The synthesis and electrochemical characterization of new metallophthalocyanines containing 4-aminoantipyrine moieties on peripherally positions

Article abstract of DOI:10.1016/j.ica.2017.03.021

The electrochemical characterization and synthetic procedures of novel metallophthalocyanines (Co, Cu and Mn) 5, 6 and 7 fused eight N-(2,3-dihydro-1,5-dimethyl-3-oxo-2-phenyl-1H-pyrazol-4-yl)-4-methylbenzenesulfonamide groups connected to ethylmercapto a

Full text of DOI:10.1016/j.ica.2017.03.021

Inorganica Chimica Acta 462 (2017) 123–129
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Inorganica Chimica Acta
journal homepage: www.elsevier.com/locate/ica
Research paper
The synthesis and electrochemical characterization of new
metallophthalocyanines containing 4-aminoantipyrine moieties
on peripherally positions
Beytullah Ertem a, , Gülbınar Sarkı b, Halise Yalazan b, Zekeriya Bıyıklıog˘lu b, Halit Kantekin b
⇑
a Vocational School of Health Services, Karadeniz Technical University, 61080 Trabzon, Turkey
b 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:
The electrochemical characterization and synthetic procedures of novel metallophthalocyanines (Co, Cu
and Mn) 5, 6 and 7 fused eight N-(2,3-dihydro-1,5-dimethyl-3-oxo-2-phenyl-1H-pyrazol-4-yl)-4-methyl-
benzenesulfonamide groups connected to ethylmercapto arms on peripherally positions were reported in
this work. The metal complexes 5, 6 and 7 were prepared by a tetramerization reaction of the phthaloni-
trile derivative 4 with corresponding metal salts and materials. The characterization of new products was
made by a combination of elemental analysis, FT–IR, MALDI–TOF mass spectral data, UV–Vis, 1H NMR and
13C NMR. Electrochemical characterization of metallophthalocyanines was determined by using cyclic
voltammetry (CV) and square wave voltammetry (SWV) techniques. Copper(II) phthalocyanine showed
Pc based electron transfer processes because of redox inactive metal center. On the other hand, MnIII
and CoII metal ions behave as redox active cations in the core of the phthalocyanines. Therefore,
MnIIIClPc and CoIIPc gave metal and ligand based reduction reactions as expected.
Received 27 January 2017
Received in revised form 14 March 2017
Accepted 15 March 2017
Available online 18 March 2017
Keywords:
Synthesis
Electrochemical characterization
Phthalocyaninato cobalt(II)
4-Aminoantipyrine
p-Toluenesulfonyl chloride
Ó 2017 Elsevier B.V. All rights reserved.
1. Introduction
Metallophthalocyanines (MPcs) are composed of a central metal
atom that is bound to a p-conjugated ligand. The physicochemical
Phthalocyanines (Pcs) are versatile and stable compounds.
Structurally, Pcs are similar to porphyrins, but they are synthetic
macrocyclic derivatives. Pcs have found numerous applications in
materials science such as gas and chemical sensors, molecular solar
cells, industrial catalytic systems, electrochromic display devices,
optical switching, nanotechnology and light-emitting devices in
recent years [1]. The optical and electronic properties of the
phthalocyanine (Pc) macrocycle make it suitable for a wide range
of technological applications such as photoconductors in xero-
graphic machines [2], electrochromic displays [3], photovoltaic
materials in solar cells [4,5], systems for fabrication of light emit-
ting diodes (LED) [6], optical limiters [7], dyes at recording layers
in recordable digital versatile discs (DVDs) [8], liquid crystalline
[9], organic conductors [10] diverse catalytic systems [11], photo-
catalysts [12], photosensitizers in the cancer treatment [13], the
photoinactivation of bacteria and viruses [14], semiconductor
devices [15] and in routine diagnostic procedure [16]. It has been
also reported antioxidant properties of some phthalocyanine com-
pounds [17].
characteristics of the MPcs can be precisely changed by modifying
the central metal atom and the peripheral substituents. MPcs cre-
ate one of the most studied categories of organic functional mate-
rials with potential application in many diverse areas since they
have interesting and varied properties. Metal phthalocyanines
have become a very popular choice of materials owing to their var-
ious electrochemical activity [18–20].
The electrochemistry of metallophthalocyanines (MPcs), espe-
cially those involving redoxactive metal centers such as Co(II), Fe
(II) and Mn(II) or Mn(III), have received great interest due to
their rich ligand- and metal-based redox properties and colour
changes, leading to potential applicability especially in the areas
of electrocatalysis [21,22] and electrochromism [23]. The redox
properties of MPcs with redox active metal centers are strongly
affected by various factors such as the nature of the solvent
and supporting electrolyte, the presence or absence of oxygen,
and peripheral or non-peripheral substituents, due to their abil-
ity to coordinate axial ligands [24]. The redox properties of Pcs
are generally determined by voltammetric methods such as cyc-
lic voltammetry, differential pulse voltammetry and square wave
voltammetry [25,26].
⇑
Corresponding author.
E-mail address: bertem@ktu.edu.tr (B. Ertem).
http://dx.doi.org/10.1016/j.ica.2017.03.021
0020-1693/Ó 2017 Elsevier B.V. All rights reserved.

124
B. Ertem et al. / Inorganica Chimica Acta 462 (2017) 123–129
Antipyrine derivatives have elicited great interest particularly
2.4. Synthesis
in medicine due to their wide range of pharmacological activities
and clinical applications, including antifungal, antibacterial, anti-
pyretic, analgesic, anti-inflammatory as well as antitumoractivity
[27,28]. 4-Aminoantipyrine has been utilized as a key intermediate
for the synthesis of heterocycles bearing biologically active moi-
eties [29–32]. In addition, it is used as a reagent for biochemical
reactions producing peroxides or phenols [33,34] and is also be
used to detecting phenols in environment [35,36].
In view of great importance of 4-aminoantipyrine derived com-
pounds, its wide range of applications in various fields, we focused
on synthesizing the octa substituted 4-aminoantipyrine containing
phthalocyanine complexes with transition metal ions such as Co
(II), Cu(II) and Mn(III) and also we purposed to investigate the elec-
trochemical characterization and possible applications in various
electrochemical technologies such as electrocatalytic, electrosens-
ing and electrochromic fields.
2.4.1. N-(2,3-dihydro-1,5-dimethyl-3-oxo-2-phenyl-1H-pyrazol-4-yl)-
4-methylbenzenesulfonamide (2)
4-Aminoantipyrine (1) (1.5 g, 7.38 mmol) was dissolved in dry
pyridine (10 mL) inside a two-necked round bottomed flask under
nitrogen atmosphere and degassed several times on a vacuum line.
p-Toluenesulfonyl chloride (1.547 g, 8.11 mmol) in dry pyridine
(10 mL) was added dropwise within 1 h to the reaction mixture
at –5 °C. The colour of the flask content was changed from orange
to claret. After the addition of p-toluenesulfonyl chloride solution,
it was stirred at the same temperature under N2 atmosphere for
4 h and then kept stirring at room temperature for overnight.
Thereafter, 200 g of crushed ice was added and stirred at room
temperature for 2 h. Conc. HCl (75 mL) was added dropwise within
1 h to acidify the mixture. A distinct change in colour was observed
from claret to pale yellow. Pale yellow solid was then filtered off
and dried in vacuo. The solid residue was crystallized from ethanol
yielding as white crystals. Yield: 0.72 g (27%), m.p. 225–228 °C. Ele-
mental analysis: Calc. (%) for C18H19N3O3S: C, 60.49; H, 5.36; N,
11.76; S, 8.97, Found C, 59.67; H, 5.10; N, 10.98; S, 8.40. FT–IR: tmax
(cmÀ1) = 3266 (NAH), 3099–3028 (CAH aromatic), 2922–2823
(CH3), 1654 (C@O), 1592 (C@C), 1322–1140 (SO2–tosyl group),
1295, 1055 (NAH) and 694 (C–S). 1H NMR (ppm, CDCl3):
d = 7.65–7.63 (d, 2H, Tosyl, Ar–H), 7.42–7.38 (d, 2H, Tosyl, Ar–H),
7.29 (broad s, 1H, N–H), 7.25–7.11 (m, 5H, N–Ar–H), 3.06 (s, 3H,
N–CH3), 2.34 (s, 3H, Tosyl, CH3), 2.31 (s, 3H, C@C–CH3). 13C NMR
(ppm, CDCl3): d = 161.99 (C@O), 153.79, 143.35, 136.92, 134.43,
129.24, 127.36, 127.16, 124.44, 106.66, 35.63 (N–CH3), 21.60
(Tosyl, –CH3), 11.28 (C@C–CH3). MALDI–TOF–MS m/z: Calculated:
357.43, Found: 358 [M+H]+.
2. Experimental
2.1. Materials
Reactions were performed under an atmosphere of nitrogen and
new phthalocyanine derivatives were synthesized by using stan-
dard Schlenk techniques. 1,2-bis(2-tosyloxyethylmercapto)-4,5-
dicyanobenzene 3 was prepared according to the literature proce-
dure [37]. Following the similar procedure [38], N-(2,3-dihydro-
1,5-dimethyl-3-oxo-2-phenyl-1H-pyrazol-4-yl)-4-methylbenzene-
sulfonamide (2) was synthesized as white crystals starting from 4-
aminoantipyrine and p-toluenesulfonyl chloride. All other reagents
and solvents were of reagent grade quality from commercial sup-
pliers and were dried before use as described in the literature
[39]. Column chromatography was carried out on silica gel (70–
230 mesh) and Merck 90 active neutral alumina columns with
the indicated eluents.
2.4.2. N,N’-(((4,5-dicyano-1,2-phenylene)bis(sulfanediyl))bis(ethane-
2,1-diyl))bis(N-(2,3-dihydro-1,5-dimethyl-3-oxo-2-phenyl-1H-
pyrazol-4-yl)-4-methylbenzenesulfonamide (4)
A 100-mL two necked round-bottomed flask containing 40 mL
of dry acetonitrile and fitted with a condenser was evacuated,
refilled three times with nitrogen gas and connected to a vacuum
line. The flask was charged with compound 2 (0.7 g, 1.96 mmol),
finely ground anhydrous Na2CO3 (1.04 g, 9.81 mmol) and 1,2-bis
2.2. Equipment
A Perkin Elmer Spectrum One FT–IR spectrometer was used to
record the infrared spectra. The 1H and 13C NMR spectra were
recorded on a Varian XL–400 NMR spectrometer with CDCI3/
DMSO-d6 and chemical shifts were reported (d) relative to Me4Si
(tetramethylsilane) as the internal standard. Melting points were
determined by an electrothermal apparatus and were uncorrected.
Mass spectra were measured with Bruker Microflex LT MALDI–
TOF–MS and Micromass Quattro LC-MS/MS spectrometer. Elec-
tronic absorption (ultraviolet–visible) spectrum was recorded with
a Perkin Elmer Lambda 25 UV/Vis spectrophotometer by using a
1 cm pathlength cuvette at room temperature. Elemental analysis
of the compounds was determined on a LECO TruSpec Micro
instrument.
(2-tosyloxyethylmercapto)-4,5-dicyanobenzene
3
(0.577 g,
0.98 mmol). Under the nitrogen atmosphere, the reaction mixture
was refluxed at 95 °C for 6 days. The reaction was monitored by
TLC using chloroform:petroleum ether:methanol (7:2:1). After
cooling to room temperature, the residue was dissolved in
150 mL of chloroform and extracted with (3 Â 20 mL) water. The
combined organic extract was dried over MgSO4, filtered and the
solvent was removed by evaporation. The purification of the crude
product was made by column chromatography on neutral alumina
with chloroform:ethanol (100:1 v/v) to give the phthalonitrile
derivative 4 as a brown viscous oily product. Yield: 0.96 g (61%).
Elemental analysis: Calc. (%) for C48H46N8O6S4: C, 60.10; H, 4.83;
N, 11.68; S, 13.37, Found C, 60.51; H, 4.42; N, 10.77; S, 12.82. FT–
IR: tmax (cmÀ1) = 3068–3030 (CAH aromatic), 2922–2853 (CH2,
CH3), 2229 (C„N), 1660 (C@O), 1593 (C@C), 1333–1155 (SO2–tosyl
groups), 1290, 695 and 663 (C–S). 1H NMR (ppm, CDCl3): d = 8.48
(s, 2H, Ar–H), 8.07 (d, 4H, Tosyl, Ar–H), 7.76–7.63 (d, 4H, Tosyl,
Ar–H), 7.19–6.89 (m, 10H, N–Ar–H), 3.87 (t, 4H, N–CH2), 3.83 (t,
4H, Ar–S–CH2), 1.73 (s, 6H, N–CH3), 1.44 (s, 6H, Tosyl, CH3), 1.23
(s, 6H, C@C–CH3). 13C NMR (ppm, DMSO-d6): d = 161.75 (C@O),
153.16, 138.46, 136.84, 135.53, 133.38, 130.49, 124.02, 122.40,
121.68, 120.31, 118.55, 115.78 (C„N), 113.46, 109.49, 56.15 (N–
CH2), 40.39 (S–CH2) 35.41 (N–CH3), 22.08 (Tosyl, –CH3), 12.04
(C@C–CH3). MALDI–TOF–MS m/z: Calculated: 959.19, Found:
959.95 [M]+.
2.3. Electrochemical measurements
All electrochemical measurements were carried out with Gamry
Interface 1000 potentiostat/galvanostat utilizing a three–electrode
configuration at 25 °C. The working electrode was a Pt disc. A Pt
wire was served as the counter electrode and saturated calomel
electrode (SCE) was employed as the reference electrode and sep-
arated from the bulk of the solution by a double bridge. Electro-
chemical grade tetrabutylammonium perchlorate (TBAP) in extra
pure dichloromethane (DCM) was employed as the supporting
electrolyte at a concentration of 0.10 mol dm–3
.

B. Ertem et al. / Inorganica Chimica Acta 462 (2017) 123–129
125
2.4.3. Synthesis of phthalocyaninato cobalt(II) (5)
MALDI–TOF–MS m/z: Calculated: 3927.14, Found: 3891.74
[MÀCI]+.
Compound 4 (0.2 g, 0.208 mmol) was dissolved in 5 mL of dry n-
pentanol into a Schlenk tube under a nitrogen atmosphere. Anhy-
drous CoCl2 (14 mg, 0.108 mmol) and 3 drops of 1,8-diazabicyclo
[5.4.0] undec-7-ene (DBU) were added. The reaction mixture was
heated at 160 °C for 5 h. After cooling to room temperature, the
blue reaction mixture was diluted and the product was precipi-
tated by adding 10 mL of ethanol. The resulting precipitate was fil-
tered off, washed with EtOH and H2O separately and dried in vacuo.
Afterwards, it was dissolved in minimum amount of chloroform
and eluted on neutral alumina using chloroform:ethanol (100:1)
as eluent. The extract was evaporated to dryness and dried under
vacuum to give blue coloured compound 5. Yield: 70 mg (35%),
m.p.>300 °C. Elemental analysis: Calc. (%) for C192H184N32O24S16Co:
C, 59.20; H, 4.76; N, 11.51; S, 13.17, Found C, 58.62; H, 4.60; N,
10.74; S, 12.43. FT–IR: tmax (cmÀ1) = 3044 (CAH aromatic), 2921–
2851 (CH2, CH3), 1662 (C@O), 1638 (C@N), 1521, 1494, 1335–
1156 (SO2–tosyl groups), 1287, 695 and 664 (C–S). UV–Vis (chloro-
3. Results and discussion
3.1. Synthesis and characterization
The synthetic route of 4–7 is exhibited in Scheme 1. Herein, we
report the synthesis and electrochemical characterization of a ser-
ies of novel metallophthalocyanines 5–7. The verification of the
synthesized new compounds was made by using FT–IR, UV–Vis,
MALDI–TOF mass spectral data, elemental analysis, 1H NMR and
13C NMR.
We synthesized the compound 2 by adopting the synthetic pro-
cedure described in the literature [38] by the reaction of 4-
aminoantipyrine 1 and p-toluenesulfonyl chloride in the presence
of dry pyridine at À5 °C with the yield of 27% after crystallized
from ethanol. In the 1H NMR spectrum of 1, the signal correspond-
ing to the NH2 group disappeared and a new broad signal related to
the N–H proton at d = 7.29 ppm was observed for the compound 2.
The resonance peaks were in a good agreement with the proposed
structure in the 1H NMR spectrum of 2, being at d = 7.65–7.63 and
7.42–7.38 ppm (Tosyl, Ar–H); 7.25–7.11 ppm (N–Ar–H); 3.06, 2.34
and 2.31 ppm (methyl protons). The characteristic 13C NMR signals
of aromatic carbon atoms at d = 153.79, 143.35, 136.92, 134.43,
129.24, 127.36, 127.16, 124.44, 106.66; carbonyl carbon atom at
d = 161.99 and carbon atoms belonging to methyl groups at
d = 35.63, 21.60 and 11.28 ppm, supported the structure. The FT–
IR spectrum of 2 was easily verified with the disappearance of
the NH2 group of 1 and the presence of stretching vibrations of 2
associated with the NAH group at 3266–1055 cmÀ1 (stretching–
bending) and the tosyl group at 1322–1140 cmÀ1 which indicated
that the tosylation reaction was clearly accomplished. Other FT–IR
stretching vibrations of 2 were similar to compound 1 with slight
changes. This compound demonstrated the molecular ion peak at
m/z = 358 indicating the formation of [M+H]+. The result of ele-
mental analysis was also in accord with the proposed formula.
The phthalonitrile derivative 4 was synthesized by 2:1 substitu-
tion reaction of compound 2 with 1,2-bis(2-tosyloxyethylmer-
form), kmax, nm (loge): 702 (5.00), 663 (4.66) and 384 (4.83).
MALDI–TOF–MS m/z: Calculated: 3895.69, Found: 3182.34 [M–
4Ts–6CH3–3H]+, 2823.39 [M–6Ts–9CH3–6H]+, 2497.50 [M–8Ts–
10CH3–7H]+, 2465.31 [M–8Ts–12CH3–9H]+, 2439.40 [M–8Ts–
14CH3–5H]+.
2.4.4. Synthesis of phthalocyaninato copper(II) (6)
Under N2 atmosphere, a standard Schlenk tube was charged
with compound 4 (0.21 g, 0.219 mmol), anhydrous CuCl2 (15 mg,
0.112 mmol), 5 mL of dry n-pentanol and 4–5 drops of 1,8-diazabi-
cyclo[5.4.0] undec-7-ene (DBU) and heated at 160 °C by stirring for
4 h. At the end of this period, the mixture was cooled to room tem-
perature, filtered off and washed with methanol and water to
remove any unreacted organic residue. The crude product was dis-
solved in minimum amount of chloroform and launched into a col-
umn and eluted on neutral alumina using chloroform as eluent.
The extract was evaporated to dryness and 5 mL of ethanol was
added and stirred for 30 min. The green product 6 was filtered
and dried in vacuo. Yield: 69 mg (33%); m.p. > 300 °C. Elemental
analysis: Calc. (%) for C192H184N32O24S16Cu: C, 59.13; H, 4.75; N,
11.49; S, 13.15, Found C, 58.48; H, 4.93; N, 10.67; S, 12.36. FT–IR:
tmax (cmÀ1) = 3066 (CAH aromatic), 2921–2851 (CH2, CH3), 1663
(C@O), 1640 (C@N), 1593 (C@C), 1493, 1334–1156 (SO2–tosyl
groups), 1289, 695 and 664 (C–S). UV–Vis (chloroform), kmax, nm
capto)-4,5-dicyanobenzene
3 in the presence of anhydrous
Na2CO3 and dry acetonitrile at 95 °C for 6 days under the nitrogen
as a brown viscous oily product. The crude product was purified by
column chromatography on neutral alumina with chloroform:
ethanol (100:1 v/v) to give 4 in 61% yield. In the infrared spectrum
of 2, the signals at 3266 and 1055 cmÀ1 which were for the N–H
bond vanished and a new peak arose in the IR spectrum of 4 at
2229 cmÀ1 that was attributed to the dicyano groups. The NAH
proton signal observed in the 1H NMR spectrum of precursor com-
pound 2 at d = 7.29 ppm was disappeared and also other character-
istic signals were seen for the N–CH2 and Ar–S–CH2 protons at
d = 3.87 and 3.83 ppm respectively, in the case of product 4. In
addition, aromatic protons of compound 4 were observed at
d = 8.48, 8.07, 7.76–7.63, 7.19–6.89 ppm. Methyl protons were
seen at d = 1.73, 1.44 and 1.23 ppm in the 1H NMR spectrum of 4.
The proton-decoupled 13C NMR spectrum of this compound also
clearly indicated signals of carbonyl groups; dicyano groups; N–
CH2; Ar–S–CH2 and methyl carbons at d = 161.75; 115.78; 56.15;
40.39; 35.41, 22.08, 12.04 ppm, respectively. In addition to the
result of elemental analysis, MALDI–TOF mass spectrum of 4,
which showed a molecular ion peak at m/z = 959.95 [M]+, con-
firmed the proposed chemical structure.
(loge): 713 (5.04), 655 (4.51) and 321 (4.99). MALDI–TOF–MS m/
z: Calculated: 3900.30, Found: 3900.95 [M]+.
2.4.5. Synthesis of phthalocyaninato manganese(III) chloride (7)
A well-stopped Schlenk tube was charged with phthalonitrile
derivative
4 (0.21 g, 0.219 mmol), anhydrous MnCl2 (14 mg,
0.111 mmol), 5 mL of dry n-pentanol and 4 drops of DBU (1,8-diaz-
abicyclo[5.4.0] undec-7-ene) under nitrogen gas. The reaction mix-
ture was refluxed at 160 °C for 4 h and then it was diluted and
precipitated with 10 mL of methanol and stirred for 30 min after
cooling to room temperature. The resulting precipitate was filtered
off, washed with methanol, water and diethyl ether and afterwards
it was dissolved in minimum amount of chloroform and eluted on
neutral alumina using chloroform:ethanol (100:1) as eluent. The
extract was evaporated to dryness under vacuum and 5 mL of etha-
nol was added and stirred for 45 min. The compound 7 was filtered
and dried in vacuo. Yield: 62 mg (29%); m.p. > 300 °C. Elemental
analysis: Calc. (%) for C192H184N32O24S16MnCI: C, 58.72; H, 4.72;
N, 11.41; S, 13.06, Found C, 58.19; H, 4.72; N, 10.63; S, 12.17. FT–
IR: tmax (cmÀ1) = 3098–3082 (C–H aromatic), 2921–2851 (CH2,
CH3), 1663 (C@O), 1642 (C@N), 1592 (C@C), 1494, 1326–1154
(SO2–tosyl groups), 1288, 695 and 663 (C–S). UV–Vis (chloroform),
Metallophthalocyanines 5, 6 and 7 were prepared from the
dicyano derivative 4 and the appropriate metal salts in dry n-pen-
tanol under inert atmosphere in yields of 35%, 33% and 29%, respec-
tively. A comparison of the IR spectra obtained for 4 with 5, 6 and 7
kmax, nm (loge): 769 (5.01), 688 (4.38), 529 (4.61) and 468 (4.68).

126
B. Ertem et al. / Inorganica Chimica Acta 462 (2017) 123–129
O
OTs
OTs
CH3
N
CH3
N
H3C
S
Cl
H3C
H2N
H3C
N
NC
NC
S
S
N
O
+
O
dry Pyridine, N2 (g), 27%
-5 ºC
H3C
S
N
H
2
O
O
O
1
2
3
N2
anhydrous Na2CO3
(g)
61% dry CH3CN
95 ºC
CoPc
5
CH3
N
N
O
anhydrous CoCl2 DBU
dry n-Pentanol 2 (g)
H3C
Ts
N
35% 160 ºC
N
NC
S
S
dry n-Pentanol, DBU, N2 (g)
anhydrous CuCl , 33%,
CuPc
6
160 ºC
2
NC
O
N
N
Ts
H3C
dry n-Pentanol N2 (g)
DBU
anhydrous MnCl2 160 ºC
N
29%
CH3
4
Ts or Tosyl = p-Toluene sulfonyl
CH3
N
N
O
O
H3C
N
N
N
CH3
H3C
N
Ts
Ts
S
S
CH3
N
N
O
H3C
CH3
Ts
H3C
Ts
N
N
O
Cl
N
N
N
N
N
N
N
Mn
N
S
S
S
S
N
O
N
O
N
N
N
N
Ts
CH3
Ts
H3C
N
N
CH3
H3C
S
S
Ts
Ts
N
N
CH3
H3C
N
N
N
CH3
O
O
N
H3C
7
MnIIICIPc
Scheme 1. Synthesis of phthalocyaninato Co (II), Cu (II) and Mn(III) chloride.
confirmed the conversion of the C„N groups into the characteris-
tic skeleton of phthalocyanine. The C„N band at 2229 cmÀ1 of
compound 4 disappeared and C@N stretching vibrations of the
inner core of the metallophthalocyanines 5, 6 and 7 appeared at
1638, 1640 and 1642 cm–1, respectively. The molecular ion cluster
for metallophthalocyanine 6 was observed at m/z: 3900.95 [M]+.
Phthalocyaninato manganese(III) chloride 7 were found together
with a reasonable fragment ion at m/z: 3891.74 [MÀCI]+. The mass
spectrum of Co phthalocyanine
5 was obtained with some
fragmentation ions at m/z: 3182.34 [M–4Ts–6CH3–3H]+, 2823.39

B. Ertem et al. / Inorganica Chimica Acta 462 (2017) 123–129
127
Fig. 1. Electronic absorption spectra of MnIIIClPc, CuPc and CoPc (1.00 Â 10À5 M) in
CHCl3.
[M–6Ts–9CH3–6H]+, 2497.50 [M–8Ts–10CH3–7H]+, 2465.31 [M–
8Ts–12CH3–9H]+, 2439.40 [M–8Ts–14CH3–5H]+. The data related
with elemental analyses of all the metallophthalocyanine com-
plexes 5–7 were consistent with the proposed structures.
The electronic absorption (ultraviolet–visible) spectrum of the
cobalt(II) 5 and copper(II) 6 phthalocyanine complexes demon-
strated the expected absorptions (Fig. 1), with the main peaks of
the Q and B bands appearing at kmax = 702 (log
(4.66) and 384 nm (log = 4.83); 713 (log = 5.04), 655 (log
and 321 nm (log = 4.99), respectively. This result is typical of
e
= 5.00), 663
e
e
e
= 4.51)
e
metal complexes of substituted and unsubstituted metallophthalo-
cyanines with D4h symmetry [40,41], where a single band of high
intensity in the visible region is observed. The main peaks of the
Q and B bands of phthalocyaninato manganese(III) chloride com-
Fig. 2. (a) CV of MnIIICIPc at various scan rates (ranging from 25 to 500 mV sÀ1) on a
Pt working electrode in DCM/TBAP. (b) SWV of MnIIICIPc recorded at 0.100 VsÀ1
scan rate on a Pt working electrode in DCM/TBAP electrolyte.
plex
(log
tion bands at around 400–550 nm in addition to the B band [42–
44] at kmax = 529 nm (log = 4.61) and 468 nm (log = 4.68), respec-
7
appeared at kmax = 769 (log
e = 5.01) and 688 nm
e
= 4.38) (Fig. 1). Besides, MnIIIClPc 7 displayed the new absorp-
(DCM)/tetrabutylammonium perchlorate (TBAP) electrolyte sys-
tem on a Pt working electrode. Basic electrochemical parameters,
the assignments of the redox couples and estimated electrochem-
ical parameters including the half-wave potentials (E1/2), peak to
e
e
tively. These new bands are sometimes observed, which can be
ascribed to metal-to-ligand charge-transfer or ligand-to-metal
charge-transfer transitions because metal ions have partially filled
d orbitals [45].
peak potential separations (
currents (Ip,a/Ip,c) and difference between the first oxidation and
reduction processes ( E1/2), were derived from the analyses of
DEp), ratio of anodic to cathodic peak
D
the complexes and these data were tabulated in Table 1.
3.2. Electrochemical studies
Fig. 2 shows CV and SWV responses of MnIIIClPc in DCM/TBAP.
MnIIIClPc gave two quasi reversible reduction processes at À0.17 V
(R1) and À0.96 V (R2) and one irreversible reduction process at
Electrochemical characterization of phthalocyanines was per-
formed with CV and SWV measurements in dichloromethane
Table 1
Voltammetric data of the phthalocyanines. All voltammetric data were given versus SCE.
Complexes
MnClPc
Redox processes
aE1/2
bDEp (mV)
cIp,a/Ip,c
dDE1/2
À1
R
R
R
1 ? [Cl-MnIIIPcÀ2]/[Cl-MnIIPcÀ2
]
À0.17
À0.96
À1.44
1.02
139
147
205
130
0.69
0.66
0.51
0.71
1.19
2 ? [MnIIPcÀ2]/[MnIPcÀ2
]
À1
3 ? [Cl-MnIIPcÀ2
1 ? [ Cl-MnIIIPcÀ2]/[Cl-MnIIIPcÀ1
] ]
À1/[Cl-MnIIPcÀ3
À2
+1
O
]
À1
CoPc
CuPc
R
R
O
1 ? [CoIIPcÀ2]/[CoIPcÀ2
2 ? [CoIPcÀ2
1 ? [CoIIPcÀ2]/[CoIIPcÀ1
]
À0.21
À1.32
0.76
78
96
148
0.93
0.91
0.67
0.97
1.63
À2
]
À1/[CoIPcÀ3
]
+1
]
À1
R
R
O
1 ? [CuIIPcÀ2]/[CuIIPcÀ3
]
À0.79
À1.12
0.84
147
150
145
0.72
0.70
0.69
2 ? [CuIIPcÀ3
] ]
À1/[CuIIPcÀ4
À2
+1
1 ? [CuIIPcÀ2]/[CuIIPcÀ1
]
a
b
c
E1/2 values ((Epa + Epc)/2) were given versus SCE at 0.100 VsÀ1 scan rate.
D
Ep = Epa À Epc
.
Ip,a/Ip,c for reduction, Ip,c/Ip,a for oxidation processes.
d
D
E1/2 = E1/2 (first oxidation)-E1/2 (first reduction).

128
B. Ertem et al. / Inorganica Chimica Acta 462 (2017) 123–129
À1.44 V (R3) respectively. First two reduction processes and oxida-
tion process were quasi reversible characters and last reduction
process was irreversible with respect to Ip,a/Ip,c, and
DEp values.
With respect to the positions of the redox processes, the first two
redox couple (R1 at À0.17 V and R2 at À0.96 V) were proposed to
the reduction of MnIII to MnII and then MnII to MnI oxidation states.
The remaining reduction (R3 at À1.44 V) was proposed to Pc based
process. These assignments are in agreements with the MnPcs in
the literature [46–48]. Also, during the cathodic scan, MnIIIClPc
gave one quasi-reversible oxidation O1 at 1.02 V within the poten-
tial window of DCM/TBAP electrolyte system (DEp = 130 mV).
CoPc complexes generally give a metal based reduction process
at around 0 V due to the electron gaining to the empty d orbitals of
CoII center located between the HOMO and LUMO orbitals of the Pc
ring. Fig. 3 represents CV and SWV responses of CoPc in DCM/TBAP
electrolyte on a Pt working electrode. CoPc underwent two reduc-
tion reactions, at À0.21 V and À1.32 V, and one oxidation reaction
at 0.76 V within the potential window of DCM/TBAP electrolyte
system. CoPc gave two reversible reductions, R1 at À0.21 V
(
D
Ep = 78 mV), R2 at À1.32 V (
ble oxidation reaction O1 at 0.76 V (
potential window of DCM/TBAP electrolyte system. These reduc-
tion processes were seemed reversible with respect to Ip,a/Ip,c
and Ep values. Since while Ip,a/Ip,c values of these couples were
approximately unity at all scan rates, Ep values are ranged
D
Ep = 96 mV) and one quasi-reversi-
D
Ep = 148 mV) within the
,
D
D
between 60 and 110 mV with respect to scan rates ranging from
25 to 500 mV sÀ1 scan rates. Electrochemical behaviors of CoPc is
in agreement with the similar CoPc complexes reported in the lit-
Fig. 4. (a) CV of CuIIPc at various scan rates (ranging from 25 to 500 mV sÀ1) on a Pt
working electrode in DCM/TBAP. (b) SWV of CuIIPc recorded at 0.100 VsÀ1 scan rate
on a Pt working electrode in DCM/TBAP electrolyte.
erature [49,50], which support the proposed structure of the com-
plex synthesized here. Also, HOMO–LUMO gap of CoPc
(DE1/2 = 0.97 V) is in compliance with the CoPc reported in the lit-
erature [51].
MPc complexes having redox inactive metal centers, such as Ni,
Cu and Zn, can give only Pc based redox reactions, since the energy
level of the d orbitals of these metal ions are placed out of the
HOMO-LUMO energy levels [52]. Fig. 4 represents CV and SWV
responses of CuPc in DCM/TBAP electrolyte on a Pt working elec-
trode. CuPc gave two reduction reactions, R1 at –0.79 V and R2 at
À1.12 V during the cathodic potential scans. These reduction reac-
tions were quasi–reversible reductions, R1 at À0.79 V (
mV), R2 at À1.12 V ( Ep = 150 mV). Furthermore, one quasi-
reversible oxidation reaction, O1 at 0.84 V ( Ep = 145 mV), was
DEp = 147 -
D
D
observed during the anodic potential scans. Two reduction pro-
cesses and oxidation process were quasi reversible characters with
respect to Ip,a/Ip,c, and
DEp values. Electrochemical behaviors of
CuPc are in harmony with the general characters of CuPcs reported
in the literature [53,54]. Especially the first reduction and first oxi-
dation processes of CoIIPc were observed at very small potentials
with respect to those of CuPc, since these processes were proposed
as metal-based electron transfer processes. Also, the peak currents
increased linearly with the square root of the scan rates for scan
rates ranging from 25 to 500 mV sÀ1 (Fig. 2a for MnIIIClPc, Fig. 3a
for CoPc, Fig. 4a for CuPc), respectively.
DE1/2 of the complexes
(1.19 V for MnIIIClPc, 0.97 V for CoIIPc, 1.63 V for CuIIPc) reflected
the energy band gap between the highest occupied molecular orbi-
tal (HOMO) and the lowest unoccupied molecular orbital (LUMO).
Fig. 3. (a) CV of CoPc at various scan rates (ranging from 25 to 500 mV sÀ1) on a Pt
working electrode in DCM/TBAP. (b) SWV of CoIIPc recorded at 0.100 VsÀ1 scan rate
on a Pt working electrode in DCM/TBAP electrolyte.

B. Ertem et al. / Inorganica Chimica Acta 462 (2017) 123–129
129
This result is in harmony with the reported MnIIIClPc, CoIIPc, CuIIPc
complexes [55–57].
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In conclusion, we reported the synthetic procedures and elec-
trochemical characterization of a new series of phthalocyanine
derivatives substituted with eight N-(2,3-dihydro-1,5-dimethyl-
3-oxo-2-phenyl-1H-pyrazol-4-yl)-4-methylbenzenesulfonamide
groups through ethylmercapto bridges by using proper materials
and equipments. MALDI–TOF mass spectral data, UV–Vis, elemen-
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all these novel compounds. Electrochemistry of MnIIIClPc, CoIIPc
and CuIIPc were studied in solution with voltammetric measure-
ments. Electrochemical responses of the phthalocyanines sup-
ported the proposed structure of the metallophthalocyanines.
While CuIIPc gave Pc ring based redox processes, MnIIIClPc and CoII-
Pc gave metal based electron transfer reactions in addition to the
Pc based redox reactions, which enriched the possible usage of
the complex in various electrochemical technologies. Also, rich
redox activities of cobalt and manganese phthalocyanines indi-
cated their possible usage in especially electrocatalytic and elec-
trochromic applications.
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