Synthesis and characterization of novel tetrakis (3-hydroxypropylmercapto)- substituted phthalocyanines

Article abstract of DOI:10.1142/S1088424613500697

A phthalonitrile precursor 4-(3-hydroxypropylmercapto)phthalonitrile (3) was synthesized via a base-catalyzed nucleophilic aromatic nitro displacement of 4-nitrophthalonitrile with the 3-mercapto-1-propanol. A novel tetrasubstituted metal-free phthalocyanine (4) (M = 2H) and its metal complexes (5-8) (M = Zn, Ni, Cu and Co) bearing 3-hydroxypropylmercapto moieties were prepared by the cyclotetramerization reaction of (3) with the appropriate materials. The visible spectra of the zinc(II) phthalocyanine (5) was recorded with different concentrations and different ions as Ag⁺, Hg²⁺ and Pb ²⁺ in DMF and also with different solvents as dimethylformamide and pyridine. Fluorescence spectrum of the compound (5) was also studied. Temperature and frequency dependence of AC conductivity for (4-8) was investigated in air and under vacuum and were found to be ～10 ^-8-10^-5 S.m^-1. Thermal properties of the phthalocyanines were examined by differential scanning calorimetry. All the novel compounds have been characterized by elemental analysis, UV-vis, FT-IR, NMR and MS spectral data and DSC techniques.

Full text of DOI:10.1142/S1088424613500697

Journal of Porphyrins and Phthalocyanines
J. Porphyrins Phthalocyanines 2013; 17: 573–586
DOI: 10.1142/S1088424613500697
Published at http://www.worldscinet.com/jpp/
Synthesis and characterization of novel tetrakis
(3-hydroxypropylmercapto)-substituted phthalocyanines
Çig˘demYag˘cı and Ahmet Bilgin*
Department of Science Education, Kocaeli University, 41380-Kocaeli, Turkey
Dedicated to Professor Özer Bekaroğlu on the occasion of his 80th birthday
Received 1 March 2013
Accepted 3 May 2013
ABSTRACT:A phthalonitrile precursor 4-(3-hydroxypropylmercapto)phthalonitrile (3) was synthesized
via a base-catalyzed nucleophilic aromatic nitro displacement of 4-nitrophthalonitrile with the
3-mercapto-1-propanol. A novel tetrasubstituted metal-free phthalocyanine (4) (M = 2H) and its metal
complexes (5–8) (M = Zn, Ni, Cu and Co) bearing 3-hydroxypropylmercapto moieties were prepared by
the cyclotetramerization reaction of (3) with the appropriate materials. The visible spectra of the zinc(II)
phthalocyanine (5) was recorded with different concentrations and different ions as Ag+, Hg2+ and Pb2+
in DMF and also with different solvents as dimethylformamide and pyridine. Fluorescence spectrum of
the compound (5) was also studied. Temperature and frequency dependence of AC conductivity for (4–8)
was investigated in air and under vacuum and were found to be ~10-8–10-5 S.m-1. Thermal properties
of the phthalocyanines were examined by differential scanning calorimetry. All the novel compounds
have been characterized by elemental analysis, UV-vis, FT-IR, NMR and MS spectral data and DSC
techniques.
KEYWORDS: Metal-free phthalocyanine, metallophthalocyanines, aggregation, AC electrical
conductivity, DSC, fluorescence.
As many phthalocyanines are not soluble in organic
INTRODUCTION
solvents nor aqueous medium, the solubility of phthalo-
Phthalocyanines (Pcs) have been extensively used as
cyanine derivatives is very important for their applications.
dyes and pigments due to their high thermal and chemical
The substitution improves the useful properties of
stability, after their accidentally discovery in early 1900s
phthalocyanines and usually enhances their solubility. It
and accurate characterization in 1930s [1]. More recently
has been reported that tetrasubstituted phthalocyanines
phthalocyanines have found high technology applications
are more soluble than their octasubstituted counterparts
and in many other fields such as in electrophotography
due to the formation of constitutional isomers and their
and ink jet printing as photoconducting agents in
high dipole moments [11].
photocopying devices [2], photosensitizers [3], gas
Chemical and physical properties of phthalocyanines
sensors [4], catalysts [5], liquid crystals [6], nonlinear
are enhanced by the introduction of alkoxy or
optics [7], sensitizers for photodynamic therapy of cancer
alkylthio substituents to the phthalocyanines [12].
[8] and Langmuir–Blodgett films [9]. Their potential
The position of the longwave absorption bands in
to adapt to such a wide range of applications originates
the electronic spectra is strongly affected by the
from their singular chemical structure, high degree of
electron-donating or electron-withdrawing groups
aromaticity, unique electronic spectra and the flexibility
on phthalocyanine [12a, 13]. The electron-donating
involved in the synthesis of phthalocyanines [10].
atoms like sulfur on the peripheral functional groups
of the phthalocyanine ring cause optical transitions by
shifting absorptions from the visible to the near-IR [14].
Thiol derivatized metallophthalocyanines are known
*Correspondence to: Ahmet Bilgin, email: abilgin@kocaeli.
edu.tr, tel: +90 262-303-2438, fax: +90 262-303-2403
Copyright © 2013 World Scientific Publishing Company

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574
Ç. YAGCI AND A. BILGIN
to have absorption at longer wavelengths (> 675 nm)
than the other metallophthalocyanines, a very useful
feature for application in photodynamic therapy (PDT),
optoelectronics, fabrication of thin films such as the
self-assembled monolayer (SAMs) and near-IR devices
[1, 15].
sandwich form covered with silver paste. The aggregation
and the fluorescence properties of the compound (5)
were examined. Thermal properties of the compounds
were investigated by DSC with a scanning rate of 10 °C/
min between -4–440 °C. The new compounds have been
characterized by using elemental analysis, UV-vis, FT-IR,
NMR, MS spectral data.
The presence of different substituents on the
phthalocyanine ring also leads to increased solubility
and supramolecular organizations with improved
physicochemical characteristics, as well as the presence
and nature of the central metal ion. Phthalocyanines
are also useful photosensitizers due to their high
molar absorption coefficients, long lifetimes of the
photoexcited triplet states and photostabilities [16].
Particularly, ZnPcs have been studied comprehensively
because d10 configuration of the central Zn2+ ion results in
optical spectra which are not complicated by additional
bands, just like in transition-metal Pc complexes. ZnPcs
have intensive red-visible region absorption and high
singlet and triplet yields, which make them valuable
photosensitizer for PDT applications [17].
Semiconductor properties of phthalocyanines are
known for a long time and a great deal of work has been
reported in improving the electrical property of these
complexes [18]. The conducting properties of these
materials are sensitive to the nature of the central metal or
metalloid, substituents at the peripheral benzene rings and
the surrounding atmosphere. The electrical conductivity
changes by many orders of magnitude under the influence
of gases [19] and in presence of dopants [20].
Inthepastfewyears,wehavedirectedourattentiontothe
synthesisofphthalocyaninesbearingvariousfunctionalized
groups as O-, S- and N- containing functionalities such
as peripherally long triazadioxa derivatives, very flexible
1,3,6,9,11-pentathiaundecane moieties and octakis(3-
hydroxypropylmercapto)substitutedphthalocyanines[21],
macrocyclic groups [22] and monomeric phthalocyanine
with ethylmercapto-tetrathiamonoaza macrocycles and
a-methylferrocenylmethoxy unit [23]. Thioether substi-
tued phthalocyanines are relatively less studied than
phthalocyanines with N- and O- donor substituents. The
thioether group essentially contains products obtained by
the cyclotetramerization of thioether-substituted phthalo-
nitrileswhichthemselves havebeen derivedbynucleophilic
aromatic nitro displacement reactions of phthalonitriles
[24]. A small number of recent patents and procee-
dings describe the use of these types of compounds as IR
absorbers [13d, 24, 25].
In the present work, we report the synthesis and
characterization of a new peripherally functionalized
4-(3-hydroxypropylmercapto)phthalonitrile (3) and its
hydroxyl-functionalized metal-free (4) and metallophth-
alocyanines (5–8) with four peripheral alkyl thioether
groups which is expected to be more soluble than the
octasubstituted ones [21d]. The AC electrical conducti-
vities of the metal-free and metallophthalocyanines
were measured in air atmosphere and under vacuum on
RESULTS AND DISCUSSION
Synthesis and characterization
The synthesis of 4-(3-hydroxypropylmercapto)
phthalonitrile (3) was performed via a base-catalyzed
nucleophilic aromatic nitro displacement [26, 30, 31]
of 4-nitrophthalonitrile with the –SH functional site
of 3-mercapto-1-propanol, in dry DMSO using finely
ground anhydrous K2CO3 with the yield of 63% after
recrystallization from toluene as described in the
Experimental section (Scheme 1). As a rule, formation
of alkylsulfanyl- and arylsulfanyl-phthalonitriles by
aromatic substitution reaction proceeds more easily
than formation of the analogous alkyloxy- and aryloxy-
phthalonitriles because of the better nucleophilicity
of thiolates compared with alkoxides [32]. The self-
condensation of the phthalonitrile derivate (3) in the
presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as
a strong base and a dry pentan-1-ol at reflux temperature
under a dry argon atmosphere afforded the metal-free
phthalocyanine (4) in 53% yield as a petroleum greenish
product after purification by column chromatography
on silica gel using CHCl3:MeOH (10:2, v/v) as eluent.
Cyclotetramerization of the compound (3) in the
presence of anhydrous metal salts Zn(CH3COO)2 or
CuCl2 gave the desired metallophthalocyanines (5) or
(7) in presence of DBU as a base catalyst in dry pentan-
1-ol. Ni(II) phthalocyanine (5) was obtained directly by
refluxing phthalonitrile derivative (3) with anhydrous
NiCl2 in dry 2-dimethylaminoethanol in the presence of
DBU. Co(II) phthalocyanine (8) was synthesized by the
reaction of (3) with anhydrous CoCl2 in 1,2-ethanediol.
The metallophthalocyanines (5–8) were purified by
column chromatography on silica gel using CHCl3:MeOH
(10:2, v/v) eluent as the mobile phase in 78–83% yields.
The structures of the novel compounds were verified
by FT-IR, UV-vis and MALDI-TOF or MICRO-TOF
MS spectroscopic methods, as well as by elemental
analysis. The IR spectrum of the starting compound (3)
clearly indicates the disappearance of S–H stretching
vibration at 2560 cm-1 and the presence C≡N and
Ar–C–S stretching vibrations at 2229 and 668 cm-l,
respectively. In the IR spectra of compounds (5–8), the
disappearance of the sharp C≡N vibration band which
belongs to precursor (3) at 2229 cm-1 confirmed the
cyclotetramerization of the phthalonitrile derivative (3).
The IR spectra of phthalocyanines (4–9) are very similar,
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SYNTHESIS AND CHARACTERIZATION OF NOVEL TETRAKIS
575
Scheme 1. Synthesis of the phthalonitrile (3) and compounds (4), (5), (6), (7) and (8)
with the exception of the metal-free phthalocyanine
(4) showing N–H stretching and pyrrole ring vibration
bands at 3290 and 1016 cm-1 due to the inner core [33].
Metal-N vibrations were expected to appear at 400–100
cm-1, but they were not detected in KBr pellets [34].
NMR spectra are particularly useful in monitoring
the transformation of the 4-nitrophthalonitrile to the
4-(3-hydroxypropylmercapto)-phthalonitrile (3) and sub-
sequently to the phthalocyanine analogs (4–6). The
spectra also provide an observation of the phthalocyanine
NMR spectrum of (4) exhibits the typical shielding of
inner core protons as a broad signal at around d = -8.68
ppm which could be attributed to the N–H resonances as
confirmed by deuterium exchange with D2O (Fig. S1b)
[10, 21d, 33, 36]. The shift to higher field for the
internal N–H protons is a result of the shielding effect
of 18p-electron system of the phthalocyanine ring. The
reported chemical shift values of N–H groups for various
substituted metal-free phthalocyanines vary from -2.0
1
to -9.0. H NMR spectra of metallophthalocyanines (7)
1
ring current effects on peripheral structures. H NMR
and (8) could not be measured due to the paramagnetic
cobalt(II) and copper(II) centers.
spectra of phthalocyanines (4–6) are almost identical
to the compound (3) except for small shifts; the broad
signals in the spectra are probably due to the mixed isomer
character of these compounds and to the aggregation of
phthalocyanine compounds (4–6) which are frequently
encountered at the concentration used for NMR [35].
In the 13C NMR spectrum (d6-DMSO) of (3) (Fig. S2),
the primary alcohol carbon atom shows a signal at 59.69
ppm. It also indicates the presence of corresponding
carbon atoms at d = 115.72 and 116.33 (C≡N).
Evaluation of mass spectra of the phthalonitrile (3)
and the phthalocyanines (4–8) confirmed the proposed
structures. The mass spectra of the compounds exhibit
peaks at m/z = 241.04 [M + Na]+ for the compound (3) and
m/z=876.533[M+2]+ (Fig.S3),939.266[M+3]+,991.675
1
The H NMR spectrum of (d6-DMSO) compound (3)
(Fig. S1a) is in accordance with the proposed structure.
With the addition of D2O in (3) the chemical shifts of
O–H at 4.66 ppm was displaced with deuterium. The 1H
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Ç. YAGCI AND A. BILGIN
[M + K + Na]+, 937.05 [M + 2]+ and 934.112 [M +3]+ for
(4–8) respectively. MS-MALDI-TOF spectrum of (4)
shows the molecular ion peak at m/z 874–877 as a
protonated and unprotonated isotopic pattern. Elemental
analyses of the compounds were satisfactory for all the
compounds.
and higher order complexes and driven by non-bonded
attractive interactions. It is dependent on concentration,
nature of solvent, nature of substituents, complexed metal
ions and temperature [45]. Here, UV-vis spectroscopy is
used to investigate the aggregation behavior of compounds
(4–8) at different concentrations. The absorbance vs.
wavelength and the molar extinction coefficient vs.
wavelength are studied and given in Figs 1 and 2,
respectively. The intensity of the Q-bands is increased
with the increase of phthalocyanines concentrations as
shown in Fig. 1. As the concentration is increased, the
intensities of Q-bands are also increased in the visible
absorption spectrum of the phthalocyanine compounds
(4–8). However, the increasing tendency in the intensities
of Q-bands is not in the same ratio for (4) in pyridine
(Fig. 1a). The increase in the intensity of the band at 688
nm was slightly more pronounced than that of the band at
712 nm up to 2.0 × 10-5 M, but this observation is more
pronounced over this concentration. This behavior is
attributed to the presence of dimeric or oligomeric species
[21b, 45a–45d] (Fig. 1a). As the concentration of (4) is
increased in pyridine, the apparent extinction coefficients
of maxima corresponding to the monomer absorptions
decrease (Fig. 2a). At the concentrations corresponding to
the large drop in apparent monomer extinction coefficient,
the spectra in Fig. 2a show the appearance of species with
an overlapping and a broader absorbance [45d]. In case
of metallophthalocyanines (5–8), as the concentration
is increased, no new bands were observed and the
Q-band of (5–8) remains essentially unshifted (Fig. 1)
[45e]. So, it cannot be concluded that whether there is
a diagnostically aggregation or not according to these
Figs 1b–1e. However, in order to understand the influence
of concentration to the aggregation on UV-vis spectra of
(5–8), these spectra are given in the A/lC vs. wavelength
(where, A: optical density, l: optical path length and
C: molar concentration) coordinates (Figs 2b–2e). As
seen in Figs 2b–2e, the molar extinction coefficients of
the Q-bands do not coincide and do not have the same
intensity when the concentration is increased for (5–8)
which can be attributed to the effect of aggregation [45].
Absorbance vs. concentration graphs were plotted to
find out if the metal-free and metallophthalocyanines
obey the Lambert–Beer law (Fig. 1). As can be
seen in Fig. 1, the phthalocyanine compounds (4–8)
nearly comply with the Lambert–Beer law at lower
concentration ranges. However, there is a deviation from
the Lambert–Beer law at higher concentrations over
4.0 × 10-5, 5.0 × 10-5, 6.0 × 10-5, 6.0 × 10-6 and 6.0 ×
10-5 M for (4–8), respectively. When compared with
the octasubstituted analogs [21d], the maxima of the
Q-bands of tetrasubstituted phthalocyanine compounds
(4–8) are at lower wavelengths (Table 1). This can be
due to the extent of p-donation from sulfur atoms to the
macrocycle core which is weaker for the tetrasubstituted
phthalocyanines with less number of sulfur atoms than
that for the octasubstituted ones.
It is well-known that cyclotetramerization of this type
of substituted phthalonitrile (3) leads to the formation
of four constructional isomers [37]. It could be deduced
1
from the broadening of absorption peaks of H NMR,
and TLC analysis that metal-free and metalloPcs are a
mixture of four isomers. There are a few papers presently
that reports the successful separation of these four
regioisomers with ordinary column chromatography
[38]. According to Hanack et al., only the two isomers
(C4h,C2v) could be isolated by column chromatography,
but the other two isomers (D2h,Cs) could not be
[38a]. Furthermore, medium- or high-pressure liquid
chromatography, HPLC and thin layer chromatography
techniques can be used to isolate the regioisomers of
the phthalocyanines [39]. Our attempts to separate these
isomers by column chromatography were not successful.
Ground-state electronic absorption spectra
UV-vis spectra of the phthalocyanine complexes
exhibit characteristic Q and B-bands, one in the visible
region at ca. 600–750 nm (Q-band) attributed to the
p⇒p* transition from the HOMO to the LUMO of
the Pc2- ring, and the other in the UV region at ca. 300–
400 nm (B-band) arising from deeper p⇒p* transitions
[40]. Tetrasubstitution with sulfur bridged groups causes
a shift of the intense Q-band to longer wavelengths
when compared with the unsubstituted derivatives
[41]. The UV-vis spectra of the metal-free (4) and the
metallophthalocyanines (5–8) were recorded in solutions
in DMF or pyridine. The UV-vis spectrum of metal-free
phthalocyanine (4) shows the two typical Q-bands of a
non-metalated phthalocyanine system with D2h symmetry
centered at lmax 712 and 688 nm with shoulders at lower
wavelengths at 653 and 624 nm in pyridine due to the
dimeric association higher aggregation [42]. On the
other hand, such split Q-band absorptions are due to the
p⇒p* transition of this fully conjugated 18-p electron
systems [40b, 43]. In the UV-vis absorption spectra of
all metallophthalocyanines, the Q-band absorptions were
observed as a single narrow band of high intensity at 689,
682, 691 and 682 respectively for (5–8) (Fig. 1). There
is a shoulder at the slightly higher energy side for the
metal-free phthalocyanine and its metal complexes. In the
phthalocyanines bearing sulfanyl substituted moieties on
the periphery, the Q-band absorption is shifted to lower
energy side as a result of the electron-donating thioether
substituents than that of phthalocyanines bearing oxa-
substituted or unsubstituted moieties [44].
Aggregation is usually depicted as a coplanar
association of rings processing from monomer to dimer
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SYNTHESIS AND CHARACTERIZATION OF NOVEL TETRAKIS
577
Fig. 1. Absorption spectra of (4) (a) in pyridine and (5) (b), (6) (c), (7) (d), and (8) (e) in DMF at different concentrations (inset: plot
of absorbance vs. concentration at 712, 689, 694, 691 and 682 nm for compounds (4), (5), (6), (7) and (8) respectively)
Aggregation behavior was also investigated with
different metal salts in methanol. In order to clarify
whether methanol has any effect on UV-vis spectra of
(5), different amounts of methanol were added to the
solution of the compound (5) in DMF. There was only a
little decrease in the intensities of Q-bands in the visible
absorption spectrum of (5) with increasing amounts of
methanol (Fig. S4). This can be due to the dilution effect
[25, 22a, 23b]. Then different concentrations of metal
salts as AgNO3, Hg(NO3)2, and Pb(NO3)2 in methanol
were added to the solution of the compound (5) in DMF
(2 × 10-5 M). WhenAg+ solutions in methanol were added
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Fig. 2. A/lC vs. wavelength spectra of (4) (a) in pyridine and (5) (b), (6) (c), (7) (d), and (8) (e) in DMF at different concentrations
to the solution of the compound (5) in DMF, with the
increase of Ag+ amount, the intensity of the main Q-band
of (5) decreased with a slight shift of 6 nm (689 to 683
nm). On the other hand the shoulder at 653 nm and the
Q-band at 621 nm displaced with a new broadened band
at 639 nm (Fig. 3). In case of Hg2+ solutions in methanol,
the Q-band of (5) was broadened and blue shifted of ~2
nm (689 to 687) as can be seen in Fig. 4. This behavior
can be attributed to the complexation of peripheral sulfur
atoms with Ag+ and Hg2+ ions that precludes p-donation
from sulfur atoms to the macrocycle core and give rise
to blue shifted Q-bands [21b, 46]. Further addition
of AgNO3 or Hg(NO3)2 did not change the spectrum.
It may be ascribed that, the extent of p-donation from
sulfur atoms to the macrocycle core is slightly weaker
for the tetrasubstituted phthalocyanines with less number
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SYNTHESIS AND CHARACTERIZATION OF NOVEL TETRAKIS
579
Table 1. The maximum Q-bands absorption wavelengths of
tetrasubstituted phthalocyanines (4–8) and their octasubstituted
analogs
Compound
Max Q-band absorption
Tetrasubstituted
phthalocyanine
Octasubstituted
phthalocyanine*
(4)
(5)
(6)
(7)
(8)
712
689
694
691
682
733
705
705
707
698
*These Q-band values are for the octasubstituted phthalo-
cyanine analogs in reference [21d].
Fig. 5. Changes in the visible spectra of (a) (5) in DMF (C = 2.0 ×
10-5M, V = 3 mL) after addition of (b) 0.2 mL, (c) 0.4 mL,
(d) 0.6 mL, (e) 0.8 mL, and (f) 1.0 mL 0.1 M Pb(NO3)2 in
methanol
of sulfur atoms than that for the octasubstituted ones
[14b, 32b, 47]. When we added Pb2+ (Fig. 5) solutions
in methanol to the compound (5), the intensity of the Q
absorption bands at 689 and 621 nm decreased without
any shift and change. This behavior can be explained by
the weak or no coordination of the peripheral S atoms
to the Pb2+ ion in addition to the dilution effect [44a].
In order to investigate solvent effect to the aggregation
behavior of the zinc(II) phthalocyanine compound (5)
we studied DMF and pyridine (Fig. S5). There is a blue
shift in the UV-vis spectrum of the compound (5) in
DMF which can be attributed to the polar character of
the solvent [35b].
The characteristic of the absorption, excitation and
emission spectra of the soluble part of the compound (5)
in THF solution is also studied (Fig. S6). The excitation
spectrum was similar to absorption spectrum and both
were mirror images of the fluorescent spectrum for
compound (5) in THF. The proximity of the wavelength of
each component of the Q-band absorption to the Q-band
maxima of the excitation spectra for compound (5)
suggests that the nuclear configurations of the ground and
excited states were similar and not affected by excitation in
THF. Fluorescence emission peak was observed at l = 694
nm. It can be said that compound (5) includes monomeric
species which flourescences at this concentration (2.0 ×
10-5) and solvent (THF) [17d, 48] (Fig. S6).
Fig. 3. Changes in the visible spectra of (a) (5) in DMF (C = 2.0 ×
10-5M, V = 3 mL) after addition of (b) 0.2 mL, (c) 0.4 mL,
(d) 0.6 mL, (e) 0.8 mL, and (f) 1.0 mL 0.001 M AgNO3 in
methanol
Conductivity measurements
In order to calculate AC conductivity values of the
phthalocyanine compounds, the capacitance and the
dielectric loss factor of each sample were measured by
a Hewlett-Packard HP 4284 A LCR meter at different
frequencies between 100 Hz-1 MHz and temperatures
between 300–400 K according to the given equations.
Fig. 4. Changes in the visible spectra of (a) (5) in DMF (C = 2.0 ×
10-5 M, V = 3 mL) after addition of (b) 0.2 mL, (c) 0.4 mL,
(d) 0.6 mL, (e) 0.8 mL, and (f) 1.0 mL 0.1 M Hg(NO3)2 in
methanol
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Ç. YAGCI AND A. BILGIN
580
Table 2. The AC conductivity values of (4–8) at different frequencies
Compound
Pellet
Conductivity, S.m-1
thickness, mm
1 kHz
In vacuum
10 kHz
1 MHz
In air In vacuum
In air
In air
In vacuum
(4)
(5)
(6)
(7)
(8)
0.554
0.558
0.638
0.549
0.720
7.05 × 10-8 1.61 × 10-8 4.01 × 10-7 1.39 × 10-7 2.52 × 10-5 1.14 × 10-5
1.82 × 10-8 1.28 × 10-8 1.33 × 10-7 8.87 × 10-8 1.53 × 10-5 6.53 × 10-6
4.98 × 10-8 1.24 × 10-8 3.20 × 10-7 1.11 × 10-7 2.19 × 10-5 7.90 × 10-6
1.59 × 10-6 3.74 × 10-6 3.23 × 10-6 5.67 × 10-6 2.93 × 10-5 4.28 × 10-5
5.39 × 10-8 2.25 × 10-8 3.49 × 10-7 1.95 × 10-7 3.47 × 10-5 2.19 × 10-5
The electrical conductivities of the
phthalocyanines were measured as Ag/
MPc/Ag sandwiches in vacuum and in
air atmosphere.
e0er A
d
C =
σAC = 2pf e0er tand
where C is the capacitance of the sample,
e0 is the permittivity of atmosphere, A is
the surface area of the sample, d is the
thickness of the sample, er is the dielectric
permittivity of the sample, f is the frequ-
ency and tan d is the dielectric loss [49].
The AC conductivity values of metal-free
phthalocyanine and metal complexes at
different frequencies are given in Table 2.
In most of the substituted phthalocyanines
the AC electrical conductivity values
are coherent with the semi-conductive
materials [50] as in this case. Although
there is an increase in the conductivity
Fig. 6. The frequency vs. AC conductivity values of the compounds (4–8) at
300 K (inset: plot of frequency vs. AC conductivity)
hydrogen bonding may be more dominant. In Fig. 6, the
for the measurements in air, the values are of the same
order [51]. The AC conductivity values obtained under
air conditions were higher than those of under vacuum
probably due to the absorbed oxygen in the air atmosphere.
AC conductivities were found to be between ~10-8 and 10-5
S.m-1 for phthalocyanines (4–8). In case of octasubstituted
analogs of (4–8), AC conductivities were found between
~10-9 and 10-5 S.m-1 [21d]. This slight increase may be
the result of the higher Pc–Pc interactions due to the
stacking mode of tetrasubstituted ones. The number of
peripheral groups in tetrasubstituted phthalocyanines
is lower than that of octasubstituted phthalocyanines.
As a result, steric hindrance is lower in tetrasubstituted
(4–8) phthalocyanines, thus p–p interactions between
phthalocyanine units are higher. The increase in the
AC conductivities of (4–8) may also be attributed to the
stronger intermolecular hydrogen bonding in case of the
tetrasubstituted phthalocyanines (4–8), whereas in case of
the octasubstituted phthalocyanine analogs, intramolecular
frequency vs. AC conductivity graph at 300 K is given.
Despite the AC conductivity values of the complexes are
not strongly frequency dependent at lower frequencies and
do not show a clear variation, at higher frequencies, above
about 105 Hz, AC conductivity shows strong frequency
dependence and there is a significant increase with
frequency [21c, 50b]. The AC conductivity values of the
phthalocyanine compounds vs. temperature at 1 kHz and
10 kHz is given in Fig. 7. As consistent with the classical
theory of conductivity, there is an increase in the AC
conductivity values with the increase of temperature. This
behavior can be attributed to the increase in free volume
and thermal mobility of charge carriers.
DSC measurements
The differential scanning calorimetry (DSC) measure-
ments of the metal-free (4) and the metallophthalocy-
anines (5–8) were performed on raw materials with a
Copyright © 2013 World Scientific Publishing Company
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SYNTHESIS AND CHARACTERIZATION OF NOVEL TETRAKIS
581
Fig. 7. Temperature vs. AC conductivity values of the compounds (4–8) at 1 kHz and 10 kHz
Table 3. Thermal properties of phthalocyanines
(4–8)
peak is not very significant in the other compounds (4)
and (7). The thermal history study did not show any
heat flow effects during the second heating to 440 °C.
The initial decomposition effect decreased in order (5)
> (6) > (8) > (4) > (7) (Table 3). The Cu-containing
metallophthalocyanine (7) was the most rapidly
degraded metallophthalocyanine meanwhile Zn-, Ni-
and Co-containing metallophthalocyanines showed good
thermal stability under working conditions. These results
are in good agreement with literature [21a, 54].
Compound
Initial
Main
decomposition
temperature, °C
decomposition
temperature, °C
(4)
(5)
(6)
(7)
(8)
313
371
370
311
344
347
387
393
341
380
EXPERIMENTAL
scanning rate of 10 °C/min between -4–440 °C (Fig. S7).
Both endothermic and exothermic changes were detected
in the region investigated for all the phthalocyanines [52].
The broad peak between 50 and 125 °C is attributed to the
desorption of water and alcohol during the preparation or
the desorption of adsorbed humidity or air gases during
the storage of all the phthalocyanine complexes [21c,
53]. There is a broad melting peak for each compounds
(5), (6) and (8) at 328, 309 and 297 °C, respectively.
The DSC curves of the compounds (4) and (7) do not
show melting points. There is a significant exothermic
peak indicating oxidation right before decomposition
effect for compound (5), (6) and (8), but this exothermic
Materials
Reactions were performed under an atmosphere of
argon using standard Schlenk techniques unless otherwise
specified. 4-Nitrophthalonitrilewassynthesizedaccording
to literature method [26]. 3-Mercapto-1-propanol, 1,8-
diazabicyclo[5.4.0]undec-7-ene (DBU), hydrochloric
acid (HCl), dichloromethane (CH2Cl2), methanol
(MeOH), phosphorus pentoxide (P2O5), pentan-1-ol,
dimethylsulfoxide (DMSO), dimethylformamide (DMF),
tetrahydrofuran (THF), chloroform (CHCl3), pyridine,
2-dimethylaminoethanol (DMAE), petroleum ether,
toluene, 1,2-ethanediol, ethanol, acetone, diethyl ether
Copyright © 2013 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2013; 17: 581–586

˘
582
Ç. YAGCI AND A. BILGIN
were received from commercial suppliers. Anhydrous
metal salts were prepared by using Zn(CH3COO)2∙2H2O,
NiCl2∙6H2O, CuCl2∙2H2O and CoCl2∙6H2O after drying
in a vacuum oven for 4 h at 150°C, 290°C, 120°C and
150°C respectively [27]. K2CO3 was used after drying
in a vacuum oven at 140°C for 20 h [28]. All organic
solvents were dried and purified as described by Perrin
and Armarego [29].
finely ground anhydrous potassium carbonate (8.37g,
60mmol) was added the reaction medium in six equal
portions at 30-min intervals and degassed one more
time. The reaction mixture was stirred efficiently under
argon at 55°C for 2 days. After the reaction mixture
was cooled to room temperature it was poured into ice-
water mixture (600 mL). The creamy precipitate thus
formed was filtered off and washed with water until
the washings became neutral. After the resultant crude
product was crystallized two times from toluene, the
obtained crystals were washed with cold hexane and
cold diethyl ether, respectively. The pure product (3) was
dried over P2O5 at 50 °C in vacuum atmosphere. Rf: 0.59
(7:2:1 Chloroform:petroleum ether:MeOH). Yield 4.2 g
(63%), mp 72 °C. Anal. calcd. for C11H10N2OS: C, 60.53;
H, 4.62; N, 12.83; S, 14.69%. Found C, 60.56; H, 4.59;
N, 12.87; S, 14.65%. 1H NMR (d6-DMSO): d, ppm 8.02
(d, H, ArH), 7.97 (dd, H, ArH), 7.74 (d, H, ArH), 4.66 (t,
H, OH), 3.51 (q, 2H, CH2OH), 3.15 (t, 2H, SCH2), 1.74
(p, 2H, CH2). 13C NMR (d6-DMSO): d, ppm 147.60 (C4),
134.43 (C3), 131.14 (C4), 130.94 (C6), 116.85 (C2), 116.35
(C8), 115.72 (C7), 110.29 (C1), 59.69 (C11), 31.80 (C9),
27.93 (C10). IR (KBr): nmax, cm-1 3290 (–OH), 3099 (=CH
aromatic), 2941, 2881 (–CH2 aliphatic), 2229 (–C≡N),
1581 (aromatic –C=C), 668 (C–S). MS (ESI-MS): m/z
241.0441 (calcd. for [M + Na]+ 241.0411).
Equipment
1H NMR spectra were recorded on a BRUKER DRX-
500 AVANCE spectrometer at 500 MHz and Varian
Mercury Plus 300 MHz spectrometer with d6-DMSO as
solvent and tetramethylsilane as the internal standard. 13C
NMR spectra were recorded on a Varian Mercury Plus
75 MHz spectrometer with d6-DMSO as the solvent and
tetramethylsilane as the internal standard. Transmission
IR spectra of the samples were recorded on a FTIR
spectrophotometer (Schimadzu FTIR-8201 PC) in the
spectral range 4000–400 cm–1 with samples in KBr
pellets. UV-vis spectra were recorded on a model T80+
UV-vis Spectrometer using a 1 cm pathlength quartz
UV cell. Fluorescence excitation and emission spectra
were recorded on a Varian Eclipse spectrofluoremeter
in 1 cm pathlength cuvettes at room temperature. Mass
spectra were acquired in linear modes with average of
50 shots on a Bruker Daltonics Microflex Maldi-TOF
mass spectrometer (Bremen, Germany) equipped with a
nitrogen UV-Laser operating at 337 nm and Bruker
Daltonics Micro-TOF mass spectrometer with an
orthogonal electrospray ionization (ESI) source. All
melting points were taken in capillary tubes with an
electrothermalmeltingpointapparatus(BarnsteadElectro-
thermal IA9100) and were uncorrected. The elemental
analysis of the compounds was determined on a CHNS-
932 LECO and ElementarVario MICRO Cube instrument.
The metal contents of the metallophthalocyanines were
determined on a Unicam 929 AA spectrophotometer. For
the electrical measurements, the surfaces of the samples
were covered with silver paste to form electrodes.An LCR
meter (AGILENT 4284A) equipped with an OXFORD-
ITC-502 temperature controller was used for dielectric
measurements at the range of 1 kHz to 1 MHz frequency
and 300–400 K temperature under vacuum (~10-3 Torr).
Thermal properties were determined by DSC (Perkin
Elmer DSC 4000) measurements with 10 °C.min-1 heating
rate between -4 and 440°C.
Preparation of 2(3),9(10),16(17),23(24)-tetrakis(3-
hydroxypropylmercapto)phthalocyanine (4). A
standard Schlenk tube was charged with (0.218 g,
1.00 mmol) (3), dry pentan-1-ol (4.0 mL) and
1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) (0.15 mL,
0.16 g, 1.0 mmol) and degassed for several times. The
temperature was gradually increased up to 90 °C and the
flask was degassed again with argon. Then the reaction
mixture was stirred at 145 °C for 3 days. After cooling
to room temperature, the reaction mixture was poured
into 100 mL of ice-water mixture and stirred until the
ice was melted. The obtained dark green product was
filtered off and washed with chloroform, petroleum
ether and ethyl acetate respectively. The crude residue
was purified by silica gel column chromatography
(eluant: THF/MeOH, 9:1, v/v). The final petroleum
greenish product was dried under vacuum over P2O5 at
55 °C until dryness. Yield 115 mg (53%), mp 310 °C
(decomposed). Anal. calcd. for C44H42N8O4S4: C, 60.39;
H, 4.84; N, 12.80; S, 14.65%. Found C, 60.31; H, 4.89;
1
N, 12.76; S, 14.67%. H NMR (d6-DMSO): d, ppm
7.52–6.76 (br, 12H, ArH), 4.79 (s, 4H, OH), 3.68 (br,
8H, CH2OH), 2.98 (br, 8H, SCH2), 1.88 (br, 8H, CH2),
-8.68 (br, 2H, NH). IR (KBr): nmax, cm-1 3400 (–OH),
3290 (–NH), 3067 (=CH aromatic), 2927–2869 (–CH2
aliphatic), 1637–1598 (aromatic –C=C–), 1016 (–N–H),
669 (–C–S), UV-vis spectra (pyridine, 1 × 10-5 M):
General synthesis
Preparation of 4-(3-hydroxypropylmercapto)phtha-
lonitrile(3). 3-Mercapto-1-propanol (3.0mL,33.3mmol)
and 4-nitrophthalonitrile (5.25g, 30mmol) were
dissolved in dry DMSO at room temperature in argon
atmosphere and the reaction mixture was degassed
twice. Temperature was increased to 45°C and then
l
max, nm (log e) 712 (4.45), 688 (4.47), 653 (4.15),
624 (4.05), 346 (4.46), 298 (4.54). MS (MALDI-TOF,
2,5-dihydroxybenzoic acid (DHBA as matrix)): m/z
876.553 (calcd. for [M + 2]+ 876.237).
Copyright © 2013 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2013; 17: 582–586

SYNTHESIS AND CHARACTERIZATION OF NOVEL TETRAKIS
583
Preparation of 2(3),9(10),16(17),23(24)-tetrakis
(3-hydroxypropylmercapto)phthalocyaninatozinc(II)
(5). Compound (3) (0.218 g, 1.00 mmol), anhydrous
Zn(CH3COO)2 (0.187 g, 1.00 mmol) and dry pentan-
1-ol (4.0 mL) was placed in a standard Schlenk tube
under argon atmosphere and degassed several times. The
temperature was gradually increased up to 90 °C and DBU
(0.15 mL, 0.16 g, 1.0 mmol) was added to the reaction
medium. After degassing with argon, temperature was
increased up to 160 °C and held at reflux temperature
for 3 days in argon atmosphere. Thereafter the reaction
mixture was cooled to room temperature and poured
into 20 mL 1:1 MeOH:water mixture and stirred for an
h. The resulting greenish precipitate was filtered off and
washed with water and diethyl ether to remove organic
and inorganic residues. The final green product (5) was
then isolated by silica gel column chromatography with
THF/MeOH (9:1, v/v) and dried under vacuum over P2O5
until dryness at 55 °C. Yield 195 mg (83%), mp 335 °C.
Anal. calcd. for C44H40N8O4S4Zn: C, 56.31; H, 4.30; N,
11.94; S, 13.66; Zn, 6.97%. Found C, 56.34; H, 4.33;
N, 11.92; S, 13.64; Zn, 6.95%. 1H NMR (d6-DMSO): d,
ppm 9.28 (br, 4H, ArH), 8.10 (br, 4H, ArH), 7.48 (br, 4H,
ArH), 4.87 (br, 4H, OH), 3.74 (br, 8H, OCH2), 3.13 (br,
8H, SCH2), 2.07 (br, 8H, CH2). IR (KBr): nmax, cm-1
3402 (–OH), 3061 (=CH aromatic), 2952–2846 (–CH2
aliphatic), 1656–1598 (aromatic –C=C–), 682 (–C–S).
UV-vis (DMF, 1.5 × 10-5 M): lmax, nm (log e) 689 (4.72),
657 (3.99), 621 (4.01), 364 (4.31), 293 (4.22). MS
(MALDI-TOF, 2,5-dihydroxybenzoic acid (DHBA as
matrix)): m/z 939.266 (calcd. for [M + 3]+ 939.158).
Preparation of 2(3), 9(10), 16(17), 23(24)-tetrakis (3-
hydroxypropylmercapto)phthalocyanino-tonickel(II)
(6). A mixture of (3) (0.218 g, 1.00 mmol), anhydrous
NiCl2 (0.130 g, 1.00 mmol) and 2-dimethylaminoethanol
(DMAE) (3 mL) was placed in a Schlenk tube under
argon atmosphere. Then the temperature was gradually
increased up to 90 °C and DBU (0.15 mL, 0.16 g, 1.0
mmol) was added to the reaction mixture. The reaction
system was stirred at 170 °C for 3 days under argon
atmosphere. The resulting green reaction mixture was
cooled to room temperature and the solvent was evaporated
at reduced pressure until dryness. Ethanol/water (20 mL,
2:1) mixture was added to the reaction medium and stirred
for 30 min. The obtained crude product was washed
with water, ethanol and acetone respectively. The final
petroleum greenish product (6) was isolated by silica
gel column chromatography (eluant: THF/MeOH, 9:1,
v/v) and then dried under vacuum over P2O5 at 55 °C
until dryness. Yield 187 mg (80%), mp 312 °C. Anal.
calcd. for C44H40N8O4S4Ni: C, 56.72; H, 4.33; N, 12.03;
S, 13.76; Ni, 6.30%. Found C, 56.69; H, 4.35; N, 12.07;
(–C–S). UV-vis (DMF, 1 × 10-5 M): lmax, nm (log e) 694
(4.48), 638 (4.01), 361 (4.26), 292 (4.19). MS (MALDI-
TOF, 2,5-dihydroxybenzoic acid (DHBA as matrix)): m/z
991.675 (calcd. for [M + Na + K]+ 991.167).
Preparation of 2(3), 9(10), 16(17), 23(24)-tetrakis(3-
hydroxypropylmercapto)phthalocyanino-
tocopper(II) (7). A well-stopped Schlenk tube was
charged with (3) (0.218 g, 1.00 mmol), anhydrous
CuCl2 (0.135 g, 1.00 mmol) and DMAE (4.0 mL)
and then the temperature was gradually increased up to
90 °C and DBU (0.15 mL, 0.16 g, 1.0 mmol) was added
under argon atmosphere. Then temperature was increased
up to 160 °C and the reaction medium was stirred at 160
°C for 3 days under argon atmosphere. The resulting
green reaction mixture was cooled to room temperature
and poured into EtOH:water mixture (20 mL, 1:1) and
stirred for an h. The obtained green product was filtered
off washed with water, ethanol, acetone and diethylether
respectively. The crude residue was purified by silica gel
column chromatography (eluant: THF/MeOH, 9:1, v/v).
The final bright green product was dried under vacuum
over P2O5 at 55 °C until dryness.Yield 190 mg (81%), mp
325 °C (decomposed). Anal. calcd. for C44H40N8O4S4Cu:
C, 56.42; H, 4.30; N, 11.96; S, 13.69; Cu, 6.78%. Found
C, 56.40; H, 4.33; N, 11.98; S, 13.65; Cu, 6.81%.
IR (KBr): nmax, cm-1 3409 (–OH), 3061 (=CH aromatic),
2925–2872 (–CH2 aliphatic), 1624–1600 (aromatic
– C=C–), 682 –C–S. UV-vis (DMF, 1 × 10-5 M): lmax
,
nm (log e) 691 (4.99), 658 (4.37), 622 (4.37), 349 (4.62),
296 (4.62). MS (MALDI-TOF, 2,5-dihydroxybenzoic
acid (DHBA as matrix)): m/z 937.05 (calcd. for [M + 2]+
937.151).
Preparationof2(3),9(10),16(17),23(24)-tetrakis(3-
hydroxypropylmercapto)phthalocyanina-
tocobalt(II) (8). A mixture of compound (3) (0.218 g,
1.00 mmol), 1,2-ethanediol (4.0 mL), and CoCl2
(0.130 g, 1.00 mmol) was kept in a Schlenk tube and
degassed several times with argon. The reaction was
treated at 195 °C for 3 days in argon inert atmosphere.
The reaction mixture was cooled to room temperature
and ethanol (3.0 mL) was added to the mixture.
Thereafter the mixture was poured into 50 mL ice-
water mixture and stirred until the ice was melted. The
solid part was filtered off and washed with acetone and
diethyl ether. The crude residue was purified by silica
gel column chromatography (eluant: THF/MeOH, 9:1,
v/v). The final dark green product (8) was dried under
vacuum over P2O5 at 55 °C. Yield 181 mg (78%), mp
305 °C. Anal. calcd. for C44H40N8O4S4Co: C, 56.70; H,
4.33; N, 12.02; S, 13.76; Co, 6.32%. Found 56.74; H,
4.31; N, 12.06; S, 13.79; Co, 6.35%. IR (KBr): nmax, cm-1
3409 (–OH), 3054 (=CH aromatic), 2920–2852 (–CH2
aliphatic), (aromatic –C=C–) 1621–1600, 681(–C–S).
UV-vis (DMF, 1 × 10-5 M): lmax, nm (log e) 682 (4.70),
615 (4.24), 296 (4.55), 271 (4.49). MS (MALDI-TOF,
2,5-dihydroxybenzoic acid (DHBA as matrix)): m/z
934.112 (calcd. for [M + 3]+ 934.162).
1
S, 13.78, Ni, 6.32%. H NMR (d6-DMSO): d, ppm 7.68
(m, 12H, ArH), 4.75 (br, s, 4H, OH), 3.71 (br, 8H, OCH2),
3.01 (br, 8H, SCH2), 1.98 (br, 8H, CH2). IR (KBr): nmax
,
cm-1 3394 (–OH), 3070 (=CH aromatic), 2929–2868
(–CH2 aliphatic), 1664–1600 (aromatic –C=C–), 682
Copyright © 2013 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2013; 17: 583–586

˘
584
Ç. YAGCI AND A. BILGIN
mass spectrum of (4), changes in the visible spectra of
(5) in DMF after the addition of different amounts of
methanol, changes in the visible spectra of (5) in different
solvents, absorption, excitation and emission spectra of
the compound (5) in THF and the DSC thermograms of
(4–8) are given in the supplementary material (Figs S1–
S7). This material is available free of charge via the
Internet at http://www.worldscinet.com/jpp/jpp.shtml.
CONCLUSION
We have synthesized and characterized new
phthalonitrile precursor 4-(3-hydroxypropylmercapto)
phthalonitrile (3) and its hydroxyl-functionalized metal-
free phthalocyanine (4) and metal complexes (5–8)
with four peripheral alkyl thioether groups. Compound
(3) was synthesized by a base-catalyzed nucleophilic
aromatic nitro displacement of 4-nitrophthalonitrile
with the 3-mercapto-1-propanol in dry DMSO. The
metal-free phthalocyanine (4) was prepared with
precursor compound (3) and DBU in dry pentane-1-ol.
The metallophthalocyanines (5–8) (M = Zn, Ni, Cu and
Co) were prepared by the reaction of the compound
(3) with appropriate materials. The compounds were
characterized by elemental analysis, UV-vis, IR, 1H
NMR, 13C NMR, MS spectral data and DSC techniques.
The electronic spectra of the metal-free phthalocyanine in
pyridine and metallophthalocyanine compounds in DMF
were studied at different concentrations. The maximum
Q-band absorptions of tetrasubstituted phthalocyanine
compounds (4–8) were shifted to higher energy side when
compared with the octasubstituted analogs. With the
addition of Ag+ and Hg2+ to the zinc(II) phthalocyanine
(5), Q-bands were slightly blue shifted as a result of the
complexation of peripheral sulfur atoms with Ag+ and
Hg2+ ions that precludes p-donation from sulfur atoms
to the macrocycle core. On the other hand, there was no
shift or optical change with the addition of Pb2+. In the
electronic spectrum of zinc(II) phthalocyanine in pyridine
and DMF, a slight blue shift was detected in case of DMF.
Fluorescence spectrum of the compound (5) was also
studied in THF. Temperature and frequency dependence
of AC conductivity for (4–8) was measured in air and
under vacuum and were found to be ~10-8–10-5 S.m-1.
Thermal properties of the phthalocyanines were examined
by differential scanning calorimetry. The DSC curves of
all the phthalocyanines showed both endothermic and
exothermic changes. Compounds (5), (6) and (8) showed
broad melting points whereas the DSC curves of the
compounds (4) and (7) did not show melting points. The
Cu-containing metallophthalocyanine (7) was the most
rapidly degraded metallophthalocyanine meanwhile Zn-,
Ni- and Co-containing metallophthalocyanines showed
good thermal stability under working conditions.
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Acknowledgements
This work has been supported by Kocaeli University,
Scientific Research Projects Unit, Project number: BAP-
2010/38 (Kocaeli, Turkey). We are also indebted to
Asisst. Prof. Dr. Ersel Özkazanç (Kocaeli University) for
assistance with DSC and conductivity measurements.
Supporting information
1
The H NMR spectra of the compounds (3) and (4),
13C NMR spectrum of the compound (3), MALDI-TOF
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