvents such as chloroform, tetrahydro-
furan, DMSO and DMF. The electrochemical studies of the metal
complexes showed that the reduction potential of ZnPc shifted more
negative potential as a result of coordination to zinc ion causes elec-
tron enrichment of the ring system. Electrochemical behaviour of
CoPc is departed from CuPc and ZnPc with a metal based reduction.
Fig. 3. Cyclic and differential pulse voltammograms of Cu(II) phthalocyanine 6 at
0.100
width ¼ 50 ms, pulse height ¼ 50 mV, step height ¼ 4 mV, step time ¼ 200 ms).
Fig. 2. Cyclic and differential pulse voltammograms of zinc(II) phthalocyanine 4 at
0.100
width ¼ 50 ms, pulse height ¼ 50 mV, step height ¼ 4 mV, step time ¼ 200 ms).
V , Pulse
sꢁ1 scan rate on Pt in DCB/TBAHFP (CuPc 1$10ꢁ4 mol dmꢁ3
V , Pulse
sꢁ1 scan rate on Pt in DCB/TBAHFP (ZnPc 1$10ꢁ4 mol dmꢁ3

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I. Acar et al. / Journal of Organometallic Chemistry 752 (2014) 25e29
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Fig. 4. Cyclic and differential pulse voltammograms of Co(II) phthalocyanine 5 at
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This study was supported by the Research Fund of Karadeniz
Technical University, project no: 8202.
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