Synthesis, electrochemical, in-situ spectroelectrochemical and in-situ electrocolorimetric characterization of new phthalocyanines containing macrocyclic moieties

Article abstract of DOI:10.1016/j.dyepig.2013.10.037

In this work, we synthesized new phthalocyanine compounds containing optically active 1,1′-binaphthyl crown ethers units. The metal-free phthalocyanine (3) was synthesized by the cyclotetramerization of dinitrile derivative (2) in dry n-pentanol by a classical method. However, metal phthalocyanines complexes (4, 5, 6), were synthesized by the reaction of dinitrile derivative (2) in DMAE. The structure of the new compounds were characterized by using spectroscopic data and elemental analysis. Electrochemical properties of Co (II) and Zn (II) phthalocyanines were investigated by using cyclic voltammetry and differential pulse voltammetry techniques. They exhibited two reversible Pc ring-based one-electron reduction couples. The Co (II) and Zn (II) phthalocyanines gave very similar voltammetric responses with slight potential shift due to different metal center.

Full text of DOI:10.1016/j.dyepig.2013.10.037

Dyes and Pigments 103 (2014) 95e105
Contents lists available at ScienceDirect
Dyes and Pigments
journal homepage: www.elsevier.com/locate/dyepig
Synthesis, electrochemical, in-situ spectroelectrochemical and in-situ
electrocolorimetric characterization of new phthalocyanines
containing macrocyclic moieties
Meltem Betül Kılıçaslan , Halit kantekin ,*, Atıf Koca b
a
a
a
Department of Chemistry, Faculty of Science, Karadeniz Technical University, 61080 Trabzon, Turkey
Department of Chemical Engineering, Engineering Faculty, Marmara University, 34722 Göztepe, Istanbul, Turkey
b
a r t i c l e i n f o
a b s t r a c t
0
Article history:
Received 1 July 2013
Received in revised form
In this work, we synthesized new phthalocyanine compounds containing optically active 1,1 -binaphthyl
crown ethers units. The metal-free phthalocyanine (3) was synthesized by the cyclotetramerization of
dinitrile derivative (2) in dry n-pentanol by a classical method. However, metal phthalocyanines com-
plexes (4, 5, 6), were synthesized by the reaction of dinitrile derivative (2) in DMAE. The structure of the
new compounds were characterized by using spectroscopic data and elemental analysis. Electrochemical
properties of Co (II) and Zn (II) phthalocyanines were investigated by using cyclic voltammetry and
differential pulse voltammetry techniques. They exhibited two reversible Pc ring-based one-electron
reduction couples. The Co (II) and Zn (II) phthalocyanines gave very similar voltammetric responses with
slight potential shift due to different metal center.
27 September 2013
Accepted 27 October 2013
Available online 12 November 2013
Keywords:
Cyclotetramerization
Phthalonitrile
Chirality
Ó 2013 Elsevier Ltd. All rights reserved.
Dicarbonitrile
Electrochemistry
Spectroelectrochemistry
1. Introduction
phthalocyanines first explored by Leznoff and Kobayashi research
groups [17]. The precursors phthalonitriles can be prepared by
Metal-free phthalocyanine and its metal complexes have been
intensively investigated since the early-1930s [1]. They play an
important role in many advanced applications and modern tech-
nologies, mostly by virtue of their characteristic optical absorption
and high chemical stability. The functions of phthalocyanine, its
derivatives and phthalocyanine metal complexes are almost based
on a redox or electron transfer reaction [2e4].
Much attention has been paid to preparation of new phthalo-
cyanine derivatives because of their application as colorants,
chemical sensors, electrochromic compounds, liquid crystalline
materials and organic conductors [5e8]. They are generally insol-
uble in common organic solvents, although their solubility can be
improved by incorporation of substituents such as phenoxy, alkyl
or alkoxy of different chain lengths [9,10] or branched system at
peripheral positions [11e16].
aromatic nucleophilic substitution of 3- or 4- nitrophthalonitrile
with appropriate diols in DMF using K CO as a base. The
resulting bisphthalonitriles can be cyclotetramerized into corre-
sponding symmetric bridged phthalocyanines. Their low yields
can be explained by the expected formation of oligomeric
products.
Chirality is one of the most fascinating and complicated features
commonly found in nature [18]. Inspired by the elegance of natural
chiral structures with biological activity, numerous artificial chiral
compounds including optically active porphyrins and phthalocya-
nines have been developed depending on various asymmetric
synthetic methods [19].
2
3
Up to now, few reports have explored the process of
combining chiral binaphthol groups with a phthalocyanine core
[20]. Since the first report on the use of chiral binaphthy-based
crown ethers as hosts for molecular recognition, chiral binaph-
thol has attracted much attention. Chiral macrocycles, metal
Another interesting class of alkoxy- and aryloxy- substituted
phthalocyanines are 1:25, 11:15- and 2:24,10:16- bridged
0
complexes, linear oligomers and polymers based on the 1,1 -
binaphthyl structure have been synthesized for use in molecular
recognition, asymmetric catalysis and as new functional materials
[21].
*
Corresponding author. Tel.: þ90 462 377 2589; fax: þ90 462 325 3196.
E-mail address: halit@ktu.edu.tr (H. kantekin).
0143-7208/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.dyepig.2013.10.037

96
M.B. Kılıçaslan et al. / Dyes and Pigments 103 (2014) 95e105
In the last decade, microwave energy has attracted interest as an
Vis absorption spectra and chromaticity diagrams were measured
by an Ocean Optics QE65000 diode array spectrophotometer.
In-situ spectroelectrochemical measurements were carried
out by utilizing a three-electrode configuration of thin-layer
alternative to traditional heating, because microwave-assisted
synthesis can result in increased yields and lowered reaction
times [22e25].
ꢀ
Electrochemical and spectroelectrochemical measurements
show that while copper phthalocyanine gives only ring-based
electron transfer reactions, incorporating redox active metal cen-
quartz thin-layer spectroelectrochemical cell at 25 C. The
working electrode was a semipermeable Pt sheet. Pt wire counter
electrode separated by a glass bridge and a SCE reference elec-
trode separated from the bulk of the solution by a double bridge
were used. In-situ electrocolorimetric measurements, under
potentiostatic control, were obtained using an Ocean Optics
QE65000 diode array spectrophotometer at color measurement
mode by utilizing a three-electrode configuration of thin-layer
quartz spectroelectrochemical cell. Prior to each set of mea-
surements, background color coordinates (x, y and z values) were
taken at open-circuit, using the electrolyte solution without the
complexes under study. During the measurements, readings
were taken as a function of time under kinetic control, however
only the color coordinates at the beginning and end of each
redox process were reported.
II
III
III
ters, Co , Fe Ac, and Mn Ac, into the phthalocyanine core extends
the redox richness of the phthalocyanine ring with the metal-based
reduction and oxidation couples of the metal centers in addition to
the common phthalocyanine ring-based electron transfer pro-
cesses. In-situ electrocolorimetric measurements of the complexes
allow quantification of color coordinates of each electrogenerated
anionic and cationic redox species. Presence of O
2
in the electrolyte
system influences the redox couples of the complexes due to the
interaction between O
active metal center.
2
and metallophthalocyanines having redox
In our previous papers, we reported electrochemical and spec-
troelectrochemical properties of metallophthalocyanines synthe-
sized by our research groups [26e32]. Electrochemical and
spectroelectrochemical responses of the complexes were used
propose application of the complexes in different electrochemical
2.3. Synthesis
þ
’
0
’
application fields, such as, electrocatalysts for H reduction [33e
2.3.1. Synthesis of 2,2 -[1,1 -Binaphtalene-2,2 -diyl bis(oxy)]
diethanol (1)
3
5], electrochemical oxygen reduction reaction [27,36,37], elec-
trochemical metal ion sensor [38e42] and electrochromism [31e
3]. In this work, we have investigated the electrochemical and
spectroelectrochemical properties of these newly synthesized
complexes and proposed possible application fields.
0
0
1,1 -Binaphthalene-2,2 -diol (10 g, 35 mmol) was dissolved in
4
60 mL absolute ethanol under a N
2
(g) atmosphere and NaOH (35 g,
ꢀ
87.5 mmol) was added. The mixture was heated at 50 C, and 2-
chloroethanol (6 mL, 87.4 mmol) and 17 mL absolute ethanol
were added dropwise for 15 min. Then it was refluxed for two days
2
under N (g) atmosphere. The mixture was controlled with chlo-
2
. Experimental
roform/methanol (9.5:0.5) solvent system and then the synthesis
was completed. The cream-like mixture was cooled to room tem-
perature, filtered and evaporated to dryness under vacuum and
finally a viscous liquid product was obtained. This product was
redissolved in chloroform (200 mL), and then washed with 10%
NaOH and water, respectively. The combined organic extracts were
2.1. Materials
0
0
1
,1 -binaphthalene-2,2 -diol was purchased from Aldrich. 4,5-
dichloro-1,2-dicyanobenzene was synthesized according to the
procedure reported in the literature [44e46]. All solvents were
dried and purified as described by Perrin and Armarego [47].
4
dried with anhydrous MgSO and evaporated to dryness. The
product was isolated as a cream-like solid following recrystalliza-
tion of the crude residue from ethanol. Yield: 7 g (54%). m.p.: 100e
ꢀ
2
.2. Equipment
102 C. Anal. Calcd for C24
22 4
H O : C: 77.01; H: 5.88. Found: C: 77.20;
n
ꢁ1
H: 5.76%. IR (KBr tablet),
max/cm : 3516e3240 (OH), 3055(Are
),
:ppm): 8.06e7.87 (m, 4H, ArH), 7.47e7.11
(m, 8H, ArH), 4.19e4.03 (m, 4H, OeCH ), 3.57 (br s, 4H, OeCH ),
3
2.29 (s, 2H, OH). C NMR (CDCl ), (d:ppm): 155.03, 134.02, 130.12,
The IR spectra were recorded on a Perkin Elmer 1600 FT-IR
H), 2917 (Alif. CeH), 1619, 1456, 1242 (Ar-O-C),1141e1047 (eOCH
2
1
13
1
Spectrophotometer, using KBr pellets. H and C NMR spectra
were recorded on a Varian Mercury 200 MHz spectrometer in
CDCl
3
972. H NMR (CDCl ), (d
2
2
13
3
, and chemical shifts were reported (
d
) relative to Me
4
Si as
internal standard. Mass spectra were measured on a Micromass
Quatro LC/ULTIMA LC-MS/MS spectrometer. The elemental ana-
lyses were performed on a Costech ECS 4010 instrument. Melting
points were measured on an electrothermal apparatus and are
uncorrected. The cyclic voltammetry (CV) and square wave vol-
tammetry (SWV) measurements were carried out with Gamry
Reference 600 potentiostat/galvanostat controlled by an external
129.87,127.66, 126.92,124.44,123.69,117.84,111.14, 71.96, 61.46. MS
(FAB) (m/z): 374 [M] .
þ
2.3.2. Synthesis of 6,7,22,23-Tetrahydrobenzo[e]dinaphtho [1,2-
m:2’,1’- k][1,4,7,10] tetraoxacyclotetradecine-2,3-dicarbonitrile(2)
0
Compound 2 was prepared as follows: 2,2’-[1,1 -Binaphtalene-
2,2’-diyl bis(oxy)]diethanol (3 g, 8.16 mmol), 192 mL dry acetoni-
ꢀ
PC and utilizing a three-electrode configuration at 25 C. The
trile, anhydrous K
40.08 mmol) and 4,5-dichloro-1,2-dicyanobenzene (1.6 g,
8.16 mmol) were refluxed under N (g) atmosphere for 7 days. The
2 3
CO (5.58 g, 40.08 mmol), anhydrous NaI (6.12 g,
2
working electrode was a Pt disc with a surface area of 0.071 cm . A
Pt wire served as the counter electrode. Saturated calomel elec-
trode (SCE) was employed as the reference electrode and separated
from the bulk of the solution by a double bridge.
2
reaction system was controlled with chloroform/methanol (9.5:0.5)
solvent system and then the procedure was completed. The resul-
tant mixture was evaporated to dryness under vacuum and finally a
viscous liquid product was obtained. This cream-like product was
redissolved in chloroform (200 mL) and washed with water. The
Electrochemical grade TBAP in extra pure DCM and DMSO was
employed as the supporting electrolyte at a concentration of
ꢁ
3
0
.10 mol dm . For each measurement, the reference electrode tip
was moved as close as possible to the working electrode so that
uncompensated resistance of the solution was a smaller fraction of
the total resistance and therefore the potential control error was
low. Moreover, IR compensation was also applied to the voltam-
metric measurements to minimize the potential control error. UV-
4
combined organic extracts were dried with anhydrous MgSO and
evaporated to dryness. The product was isolated as a cream-like
solid following recrystallization of the crude residue from
ꢀ
ethanol. Yield: 2.4 g (60%). m.p.: 94e96 C. Anal. Calcd for
32 22 2 4
C H N O : C: 77.10; H: 4.41; N: 5.62. Found: C: 77.00; H: 4.37; N:

M.B. Kılıçaslan et al. / Dyes and Pigments 103 (2014) 95e105
97
ꢁ
1
5
.58%. IR (KBr tablet),
CeH), 2235 (C^N), 1211(Ar-O-C), 1144e 1015(eOCH
NMR (CDCl ), ( : ppm): 8.15e7.71 (m, 5H, ArH), 7.60e7.11 (m, 9H,
ArH), 4.28e4.08 (m, 4H, OeCH
NMR (CDCl ), ( :ppm): 157.09, 153.21, 131.07, 130.96, 129.59, 128.10,
26.78, 124.95, 123.44, 116.11, 114.48, 113.23, 110.64, 108.34, 71.70,
n
max/cm : 3057 (AreH), 2924e2854 (Alif.
refluxed with ethanol (40 mL) to precipitate the product, which
was then filtrated and dried in vacou. The solid product was puri-
fied by preparative thin layer chromatography (TLC) using chloro-
1
2
), 809. H
3
d
13
2
), 3.99e3.66 (m, 4H, OeCH
2
).
C
form/methanol (9.5:0.5) solvent system. Yield: 0.19 g (38%), m.p:
ꢀ
3
d
>300 C. Anal. Calc. for C128
90
H N
8
O
16: C: 77.03; H: 4.51; N: 5.62.
ꢁ1
1
7
Found: C: 77.08; H: 4.43; N: 5.66%. IR (KBr tablet),
nmax/cm
:
þ
0.24. MS (FAB) (m/z): 537 [M þ K] .
3285 (NeH), 3060 (AreH), 2923e2853 (Alif. CeH), 1610(NeH,
1
bending), 1260 (Ar-O-C), 1122e1022 (-OCH
(CDCl ), ( : ppm): 7.44e7.38 (m,18H, ArH), 7.22e7.20 (m, 18H, ArH),
.95(m, 18H, ArH), 3.93e3.89 (m, 18H, OeCH ), 3.79e3.76(m, 16H,
:ppm): 155.06, 153.73, 134.06, 131.32,
2
), 1022, 807. H NMR.
2
.3.3. Metal-free phthalocyanine (3)
3
d
6
2
A standard schlenk tube was charged with compound 2 (0.5 g,
mmol), 5 mL n-pentanol, 0.05 mL 1,8-diaza bicyclo[5.4.0]undec-
-ene(DBU) and 0.03 mL anhydrous pyridine under argon atmo-
sphere and degassed several times. The temperature of the mixture
was gradually increased up to 160 C before it was stirred for 24 h.
13
1
7
2 3
OeCH ). CNMR (CDCl ), (d
130.24, 130.11, 128.54, 128.41, 127.68, 127.02, 126.90, 125.25, 124.41,
123.68, 71.96, 71.38. UV-Vis (chloroform):
l
max/nm
:
ꢁ5
3
ꢁ1
ꢁ1
ꢀ
[(10 ε dm mol cm )]: 710 (5.10), 677 (5.05), 644 (4.80), 338
þ
After cooling to room temperature, the reaction mixture was
(5.09). MS (FAB) (m/z): 2015 [Mþ3 þ H
2
O] .
Scheme 1. The synthesis of the metal-free phthalocyanine and metallophthalocyanines derivatives.

98
M.B. Kılıçaslan et al. / Dyes and Pigments 103 (2014) 95e105
ꢀ
88 8
.205 g (40%), m.p:>300 C. Anal. Calc. for C128H N O16Cu: C:
0
7
4.80; H: 4.28; N: 5.45. Found: C: 74.87; H: 4.18; N: 5.56%. IR (KBr
ꢁ1
tablet),
nmax/cm : 3054 (AreH), 2924e2840 (Alif. CeH), 1428,
1
332, 1248(Ar-O-C),1072e1069(eOCH ), 888. UV-Vis (chloroform):
2
ꢁ
5
3
ꢁ1
ꢁ1
lmax/nm: [(10 ε dm mol cm )]: 689 (5.07), 626 (4.93), 338
þ
(4.83). MS (FAB) (m/z): 2073 [M þ H
2
O] .
2.3.4.3. Zn(II) phthlaocyanine (6). Compound 6 was prepared ac-
cording to general procedure for metallophthalocyanines. The
solid product was purified by preparative thin layer chromatog-
raphy (TLC) using chloroform/acetone (8.5:1.5) solvent system.
ꢀ
Yield: 0.277
g
(53%), m.p:>300
C. Anal. Calc. for
C
4
128 88 8
H N O16Zn: C: 74.67; H: 4.28; N: 5.44. Found: C: 74.58; H:
ꢁ
1
.16; N: 5.48%. IR (KBr tablet),
n
max/cm : 3049 (AreH), 2924e
), 806.
:ppm): 7.72e7.68 (m, 28H, ArH), 7.55e
.35 (m, 28H, ArH), 4.86e4.52 (m, 16H, OeCH ), 3.66e3.42 (s,
:ppm): 134.12, 133.40, 132.53,
131.19, 130.65, 129.08, 127.42, 126.36, 121.35, 114.26, 115.72,
08.96, 106.43, 105.34, 73.82, 68.40. UV-Vis (CHCl ):
2
851 (Alif. CeH), 1427, 1247(AreOeC), 1087e1069 (eOCH
2
Fig. 1. Absorption spectra of compounds 3(ꢁ),4(—),5(-..-),6(.) in chloroform.
1
H NMR. (chloroform), (
d
7
2
13
2 3
16H, OeCH ). C NMR (CDCl ), (d
2
.3.4. General procedure of metallophthlaocyanines
6
’
’
,7,22,23-Tetrahydrobenzo[e]dinaphtho[1,2-m:2 ,1 -k][1,4,7,10]
tetraoxacyclo- tetradecine-2,3-dicarbonitrile (2) (0.5 g, 1 mmol)
and respectively anhydrous CoCl , anhydrous CuCl , anhydrous
1
3
max
l /
ꢁ5
3
ꢁ1
ꢁ1
nm:[(10 ε dm mol cm )]: 689 (5.42), 620 (4.95), 347 (5.28).
MS (FAB) (m/z): 2057 [M] .
2
2
þ
Zn(CH
3
COO)
2
(0.5 mmol) and 2-(dimethylamino)ethanol (5 mL)
ꢀ
were added in a microwave oven at 135 C, 350 W about 6e8 min.
After cooling to room temperature the reaction mixture was
refluxed with ethanol to precipitate the product, which was filtered
off and washed with hot ethanol and dried in vacuum.
3. Results and discussion
3.1. Synthesis and characterization
2
.3.4.1. Co(II) phthlaocyanine (4). Compound 4 was prepared ac-
Compound 1 was prepared as a result of the reaction between
1,1 -binaphthalene-2,2 -diol and 2-chloroethanol at 78 C in abso-
0
0
ꢀ
cording to general procedure for metallophthalocyanines. The solid
product was purified by preparative thin layer chromatography
lute ethanol. The yield was obtained as 54%. In the IR spectrum of 1,
stretching vibrations of OeH band at 3486-3402 cm seemed to
ꢁ1
(
0
TLC) using chloroform/ethanol (8.5:1.5) solvent system. Yield:
ꢀ
.225 g (44%), m.p:>300 C. Anal. Calc. for C128
88
H N
8
O
16Co: C:
have shifted after the reaction. In addition, the stretching vibrations
ꢁ1
7
4.89; H: 4.29; N: 5.46. Found: C: 74.55; H: 4.34; N: 5.40%. IR (KBr
of OeCH2 were also observed at 1141e1047 cm . Singlet peak at
ꢁ1
0
0
tablet),
n
max/cm : 3049 (AreH), 2923e2851 (Alif. CeH), 1593,
), 806. UV-Vis (chloro-
d
¼ 5.00 ppm of OH protons of compound 1,1 -binaphthalene-2,2 -
1434, 1248 (AreOeC), 1088e1073 (eOCH
2
diol ppm was seen at
d
¼ 2.29 ppm for compound 1 and it dis-
ꢁ5
3
ꢁ1
ꢁ1
1
form):
l
max/nm: [(10 ε dm mol cm )]: 680 (5.36), 623 (5.14),
appeared after addition of D O. The H NMR spectrum of 1 indi-
2
þ
3
26 (4.76). MS (FAB) (m/z) 2087 [M þ 2H
2
O] .
cated aromatic protons at 8.06-7.87, 7.47e7.11 ppm and aliphatic
13
protons at 4.19e4.03, 3.57 ppm. The C NMR spectrum of 1 indi-
cated the presence of carbon resonance at
2.3.4.2. Cu(II) phthlaocyanine (5). Compound 5 was prepared ac-
d
¼ 71.96 and
cording to general procedure for metallophthalocyanines. The solid
product was purified by preparative thin layer chromatography
d
¼ 61.46 ppm, showing to eOCH
2
. The MS spectrum of 1 displayed
þ
the [M] parent ion peak at m/z ¼ 374, confirming the structure.
The elemental analysis confirms the expected 1.
(
TLC) using ethyl acetate/methanol (9.5:0.5) solvent system. Yield:
Table 1
Voltammetric data of the complexes with the related MPcs. All voltammetric data were given versus SCE.
aE1/2
bD
E
p
(mV)
cIp,a/Ip,c
dD
E
eColor 1
fColor2
gColor coordinates
1/2
II ꢁ2
II ꢁ1 þ1
0.91h (0.79)
ꢁ0.77
ZnPc 6 (in DCM)
ZnPc 6 (in DMSO)
CoPc 4 (in DCM)
CoPc 4 (in DCM)
[Zn Pc ]/[Zn Pc
[
[
]
210
100
250
e
0.72
0.96
0.87
e
Blue
x:0.2891
y:0.3327
Bluish purple
Light blue
Green
x:0.2482; y:0.3359
x0.2929; y:0.3414
x:0.2850; y:0.3644
II ꢁ2
II ꢁ3 ꢁ1
]
Zn Pc ]/[Zn Pc
1.66
1.68
1.09
0.82
II ꢁ3 ꢁ1
II ꢁ4 ꢁ2
Zn Pc
]
/[Zn Pc
]
ꢁ1.10
II ꢁ2
II ꢁ1 þ1
[Zn Pc ]/[Zn Pc
]
0.96
II ꢁ2
II ꢁ3 ꢁ1
]
[
[
Zn Pc ]/[Zn Pc
ꢁ0.72
60
64
153
e
0.97
0.92
0.75
e
II ꢁ3 ꢁ1
II ꢁ4 ꢁ2
Zn Pc
]
/[Zn Pc
]
ꢁ1.00
II ꢁ2
II ꢁ1 þ1
h
[Co Pc ]/[Co Pc
]
0.87 (1.08)
Blue
Purple
Yellow
Orange
Light blue
Green
x:0.3450; y:0.3257
x:0.3708; y:0.3790
x:0.3510; y:0.3820
x:0.2482; y:0.3359
x:0.2876; y:0.3748
x:0.2720; y:0.2454
II ꢁ2
I
ꢁ2 ꢁ1
h
[
[
Co Pc ]/[Co Pc
]
ꢁ0.22 (-0.68)
x:0.2884
y:0.3423
Blue
x:0.2184
y:0.3187
I
ꢁ2 ꢁ1
I
ꢁ3 ꢁ2
Co Pc
]
/[Co Pc ]
ꢁ1.08
75
90
e
0.96
0.33
e
II ꢁ2
III ꢁ2 þ1
]
[Co Pc ]/[Co Pc
0.49
II ꢁ2
I
ꢁ2 ꢁ1
h
[
[
Co Pc ]/[Co Pc
]
ꢁ0.33 (ꢁ0.75)
I
ꢁ2 ꢁ1
I
ꢁ3 ꢁ2
Co Pc
]
/[Co Pc ]
ꢁ1.12
62
0.76
Bluish purple
a
ꢁ1
E
D
I
D
1/2 values ((Epa þ Epc)/2) were given versus SCE) at 0.100 V s scan rate (only Epc or Epa values were given for completely irreversible processes).
b
c
E
p
¼ Epa ꢁ Epc
.
p,a/Ip,c for reduction,Ip,c/Ip,a for oxidation processes.
d
e
f
E
1/2 ¼ E1/2 (first oxidation)- E1/2 (first reduction).
Color and color coordinates of the neutral complex.
Color of the electrogenerated anionic or cationic species.
Color coordinates of the electrogenerated anionic or cationic species.
Redox process of the aggregated species were given in parenthesis.
g
h

M.B. Kılıçaslan et al. / Dyes and Pigments 103 (2014) 95e105
99
Fig. 3. Spectra of ZnPc recorded at different concentrations in DCM.
cyclotetramerization. The 1H NMR spectrum of 3 [49] indicates
aromatic protons at 7.44e7.38, 7.22e7.20, 6.95 ppm and aliphatic
protons at 3.93e3.83, 3.79e3.76 ppm. The inner core protons NeH
of this compound 3 could not be observed because of the probable
13
strong aggregation of the molecule [50]. The C NMR spectrum of 3
were confirmed by disappearance of the sharp eC^N vibration at
Fig. 2. (a) CVs and (b) SWV of ZnPc at various scan rates on a Pt working electrode in
DCM/TBAP.
0
Compound 2 was prepared with a reaction of 2,2’-[1,1 -
’
Binaphtalene-2,2 -diyl bis(oxy)]diethanol and 4,5-dichloro-1,2-
dicyanobenzene at 85 C in dry acetonitrile and the yield was ob-
ꢀ
tained as 60%. In the IR spectrum of 2, stretching vibrations of OeH
ꢁ
1
band at 3516-3240 cm
disappeared and C^N groups were
ꢁ
1
1
observed at 2235 cm . The H NMR spectrum of 2, belonging to OH
group signals
d
¼ 2.29 ppm, disappeared to give the proposed
1
structure. In addition H NMR spectrum of 2 indicated aromatic
protons at 8.15e7.71, 7.60e7.11 and aliphatic protons at 4.28e4.08,
3
.99e3.66 ppm. The 13C NMR spectrum of 2 indicated the presence
of nitrile carbon atoms (C^N) in 2 at 113.23 ppm. The MS spectrum
þ
of 2 displayed the [M þ K] parent ion peak at m/z ¼ 537, con-
firming the structure. The elemental analysis confirms the
expected 2.
The mode of preparation of the metal free (3) and metal-
lophthalocyanines (4, 5, 6) are shown in Scheme 1. The metal-
lophthalocyanines (4, 5, 6) were obtained from dry metal salts
2 2 3 2
CoCl , CuCl , Zn(CH COO) , respectively in 2-(dimethylamino)
ethanol by microwave irradiation and we used a 350 W domestic
ꢀ
oven at 135 C for synthesis of 4, 5, 6.
We synthesized metal free phthalocyanine (3) by a classical
method, using n-pentanol, few drops of diazabicyclo[5.4.0]undec-
7
N
-ene (DBU) and anhydrous pyridine at boiling point under
(g) and the yield was obtained as 38%. Template effect of metal
ions plays an important role in formation of some phthalocyanines
2
[
(
48]. Since stretching vibration observed for starting compound
2) at 2235 cm , which is characteristic for C^N groups, was not
ꢁ
1
observed in IR spectrum of metal-free phthalocyanine com-
pound (3), however, NeH stretching vibrations were seen in
ꢁ1
phthalocyanine ring at 3285 cm , it was concluded that these
demonstrate formation of the relevant structure as a result of
Fig. 4. (a) CVs (inset: CV recorded with different switching potentials) and (b) SWV of
ZnPc at various scan rates on a Pt working electrode in DMSO/TBAP.

100
M.B. Kılıçaslan et al. / Dyes and Pigments 103 (2014) 95e105
þ
1
13.23 ppm. The MS spectrum of 3 displayed the [M þ 3 þ H
2
O]
parent ion peak at m/z ¼ 2015, confirming the structure. The
elemental analysis confirms the expected 3.
In the IR spectrum of metallophthalocyanines (4, 5, 6),
cyclotetramerization of dinitrile 2 to phthalocyanines 4, 5, 6 was
confirmed by the disappearance of the sharp eC^N vibration at
235 cm . The 1H NMR spectrum of 4, 5, 6 were almost iden-
ꢁ
1
2
tical to that of metal free 3, except for broad signals in 4, 5, 6,
from aggregation of planar phthalocyanines at the high con-
1
centration used for NMR measurements. H NMR spectra of 4, 5
were precluded owing to their paramagnetic nature. MS spectra
of 4, 5,
M þ 2H
6
showed molecular ion peaks at m/z
¼
2087
þ
þ
þ
[
2
O] , 2073 [M þ H
2
O] , 2057 [M] , respectively, con-
firming the proposed structure. The elemental analysis confirms
the expected 4, 5, 6.
Metal free phthalocyanine 3 and metallophthalocyanines (4e6),
showed typical UV-Visible spectra with two significant absorption
bands, one of them in the visible region at about 614e728 nm
corresponding to the Q band, and the other in the UV, approxi-
mately at 300 nm. The split Q bands in 3, which are characteristic
for metal-free phthalocyanines, were observed at
and 644 nm (Fig. 1). These Q band absorptions show the mono-
l
max ¼ 710, 677
meric species with D2h symmetry and due to the phthalocyanine
ring related to conjugated 18p electron system. The presence of
absorption band in 3 in the near UV region at
Soret region B band which has been ascribed to the deeper
levels of LUMO transitions [51].
l
max ¼ 338 nm shows
pep*
The UVeVis absorption spectra of metallophthalocyanines 4, 5
and 6 (Fig. 1) in chloroform showed intense Q absorption at
Fig. 6. (a) CVs and (b) SWV of CoPc at various scan rates on a Pt working electrode in
DMSO/TBAP.
l
max ¼ 680, 689, 689 nm, respectively with weaker absorptions
at 623, 626, 620 nm, respectively. The single Q band in metallo
derivatives 4, 5 and 6 was characteristic. This result is typical of
metal complexes of substituted and unsubstituted metal-
lophthalocyanines with D4h symmetry. B band absorptions of 4, 5
and 6 were observed at
expected [52].
lmax ¼ 326, 338, 347 nm, respectively as
3.2. Voltammetric measurements
With respect to the proposed structures of the complexes,
substituents on the complexes are redox inactive moieties, and
thus these groups could not give any redox processes. Zinc and
copper ions in the Pc ring centers are also redox inactive ions,
since the empty and occupied d orbitals are not located be-
tween the HOMO and LUMO orbitals of the Pc ring. Thus, ZnPc
and CuPc complexes should give only Pc based redox processes.
However, CoPc has redox inactive metal center thus should give
electron transfer reactions assigned to both the metal center
and Pc ring. To support the proposed structures for the com-
plexes, redox behaviors of the complexes were determined in
solution with CV and SWV techniques. The electrochemical
behaviors of the complexes could also be used to propose
possible applications of the complexes in various electro-
chemical technologies. Analyses of the voltammograms recor-
ded here were performed and the basic electrochemical
parameters derived from the voltammograms are tabulated in
Table. As shown in Table 1, basic electrochemical parameters of
the complexes are in harmony with the similar complexes in the
literature [53e56].
Fig. 5. (a) CVs and (b) SWV of CoPc at various scan rates on a Pt working electrode in
DCM/TBAP.

M.B. Kılıçaslan et al. / Dyes and Pigments 103 (2014) 95e105
101
Fig. 7. In-situ UV-Vis spectral changes of ZnPc in DCM.
Fig. 2 shows the CV and SWV responses of ZnPc 6 in DCM/
TBAP electrolyte system. The complex 6 gives two reduction
processes and one spitted oxidation process. The first reduction
To investigate the solvent effect on the electrochemical behavior
of the complex, CV and SWVs of ZnPc were also recorded in DMSO,
a coordinating polar solvent (Fig. 4). When compared with the
redox responses recorded in DCM, reduction reactions were more
reversible chemically and electrochemically in DMSO. Altering the
switching potentials did not affect the redox characters of the
electron transfer reactions (Fig. 4a inset). Due to the more polari-
zation effect of DMSO, these processes shifted approximately
70 mV toward the negative potentials. Moreover, an extra (CP)
wave at ꢁ1.35 V was recorded in DMSO. This wave was very small at
slow scan rate. However, its peak current increased rapidly with
increasing scan rate. During the in situ spectroelectrochemical
measurement any spectral changes assigned to the ZnPc 6 complex
was not recorded at the potential of CP process. These data indicate
that this process is not based on the ZnPc 6 reduction thus it was
assigned to the reduction of products of a chemical succeeding to
the electron transfer reaction (Fig. 4b). The oxidation process
recorded at 0.96 V is completely irreversible, while it is quasi-
reversible in DCM solvent. Consequently, it was easily concluded
that the electrolyte of the system affected the aggregation and
electron transfer processes of the complex.
reaction (R
with its reverse couple at ꢁ0.72 V at 0.100 V s
Changing values from 70 mV to 150 mV with increasing scan
1
at ꢁ0.77 V) had a broad cathodic wave at ꢁ0.82 V
ꢁ
1
scan rate.
DE
p
ꢁ1
ꢁ1
rate from 0.025 V s to 0.50 V s indicates that electrochemical
reversibility of the process at slow scan rate shifts to irreversible
character with increasing scan rate. The R
pa/Ipc at all scan rates, which indicates chemical reversibility of
the process. The first reduction process was followed by an
irreversible second reduction reaction R
1
process had unity of
I
2
at ꢁ1.10 V as shown in
Fig. 2a. Although both reduction processes gives similar CV re-
sponses (Fig. 2a), these processes gave different redox responses
during the SWV measurements (Fig. 2b). As shown in the SWV
2
graph, anodic and cathodic waves of R process have smaller
peak currents than those of the first reduction reaction. These
different redox responses recorded with different voltammetric
technique might be due to the presence of aggregation-disag-
gregation equilibrium and applied wave forms altered the state
of the equilibrium. Presence of equilibrium was well illustrated
during the anodic potential scans. The oxidation process split
Figs. 5 and 6 illustrate the CV and SWV of CoPc 4 in DCM/TBAP
and DMSO/TBAP electrolyte systems, respectively. CoPc 4 illustrates
very similar redox responses in both electrolyte systems. CoPc 4
into two waves, where O’
1
was assigned to the aggregated spe-
cies and O was assigned to the monomeric species. Analyses of
1
II
I
these waves at different concentrations and different scan rates
support the aggregation of the complex. Spectral changes
recorded with different concentrations were given in Fig. 3 to
support the aggregation of the complex. In situ spectroelec-
trochemical measurements given below also indicate the aggre-
gation of the complex.
aggregates in both solvents and due to the aggregation, Co /Co
reduction reaction split into two waves, R for monomeric species
and R’ for aggregated species. These processes were recorded at
less negative potential in DCM with respect to DMSO. The relative
peak currents of the waves R and R’ were different in these sol-
vents due to the different tendency of the complex in different
1
1
1
1

102
M.B. Kılıçaslan et al. / Dyes and Pigments 103 (2014) 95e105
Fig. 8. In-situ UV-Vis spectral changes of CoPc in DCM.
solvents. While R’
R’ in DMSO. Main difference between the redox responses of the
complex in these solvents is the position of the oxidation process of
the complex. While CoPc 4 illustrates a split oxidation reaction (O’
at 0.88 V and O at 1.10 V) in DCM, this process was recorded at
.50 V as a single wave in DMSO. These differences resulted from
changing redox mechanism of CoPc 4 in different solvents. MPc
having redox active metal center gives a metal based oxidation
reaction before the Pc ring oxidation due to the stabilization of the
higher oxidation states of the metal centers with coordinating the
polar solvent to the metal ions. However, a Pc based oxidation is
favored in noncoordinating electrolyte system. Peak assignments
performed with the in situ spectroelectrochemical measurements
supported these different mechanisms of the complex in different
solvents.
1
was bigger than R
1
in DCM, R
1
was bigger than
reduction reaction at ꢁ1.00 V (Fig. 7a), first of all, the Q band
increased in intensity and gave a sharp Q band characterizing
monomeric ZnPc 6 species. After disaggregation of the complex,
then the Q band decreased in intensity without any potential shift
and a new band was recorded at 576 nm (Fig. 7b). Moreover, small
bands at MLCT region at 875 and 967 nm were also recorded. These
spectral changes are characteristic changes for the ring based
reduction of MPcs having redox inactive metal center [54,57e60].
Well-defined isosbestic points were recorded at 340, 391, 611, 660,
and 71 nm, which demonstrate that the reduction proceeded
cleanly in deoxygenated DCM to give a single type reduced species,
1
1
1
0
II ꢁ2
monomeric Zn Pc species. To confirm the origin of the oxidation
process (O ), in-situ UVeVis changes were recorded under the
1
controlled potential application at 1.20 V (Fig. 7c). During this
process, the Q band decreased in intensity without shift and two
new bands were recorded at 524 and 838 nm. A band at 726 nm
increased at the beginning of the process, but decreased slowly
again during the oxidation reaction. Isosbestic points at especially
385, 560, and 715 nm vibrated continuously, which demonstrate
that more than two types of species are present in the system.
These species may be most probably aggregated and disaggregated
3.3. Spectroelectrochemical measurements
To perform the assignments for the redox processes recorded
with the CVs and SWVs of the complexes and to investigate effect of
the solvent to the peak assignments, spectroelectrochemical
studies were employed.
II ꢁ2
II ꢁ1
Zn Pc species and oxidized Zn Pc species. Color of the ZnPc did
not change considerably during the electron transfer reactions as
shown in the chromaticity diagram given in Fig. 7d.
ZnPc 6 illustrates similar spectral responses under the applied
potentials in both of DCM and DMSO solvents, since zinc center
could not extent its coordination and ZnPc only gave Pc based
electron transfer reactions. Fig. 7 illustrates in-situ UV-Vis spectral
changes of ZnPc 6 in DCM/TBAP electrolyte system. Under open
circuit, ZnPc 6 gave a broad Q band at 684 nm with a shoulder band
at 622 nm and a B band at 342 nm. Broadening of the Q band of the
MPc illustrate aggregation of the complex. During the first
Although CoPc 4 represents similar CV and SWV responses in
both of DCM and DMSO, spectral changes during the electron
transfer reaction, especially during the oxidation reaction were
different in both of the solvents used. Fig. 8 represents in-situ UV-
Vis spectral changes and in-situ recorded chromaticity diagram of
CoPc 4 in DCM/TBAP during the electron transfer processes.

M.B. Kılıçaslan et al. / Dyes and Pigments 103 (2014) 95e105
103
4
76 nm. Observation of a new band at 476 nm and shifting of the Q
I
ꢁ2 1ꢁ
characterized the formation of [Co Pc
] species (Fig. 8b). Clear
isosbestic points were recorded at 393, 559, and 690 nm in the
spectra. Original blue color of the solution (x ¼ 0. 2884 and y ¼ 0.
3
423) went yellow (x ¼ 0.3708 and y ¼ 0.379) after the reduction
reaction as shown in the chromaticity diagram (Fig. 8d). Fig. 8c il-
lustrates the spectral changes during the first oxidation of CoPc 4.
The Q band decreased in intensity without a potential shift and two
new bands were recorded at 530 and 750 nm, which are charac-
teristic changes of a Pc ring based oxidation reaction and assigned
II ꢁ2
II ꢁ1 1þ
to [Co Pc /[Co Pc
was obtained after the oxidation reaction as represented in Fig. 8d
]
. Purple color (x ¼ 0.345 and y ¼ 0. 3287)
[31,61e66].
In situ spectroelectrochemical and in situ electrocolorimetric
measurements of CoPc 4 were also performed in DMSO/TBAP
electrolyte system and compared with those recorded in DCM/
TBAP. Fig. 9 represents in-situ UV-Vis spectral changes of CoPc 4
recorded during the oxidation reaction under 1.00 V. The Q band of
CoPc 4 shifted from 662 nm to 675 nm with increasing in intensity.
These spectral changes are assigned to a metal based oxidation,
Fig. 9. In-situ UV-Vis spectral changes of CoPc in DMSO during oxidation reaction at
.00 V.
1
II ꢁ2
III ꢁ2 1þ
[Co Pc ]/[Co Pc ]
[31,61e66]. While the oxidation of CoPc 4 is
a ring based process in DCM solvent, it is a metal based process in
DMSO. This different mechanism of CoPc 4 in different solvent
resulted from the nature of DMSO. Since DMSO is a coordinating
solvent, coordination of DMSO to the cobalt center stabilized higher
oxidation state of the metal center, thus Co /Co process was
favored in DMSO solvent.
Fig. 10 represents in-situ UV-Vis spectral changes of CoPc 4
recorded during the reduction reactions. When spectral responses
of CoPc 4 in DMSO are compared with those in DCM, it is clear that
When ꢁ0.50 V was applied, the spectrum characterizing the mono
CoPc 4 species changed immediately and a spectrum assigned to
the aggregation was obtained (Fig. 8a). The sharp Q band decreased
in intensity a small band was observed at 624 nm and finally a
broad Q band was formed. These spectral changes clarified the
explanations on the complication of the CVs with the aggregatione
disaggregation equilibrium. Then when ꢁ0.85 V was applied, the Q
band at 672 nm shifted to 709 nm and a new band was recorded at
II
III
Fig. 10. In-situ UVeVis spectral changes of CoPc in DMSO.

104
M.B. Kılıçaslan et al. / Dyes and Pigments 103 (2014) 95e105
general trend of the spectral changes are similar in both solvents.
During the first reduction reaction, the Q band shifted to high
wavelengths and a new band was recorded between 450 and
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00 nm, which are characteristic changes for a metal based
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reduction reaction (Fig. 10a) [31,61e66]. Differently effects of the
aggregation on the spectral changes were more complicated in
DMSO with respect to DCM. This different behavior might be due to
the coordination of DMSO to the cobalt center of CoPc 4 and
presence of a coordinated-noncoordinated CoPc 4 equilibrium in
addition to the aggregation-disaggregation equilibrium. During the
first reduction reaction, first of all, while the Q band stayed as un-
changed, a new band started to increase at 623 nm in addition to
the band at 475 nm and 705 nm (from red to green spectrum)
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I
ꢁ2
at 662 nm increased in intensity, while the bands at 475 nm and
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7
05 nm followed their previous trends. These spectral changes
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2
process) under ꢁ1.50 V potential applica-
tions (Fig. 10c). Trend of the spectral changes altered continuously
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transfer reaction. The general trends were decreasing Q band and
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[
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supported the proposed structures of the complexes. CoPc 4 gave
metal based electron transfers in addition to the Pc based processes
and the electron transfer reaction mechanism was affected by the
electrolyte systems used for the electrochemical and spectral ana-
lyses. Rich redox behaviors of the complexes are the desired
properties of the electrochemical applications, especially, electro-
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