Synthesis, characterization, aggregation, fluorescence, electrical and thermal properties of novel octasubstituted metal-free and metallophthalocyanines

Article abstract of DOI:10.1016/j.poly.2012.12.023

A dinitrile precursor, 1,2-bis(3-hydroxypropylmercapto)-4,5-dicyanobenzene (3), was synthesized via base-catalyzed nucleophilic aromatic chlorine displacement of 4,5-dichlorophthalonitrile with 3-mercapto-1-propanol. A novel metal-free phthalocyanine (4) (M = 2H) and its metal complexes (5)-(8) (M = Zn, Ni, Cu and Co) were prepared by the cyclotetramerization reaction of (3) with the appropriate materials. The aggregation property of the zinc(II) phthalocyanine (5) was investigated in terms of concentration, Ag⁺, Hg²⁺, Pb²⁺ and Cd²⁺ cations and also different solvents, such as dimethylformamide and pyridine. Complexation of the peripheral dithia groups of (5) with Ag⁺ or Pd²⁺ yields the pentanuclear complex (9) or (10), respectively. The fluorescence spectrum of compound (5) was also studied. The electrical conductivities of (5)-(10) in air and under vacuum were found to be ～10^-9-10^-5 S m ^-1. All the novel compounds were characterized by elemental analysis, UV-Vis, FT-IR, NMR and MS spectral data and DSC techniques.

Full text of DOI:10.1016/j.poly.2012.12.023

Polyhedron 51 (2013) 142–155
Contents lists available at SciVerse ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
Synthesis, characterization, aggregation, fluorescence, electrical and thermal
properties of novel octasubstituted metal-free and metallophthalocyanines
⇑
Çig˘dem Yag˘cı, Ahmet Bilgin
Department of Science Education, Kocaeli University, 41380 Kocaeli, Turkey
a r t i c l e i n f o
a b s t r a c t
Article history:
A dinitrile precursor, 1,2-bis(3-hydroxypropylmercapto)-4,5-dicyanobenzene (3), was synthesized via
base-catalyzed nucleophilic aromatic chlorine displacement of 4,5-dichlorophthalonitrile with 3-mer-
capto-1-propanol. A novel metal-free phthalocyanine (4) (M = 2H) and its metal complexes (5)–(8)
(M = Zn, Ni, Cu and Co) were prepared by the cyclotetramerization reaction of (3) with the appropriate
materials. The aggregation property of the zinc(II) phthalocyanine (5) was investigated in terms of con-
centration, Ag+, Hg2+, Pb2+ and Cd2+ cations and also different solvents, such as dimethylformamide and
pyridine. Complexation of the peripheral dithia groups of (5) with Ag+ or Pd2+ yields the pentanuclear
complex (9) or (10), respectively. The fluorescence spectrum of compound (5) was also studied. The elec-
trical conductivities of (5)–(10) in air and under vacuum were found to be ꢀ10ꢁ9–10ꢁ5 S mꢁ1. All the
novel compounds were characterized by elemental analysis, UV–Vis, FT-IR, NMR and MS spectral data
and DSC techniques.
Received 2 November 2012
Accepted 11 December 2012
Available online 8 January 2013
Keywords:
Phthalocyanine
Metallophthalocyanines
Aggregation
AC Electrical conductivity
DSC
Fluorescence
Ó 2013 Elsevier Ltd. All rights reserved.
1. Introduction
in the triplet–triplet absorption spectra when alkylsulfanyl instead
of alkyloxy moieties were present. The excited states of phthalocy-
Phthalocyanines (Pcs) and their metal complexes (MPcs) have
attracted considerable attention due to their impressive and useful
chemical and physical properties. The diverse functionality of the
anines are expected to play an important role in phthalocyanine
applications. However, relatively little work has been done on
phthalocyanines in solutions [11].
phthalocyanine macrocycle originates from its 18-
p
electron aro-
Phthalocyanines are the most extensively studied materials
among organic semiconductors [12,13]. The electrical conductivi-
ties of phthalocyanines are influenced by the nature of the central
metal or metalloid, substituents at the peripheral benzene rings
and the surrounding atmosphere [14], and change by many (multi)
orders of magnitude under the influence of gases [15] and in the
presence of dopants [16].
The central metal ion and peripheral functional groups having
rich electron-donor units strongly affect the optical and electro-
chemical properties of the phthalocyanine compounds [17]. The
introduction of electron donating sulfur groups at the peripheral
position will result in the shift of the Q band to even longer wave-
lengths [18,19]. Our primary aim has been the synthesis of new
phthalocyanines with various functional groups and macrocycles.
We have previously synthesized novel polymeric phthalocyanines
having O–, S– and N– containing functionalities, such as peripher-
ally long triazadioxa derivatives and very flexible 1,3,6,9,11-penta-
thiaundecane moieties [20], macrocyclic groups [21], and
monomeric phthalocyanine with ethylmercapto–tetrathiamono-
matic system [1]. Functional phthalocyanines are of interest for
making Pcs available for further chemical reactions and new appli-
cations. In addition to their use as highly stable blue and green col-
orants, Pcs have found applications in an ever increasing number of
diverse fields, including high technology fields such as non-linear
optics [2,3], photosensitizers [4], gas sensors [5], catalysts [6], li-
quid crystals [7], optical data storage [8], sensitizers for photody-
namic therapy of cancer [9] and Langmuir–Blodgett films [10]
amongst others.
The substituents on the phthalocyanine ligand influence the
solution and solid-state properties to a large degree and the photo-
physical properties of the Pc dyes are strongly influenced by the
presence and nature of the central metal ion. Metallophthalocya-
nine complexes substituted with peripheral alkylsulfanyl derivates
show especially excellent spectroscopic and photochemical prop-
erties, such as wavelength absorption over 700 nm. A systematic
comparison of oxygen and sulfur as covalent linkers on octasubsti-
tuted zinc(II) phthalocyaninates shows a bathochromic shift of
ꢀ30 nm in the absorption and emission maxima, and of ꢀ60 nm
aza macrocycles and an
a-methylferrocenylmethoxy unit [22].
These compounds have shown a high tendency to bind alkali- or
transition-metal ions and also to form molecular assemblies
through intermolecular interactions. Although phthalocyanines
⇑
Corresponding author. Fax: +90 262 303 2403.
E-mail address: abilgin@kocaeli.edu.tr (A. Bilgin).
0277-5387/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.poly.2012.12.023

Ç. Yag˘cı, A. Bilgin / Polyhedron 51 (2013) 142–155
143
with N- and O-donor substituents have been frequently encoun-
tered, those with thioether moieties are relatively few [18]. Also
a small number of recent patents and proceedings describe the
use of these types of compounds as IR absorbers [23].
The metal contents of the metallophthalocyanines were deter-
mined on a Unicam 929 AA spectrophotometer. For the electrical
measurements, the surfaces of the samples were covered with sil-
ver paste to form electrodes. An LCR meter (AGILENT 4284A)
equipped with an OXFORD-ITC-502 temperature controller was
used for dielectric measurements in the range 1 kHz to 1 MHz fre-
quency and 300–400 K temperature under vacuum (ꢀ10ꢁ3 Torr).
Thermal properties were determined by DSC (Perkin Elmer DSC
4000) measurements with a 10 °C minꢁ1 heating rate between
ꢁ4 and 440 °C.
In this present work, we described the synthesis and character-
ization of hydroxyl-functionalized metal-free and metallophthalo-
cyanines (5–8) with eight comparatively long-chain peripheral
alkyl thioether groups which can not only enable the potential
use as surface anchors [24] but also can be adapted to preparation
of new compounds. The complexation of the thio-donor groups of
(5) with Ag+ or Pd2+ has been investigated. The AC electrical con-
ductivities of the metal free and metallophthalocyanines were
measured in air atmosphere and under vacuum in the sandwich
form covered with silver paste. The aggregation and the fluores-
cence properties of compound (5) were examined. The thermal
properties of the compounds were investigated by DSC with a
scanning rate of 10 °C/min between ꢁ4 and 440 °C. The new com-
pounds were characterized using elemental analysis, UV–Vis,
FT-IR, NMR and MS spectral data.
2.3. Synthesis
2.3.1. 1,2-Bis(3-hydroxypropylmercapto)-4,5-dicyanobenzene (3)
3-Mercapto-1-propanol (0.7 mL, 7.68 mmol) was added to a
solution of 4,5-dichlorophthalonitrile (5.25 g, 30 mmol) in dry
DMF (10 mL) at room temperature and the reaction mixture was
degassed twice. Thereafter the temperature was increased to
55 °C. Finely ground dry Na2CO3 (2.04 g, 19.2 mmol) was added
to the reaction medium in six equal portions at 30 min intervals
with efficient stirring. After degassing one more time, the reaction
mixture was stirred at the same temperature for 5 days. At the end
of this period, the reaction mixture was cooled to room tempera-
ture, filtered off and then evaporated to dryness under reduced
pressure. A minimum amount of dichloromethane was added to
the semi-solid part. After filtering off, the obtained part was
washed with cold dichloromethane. The crude product was dis-
solved in a minimum amount of MeOH at 55 °C. After filtering
the hot solution, the solution was kept in a refrigerator overnight
and the precipitated yellow colored microcrystals that subse-
quently formed were filtered. The pure product (3) was dried over
P2O5 at 50 °C in a vacuum atmosphere. Rf 0.72 (7:2:1 Chloro-
form:petroleum ether:MeOH).Yield: 0.42 g (54%); m.p.: 162 °C. C14-
H16N2O2S2 (308.06): Calc. C 54.52, H 5.23, N 9.08, S 20.79; found C
53.49, H 5.08, N 8.91, S 20.87%. IR (KBr) tmax (cmꢁ1): 3454 (-OH),
3078 (@CH aromatic), 2939, 2893 (–CH2 aliphatic), 2227 (–C„N),
1564 (aromatic –C@C), 686 (C–S). 1H NMR (ppm, d6-DMSO) d:
7.87 (s, 2H, ArH), 4.68 (t, 2H, OH), 3.49 (q, 4H, OCH2), 3.19 (t, 4H,
SCH2), 1.75 (p, 4H, –CH2). 13C NMR (ppm, d6-DMSO): 143.67 (ArCS),
128.83 (ArCH), 116.90 (C„N), 110.78 (ArC), 59.69 (CH2OH), 31.67
(SCH2), 28.77 (SCH2CH2). MS (ESI-MS) m/z: 367.11 [M+2H2O+Na]+.
2. Experimental
2.1. Materials
Reactions were performed under an atmosphere of argon using
standard Schlenk techniques unless otherwise specified. 4,5-
Dichlorophthalonitrile was synthesized according to the literature
method [25]. 3-Mercapto-1-propanol, 1,8-diazabicyclo[5.4.0] un-
dec-7-ene (DBU), hydrochloric acid (HCl), dichloromethane (CH2-
Cl2), methanol (MeOH), phosphorus pentoxide (P2O5), 1-pentanol,
dimethylsulfoxide (DMSO), dimethylformamide (DMF), tetrahy-
drofuran (THF), chloroform (CHCl3), pyridine, 2-dimethylamino-
ethanol (DMAE), petroleum ether, toluene, ethylene glycol,
ethanol, acetone and diethyl ether were received from commercial
suppliers. Anhydrous metal salts were prepared using Zn(CH3-
COO)2ꢂ2H2O, NiCl2ꢂ6H2O, CuCl2ꢂ2H2O and CoCl2ꢂ6H2O after drying
in a vacuum oven for 4 h at 150, 290, 120 and 150 °C, respectively
[26–29]. Na2CO3 was used after drying in a vacuum oven at 180 °C
for 36 h [30]. All organic solvents were dried and purified as de-
scribed by Perrin and Armarego [31].
2.2. Equipment
2.3.2. 2,3,9,10,16,17,23,24-Octakis(3-hydroxypropylmercapto)
phthalocyanine (4)
1H NMR spectra were recorded on a BRUKER DRX-500 AVANCE
spectrometer at 500 MHz and a Varian Mercury Plus 300 MHz
spectrometer with d6-DMSO as the 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 spectrophotom-
eter (Schimadzu FTIR-8201 PC) in the spectral range 4000–
400 cmꢁ1 with samples in KBr pellets. UV–Vis spectra were
recorded on a model T80+ UV/Vis spectrometer using a 1 cm path-
length 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 ac-
quired in linear modes with average of 50 shots on a Bruker Dalton-
ics Microflex Maldi-TOF mass spectrometer (Bremen, Germany)
equipped with a nitrogen UV-Laser operating at 337 nm and a Bru-
ker Daltonics Micro-TOF mass spectrometer with an orthogonal
electrospray ionization (ESI) source. The melting points of the com-
pounds were determined using an electrothermal melting point
apparatus (Barnstead Electrothermal IA9100) and were uncor-
rected. The elemental analysis of the compounds was determined
on a CHNS-932 LECO and Elementar Vario MICRO Cube instrument.
A standard Schlenk tube was charged with (0.150 g, 0.48 mmol)
(3), 4.0 mL dry 1-pentanol and 1,8-diazabicyclo[5.4.0] undec-7-ene
(DBU) (0.15 mL, 0.16 g, 1.0 mmol) and degassed 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 reac-
tion mixture was poured into 120 mL of ice–water mixture and
stirred until the ice melted. The obtained dark green product was
filtered off and washed with chloroform, petroleum ether and then
acetone. The crude residue was purified by silica gel column chro-
matography (eluant: THF/MeOH, 10:1, v/v). The final petroleum
greenish product was dried under vacuum over P2O5 at 55 °C until
dryness. Yield: 53 mg (71%); m.p. >340 °C.
C56H66N8O8S8
(1233.27): Calc. C 54.43, H 5.38, N 9.07, S 20.76; found: C 54.01,
H 5.17, N 9.51, S 20.98%. IR (KBr) tmax (cmꢁ1): 3371 (–OH), 3290
(–N–H), 3073 (@CH aromatic), 2923–2854 (–CH2 aliphatic), 1618,
1560 (aromatic –C@C–), 1058 (–N–H), 666 (–C–S). 1H NMR (ppm,
d6-DMSO) d: 8.022 (s, br, 8H, ArH), 4.92 (t, br, 8H, OH), 3.83 (q,
br, 16H, OCH2), 3.54 (t, 16H, SCH2), 2.12 (p, br, 16H, –CH2), ꢁ3.97
(br, 2H, N–H). kmax, nm (loge): 733 (4.77), 706 (4.76), 671 (4.40),
638 (4.28), 362 (4.66), 331 (4.72). MS (MALDI-TOF) m/z: 1234.80
[M+1]+.

144
Ç. Yag˘cı, A. Bilgin / Polyhedron 51 (2013) 142–155
2.3.3. 2,3,9,10,16,17,23,24-Octakis(3-hydroxypropylmercapto)
phthalocyaninatozinc(II) (5) and 2,3,9,10,16,17,23,24-octakis
THF/MeOH (10:1, v/v) and dried under vacuum over P2O5 at
55 °C until dry.
(3-hydroxypropylmercapto)phthalocyaninatocopper(II) (7)
Compound (5): Yield: 93 mg (88%); m.p.: 335 °C. C56H64N8O8S8-
Zn (1296.19): Calc. C 51.78, H 4.97, N 8.63, S 19.74, Zn 5.03; found:
C 51.57, H 4.79, N 8.57, S 19.49, Zn 5.25%. IR (KBr) tmax (cmꢁ1):
3315 (–OH), 3066 (@CH aromatic), 2925–2867 (–CH2 aliphatic),
1647–1591, (aromatic –C@C–), 698 (–C–S). 1H NMR (ppm, d6-
DMSO) d: 8.29 (s,br, 8H, ArH), 4.96 (t, br, 8H, OH), 3.82 (q, br,
16H, OCH2), 3.53 (t, br, 16H, SCH2), 2.16 (p, br, 16H, –CH2). UV/
Compound (3) (0.200 g, 0.64 mmol), anhydrous Zn(CH3COO)2
(0.119 g, 0.64 mmol) or anhydrous CuCl2 (0.064 g, 0.48 mmol)
and 4.0 mL of dry 1-pentanol were placed in a standard Schlenk
tube under an 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, the temperature was increased up to
160 °C and held at reflux temperature for 3 days in an argon atmo-
sphere. Thereafter the reaction mixture was cooled to room tem-
perature and poured into 50 mL ice–water mixture and stirred
until all the ice melted. The resultant greenish precipitate was fil-
tered off and washed with water, diethyl ether and acetone to re-
move organic and inorganic residues. The final green product (5)
was then isolated by silica gel column chromatography with
Vis (DMF) kmax, nm (loge): 705 (4.82), 669 (4.16), 633 (4.16), 372
(4.51), 283 (4.51). MS (MALDI-TOF) m/z: 1299.84 [M+3]+.
Compound (7): Yield: 58 mg (76%); m.p.: >335 °C. C56H64N8O8S8-
Cu (1295.19): Calc. C 51.85, H 4.97, S 19.77, N 8.64, Cu 4.90; found:
C 51.56, H 4.73, S 19.98, N 8.85, Cu 4.68%. IR (KBr) tmax (cmꢁ1):
3326 (–OH), 3064 (@CH aromatic), 2972–2854 (–CH2 aliphatic),
1620–1595 (aromatic –C@C–), 696 (C–S). UV/Vis (DMF) kmax, nm
(log
e): 707 (4.58), 634 (4.18), 362 (4.73), 285 (4.99). MS (MALDI-
TOF) m/z: 1297.75 [M+2]+.
Cl
Cl
CN
CN
S
O
+
H
H
1
2
Ar (g)
Dry DMF
54%
55 ºC
Dry Na2CO3
CuPc
7
CuCl2, DBU
Ar(g)
Reflux
Dry Pentan-1-ol
H2Pc
4
Ar(g), 71%
Reflux
HO
HO
76%
DBU, Dry Pentan-1-ol
CN
CN
S
S
NiCl2, DBU
Ar(g), 80%
Reflux
1,2-Ethanediol
CoCl2
Ar(g), 76%
Reflux
DMAE
CoPc
NiPc
3
6
8
Zn(CH3COO)2 Ar(g), 88%
DBU
Dry Pentan-1-ol
Reflux
HO
OH
S
S
HO
OH
S
S
N
Zn
N
N
N
N
N
N
N
S
S
OH
HO
S
S
ZnPc
OH
HO
5
Scheme 1. Synthesis of the phthalonitrile (3) and compounds (4), (5), (6), (7) and (8).

Ç. Yag˘cı, A. Bilgin / Polyhedron 51 (2013) 142–155
145
2.3.4. 2,3,9,10,16,17,23,24-Octakis(3-hydroxypropylmercapto)
phthalocyaninatonickel(II) (6)
ted at 195 °C for 3 days in an inert argon atmosphere. The reaction
mixture was cooled to room temperature and then poured into an
ice–water mixture and stirred until the ice 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, 10:1, v/v). The final dark green product (8)
was dried under vacuum over P2O5 at 55 °C. Yield: 60 mg (76%);
m.p.: > 378 °C. C56H64N8O8S8Co (1291.19) Calc.: C 52.04, H 4.99,
N 8.67, S 19.84, Co 4.56; found: C 52.25, H 4.63, N 8.24, S 19.59,
A mixture of (3) (0.200 g, 0.64 mmol), anhydrous NiCl2 (0.130 g,
1.00 mmol) and 3 mL 2-dimethylaminoethanol (DMAE) was placed
in a Schlenk tube under an argon atmosphere. Then the tempera-
ture 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 an argon atmo-
sphere. The resulting green reaction mixture was cooled to room
temperature and the solvent was evaporated at reduced pressure
until dry. Twenty milliliters of ethanol/water (2:1) mixture was
added to the reaction medium and stirred for 30 min. The obtained
crude product was washed with water, ethanol and then acetone.
The final petroleum greenish product (6) was isolated by silica
gel column chromatography (eluant: THF/MeOH, 10:1, v/v) and
then dried under vacuum over P2O5 at 55 °C until dry. Yield:
84 mg (80%); m.p. 305 °C. C56H64N8O8S8Ni (1290.19) Calc.: C
52.05, H 4.99, N 8.67, S 19.85, Ni 4.54%; found: C 51.95, H 4.78,
N 8.58, S 19.56, Ni 4.76%. IR (KBr) tmax (cmꢁ1): 3382 (–OH), 3064
(@CH aromatic), 2925–2854 (–CH2 aliphatic), 1618 (aromatic –
C@C–), 662 (–C–S). 1H NMR (ppm, d6-DMSO) d: 8.07 (s,br, 8H,
ArH), 4.72 (t, br, 8H, OH), 3.85 (q, br, 16H, OCH2), 3.53 (t, br, 16H,
Co 4.85%. IR (KBr)
2925–2856 (–CH2 aliphatic), 1620 (aromatic –C@C–), 672 (C–S).
t
max (cmꢁ1): 3353 (–OH), 3073 (@CH aromatic),
UV/Vis (DMF) kmax, nm (loge): 698 (4.43), 628 (4.13), 313 (4.90),
286 (5.09). MS (MALDI-TOF) m/z: 1292.67 [M+1]+.
2.3.6. The silver(I) complex of zinc(II) phthalocyanine 5 (9)
Compound (5) (45 mg, 0.035 mmol) was dissolved in DMF–
water (3 + 0.2 mL) and silver nitrate (0.0473 g, 0.277 mmol) in
DMF–water (3 + 0.2 mL) was added. The mixture was refluxed for
18 h. The reaction mixture was filtered to separate any silver oxide
formed. The product was obtained by evaporation of the solvent. It
was dissolved in CHCl3, filtered and reprecipitated by addition of
ethanol. Yield: 24 mg (40%). C56H64Ag4N12O20S8Zn (1971.76) Calc.:
C 34.00, H 3.26, Ag 21.81, N 8.50, S 12.96, Zn 3.30%; found: C 34.52,
H 2.97, Ag 21.32, N 8.78, S 13.17, Zn 3.02%. IR (KBr) tmax (cmꢁ1):
3413 (–OH), 3170 (@CH aromatic), 2918–2848 (–CH2 aliphatic),
1637 (aromatic –C@C–), 1384 (–NO3–), 669 (–C–S). 1H NMR
(ppm, d6-DMSO) d: 8.61 (s, br, 8H, ArH), 5.14 (t, br, 8H, OH), 4.01
(q, br, 16H, OCH2), 3.81 (t, br, 16H, SCH2), 2.24 (p, br, 16H, –CH2).
SCH2), 1.80 (p, br, 16H, –CH2). UV/Vis (DMF) kmax, nm (loge): 705
(4.98), 670 (4.30), 633 (4.31), 383 (4.66), 311 (4.54). MS (MALDI-
TOF) m/z: 1292.6 [M+2]+.
2.3.5. 2,3,9,10,16,17,23,24-Octakis(3-hydroxypropylmercapto)
phthalocyaninatocobalt(II) (8)
A mixture of compound (3) (0.150 g, 0.48 mmol), ethylene gly-
col (4.0 mL) and CoCl2 (0.062 g, 0.48 mmol) was kept in a Schlenk
tube and degassed several times with argon. The reaction was trea-
UV/Vis (DMF) kmax, nm (log
e): 705 (4.78), 672 (4.49), 632 (4.27),
367 (5.12), 288 (5.53). MS (MALDI-TOF) m/z: 1973.65 [M+2]+
.
Fig. 1. The 1H NMR spectrum of the compound (3) in d6-DMSO.

146
Ç. Yag˘cı, A. Bilgin / Polyhedron 51 (2013) 142–155
2.3.7. The palladium(II) complex of zinc(II) phthalocyanine 5 (10)
Na2[PdC14] was prepared by refluxing PdCl2 (0.061 g,
0.344 mmol) and NaCl (0.042 g, 0.688 mmol) in 30 mL ethanol over-
night. The reaction mixture was filtered to remove any unreacted
species and the solvent was evaporated under reduced pressure.
Compound (5) (45 mg, 0.035 mmol) was dissolved in DMF–water
(3 + 0.2 mL) and Na2[PdC14] (0.081 g, 0.277 mmol) in DMF–water
(3 + 0.2 mL) was added. The mixture was refluxed for 18 h. The
resulting green reaction was filtered off and then solvent was
evaporated. The product was washed several times with water
and diethyl ether. Yield: 40 mg (67%); C56H64Cl8N8O8Pd4S8Zn
(1999.55) Calc.: C 33.49, H 3.21, Cl 14.12, N 5.58, Pd 21.20, S
12.77, Zn 3.26%; found: C 33.24, H 3.56, Cl 14.75, N 5.71, S 12.64,
Zn 3.56, Pd 21.65%. IR (KBr) tmax (cmꢁ1): 3425 (–OH), 3129 (@CH
aromatic), 2921–2858 (–CH2 aliphatic), 1639 (aromatic –C@C–),
742–719 (–C–S). 1H NMR (ppm, d6-DMSO) d: 8.44 (s, br, 8H,
ArH), 5.04 (t, br, 8H, OH), 3.96 (q, br, 16H, OCH2), 3.65 (t, br, 16H,
tal analysis and mass spectral data were satisfactory: m/z = 367.11
[M+2H2O+Na]+. Compound (3) was also characterized by NMR and
IR spectroscopy techniques. The 1H NMR spectrum of compound
(3) (in d6-DMSO) shows signals at d = 7.87 (s, 2H, ArH), 4.68 (t,
2H, OH), 3.49 (q, 4H, OCH2), 3.19 (t, 4H, SCH2) and 1.75 (p, 4H, –
CH2), ppm, Fig. 1. Furthermore, when treated with D2O, the peak
at 4.69 ppm, corresponding to the protons of O–H groups, was dis-
placed with deuterium. The 13C NMR spectrum of (3) indicates the
primary alcohol atoms at d = 59.69 ppm (CH2OH) and other carbon
atoms at d = 143.67 (ArCS), 128.83 (ArCH), 116.90 (C„N), 110.78
(ArC), 31.67 (SCH2) and 28.77 (SCH2CH2) ppm, Fig. 2. In the IR spec-
trum of (3), the disappearance of the S–H stretching vibration at
2560 cmꢁ1, along with the appearance of new bands at 2227 and
686 cmꢁ1, arising from C„N and Ar–S–C groups, respectively, are
in agreement with the proposed structure.
The metal free compound (4) was synthesized by refluxing a
mixture of (3), DBU and dry 1-pentanol in a Schlenk tube under
a dry argon atmosphere. After purification with silica gel column
chromatography using THF/methanol (10:1, v/v) as the eluent,
the pure product (4) was obtained in a yield of 53%. In the IR spec-
trum of compound (4), the peaks at 3290 and 1058 cmꢁ1 are char-
acteristic peaks for the metal free phthalocyanine N–H stretching
and pyrrole ring vibration bands respectively [33]. A weak absorp-
tion for C@N at 1618 cmꢁ1 was also detected. The 1H NMR spec-
trum of (4) exhibits the typical shielding of inner core protons as
a broad signal at around d = ꢁ3.94 ppm which could be attributed
to the N–H resonances, as confirmed by deuterium exchange [34].
The elemental analysis was satisfactory. The molecular ion peak at
m/z = 1236.85 [M+1]+ also supports the proposed structure.
The zinc(II) phthalocyanine (5) was prepared from the phthalo-
nitrile compound (3) and anhydrous Zn(CH3COO)2 in the presence
SCH2), 2.21 (p, br, 16H, –CH2). UV/Vis (DMF) kmax, nm (log e): 706
(4.85), 632 (4.21), 368 (4.87), 286 (5.15). MS (MALDI-TOF) m/z:
2000.67 [M+1]+.
3. Results and discussion
3.1. Synthesis and characterization
The synthesis of 1,2-bis(3-hydroxypropylmercapto)-4,5-dicya-
nobenzene (3) was performed via based-catalyzed nucleophilic
aromatic chlorine displacement [25,32] of 4,5-dichlorophthalonitrile
with 3-mercapto-1-propanol in dry DMF using finely ground anhy-
drous Na2CO3 as described in the Experimental section (Scheme 1),
with a yield of 54% after recrystallization from methanol. Elemen-
Fig. 2. The 13C NMR spectrum of the compound (3) in d6-DMSO.

Ç. Yag˘cı, A. Bilgin / Polyhedron 51 (2013) 142–155
147
Fig. 3. The 1H NMR spectra of the compounds (9) and (10) in d6-DMSO.

148
Ç. Yag˘cı, A. Bilgin / Polyhedron 51 (2013) 142–155
of DBU as a base catalyst in dry 1-pentanol. The Ni(II) phthalocya-
nine (6) was synthesized by the reaction of compound (3) with
anhydrous NiCl2 in dry DMAE in the presence of DBU. Compound
(7) was synthesized by the reaction of anhydrous CuCl2 and com-
pound (3) in dry 1-pentanol with DBU as a base catalyst. The Co(II)
phthalocyanine (8) was prepared from compound (3) and anhy-
drous CoCl2 in ethylene glycol. The metallophthalocyanines were
purified by column chromatography on silica gel using THF/MeOH
(10:1, v/v) eluent as the mobile phase in 76–88% yields. The Ag+ or
Pd2+ complexes of compound (5) was prepared by using AgNO3 or
Na2[PdCl4] in a DMF–water mixture with yields of 40 and 67%
respectively. The IR spectra of the compounds (5)–(10) were very
similar with the exception of the N–H stretching bands at 3290
and 1058 cmꢁ1 due to the inner core of the metal free phthalocya-
nine. In the IR spectruꢁm of (9) there was a new band at 1384 cmꢁ1
corresponding to NO3 groups. Metal-N vibrations were expected
to appear at 400–100 cmꢁ1, but they were not detected for the
spectra recorded in KBr pellets [35]. The 1H NMR spectra of (5),
Fig. 4. The MALDI-TOF mass spectra of (7), (9) and (10).

Ç. Yag˘cı, A. Bilgin / Polyhedron 51 (2013) 142–155
149
(6), (9) and (10) were similar to those of the precursor phthalonit-
rile (3), but the peaks were broadened due to the phthalocyanine
aggregation at the concentrations used for the NMR measurements
and shifted to the higher resonances than those of the precursor
[36]. The 1H NMR spectra of (9) and (10) are given in Fig. 3. 1H
NMR measurements were precluded for (7) and (8) because of
the paramagnetic nature of the compounds. The mass spectra of
the compounds exhibited peaks at m/z = 1299.84 [M+2]+, 1292.6
[M+2]+, 1297.75 [M+2]+, 1292.67 [M+1]+, 1973.65 [M+2]+ and
2000.67 [M+1]+ for (5)–(10) respectively, and are given in Fig. 4
for compounds (7), (9) and (10). The elemental analyses of the
compounds were satisfactory.
gion (the Q-band); low intensity bands in the visible region to
shorter wavelength of the Q-band are vibronic in origin [37]. The
UV–Vis spectra of (4)–(10) were recorded in solutions of DMF or
pyridine. As seen in Fig. 5, there is a shoulder at the slightly higher
energy side for the metal-free phthalocyanine and its metal com-
plexes. The presence of shoulders in the UV–Vis spectra of com-
pounds corresponds to aggregated or non-aggregated species in
pyridine or DMF. There was a single Q-band for (5)–(8), whereas
there was a split Q-band, as expected, and two strong bands were
in the visible region for (4). The split Q-band, which is characteris-
tic for metal-free phthalocyanines, was observed at kmax values of
733 and 706 with shoulders at 670 and 636 nm, for (4), indicating
the monomeric species; monomeric species with D2h symmetry
show two intense absorptions around 700 nm [38,39]. On the other
3.2. Ground-state electronic absorption spectra
hand, such split Q-band absorptions are due to the
p
)
p⁄ transi-
tion of this fully conjugated 18- electron system [40]. The B-
p
The phthalocyanine system is characterized by strong absorp-
tion bands in the UV region (the Soret band) and in the visible re-
bands of compound (4) were observed at 364 and 332 nm. The
3.0
(a)
2.4
(c)
0.5
0.4
0.3
0.2
0.1
0.0
1.4
R2 : 0.99991
R2 = 0.99995
5.2E-5 M
2.4E-5 M
2.0E-5 M
1.0E-5 M
8.0E-6 M
6.0E-6 M
2.0E-6 M
1.0E-6 M
1.2
2.5
2.0
1.6
1.2
0.8
0.4
0.0
1.0
0.8
0.6
0.4
0.2
4.8E-5 M
4.4E-5 M
4.0E-5 M
3.6E-5 M
2.8E-5 M
2.4E-5 M
2.0E-5 M
1.0E-5 M
2.0
1.5
1.0
0.5
0.0
0.00 0.05 0.10 0.15 0.20 0.25
Concentration x10-4 (mol/L)
1.0x10-5 2.0x10-5 3.0x10-5 4.0x10-5 5.0x10-5 6.0x10-5
Concentration (mol/L)
400
500
600
700
800
400
500
600
700
800
Wavelength (nm)
Wavelength (nm)
2.4
(b)
0.40
(d)
2.4
0.35
0.30
0.25
0.20
0.15
0.10
0.05
0.00
R2 : 0.9999
2.4E-5 M
2.2E-5 M
2.0E-5 M
1.8E-5 M
1.6E-5 M
1.4E-5 M
1.2E-5 M
1.0E-5 M
8.0E-6 M
4.0E-6 M
1.0E-6 M
1.2
0.8
0.4
0.0
1.8
1.2
0.6
0.0
R2=0.99982
2.6E-5 M
2.4E-5 M
2.2E-5 M
2.0E-5 M
1.0E-5 M
8.0E-6 M
6.0E-6 M
4.0E-6 M
2.0E-6 M
1.8
1.2
0.6
0.0
5.0x10-61.0x10-51.5x10-52.0x10-52.5x10-53.0x10-5
0.0
Concentration (mol/L)
0.00
0.05
0.10
0.15
0.20
0.25
Concentration x 10-4 (mol/L)
400
500
600
700
800
400
500
600
700
800
Wavelength (nm)
Wavelength (nm)
3.5
(e)
1.5
1.2
0.9
0.6
0.3
0.0
1.0E-5 M
8.0E-6 M
6.0E-6 M
4.0E-6 M
2.0E-6 M
1.0E-6 M
8.0E-7 M
6.0E-7 M
R2 : 0.9947
3.0
2.5
2.0
1.5
1.0
0.5
0.0
0.00
0.02
0.04
0.06
0.08
0.10
Concentration x10-4
400
500
600
700
800
Wavelength (nm)
Fig. 5. Absorption spectra of (4) (a) in pyridine and (5) (b), (6) (c), (7) (d), (8) (e) in DMF at different concentrations. (Inset: Plot of absorbance versus concentration at 670,
705, 633, 635 and 626 nm for compounds (4), (5), (6), (7) and (8) respectively).

150
Ç. Yag˘cı, A. Bilgin / Polyhedron 51 (2013) 142–155
Q-band absorption of the metallophthalocyanines (5)–(8) is ob-
served as a single band of high intensity in the visible region at
705, 706, 707 and 698 nm, respectively, with shoulders at the
slightly higher energy side of the Q-band for each complex, as ex-
pected. All the phthalocyanine compounds exhibit intense Q-bands
at long wavelengths. It is known that the shift to the lower energy
side is a result of electron-donating -S substituents [20b,41]. The
electronic spectra of the metal free phthalocyanine in pyridine
and metallophthalocyanine compounds in DMF were investigated
at different concentrations. As the concentration of the phthalocy-
anines was increased, the intensity of the Q-band absorption also
increased. There were no shifts or new bands that can be attributed
to aggregation. In order to investigate whether or not the com-
plexes obey the Lambert–Beer law, absorbance versus concentra-
tion graphs were plotted and gave nearly straight lines. This
indicates that the prepared phthalocyanine compounds (4)–(8)
nearly comply with the Lambert–Beer law in the concentration
range given, Fig. 5. This observation indicates that the compounds
mainly exist in the monomeric form under the conditions
employed.
Aggregation is usually depicted as a coplanar association of
rings, processing from monomer to dimer and higher order com-
plexes and driven by non-bonded attractive interactions. It is
dependent on the concentration, nature of solvent, nature of sub-
stituents, complexed metal ions and temperature [42]. In this work
we studied the aggregation behavior of compound (5) using UV–
Vis spectroscopy. Thus different concentrations of metal salts, such
as AgNO3, Hg(NO3)2, Pb(NO3)2 and Cd(NO3)2 in methanol, were
added to the solution of compound (5) in DMF (1 ꢃ 10ꢁ5 M). First,
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 compound (5) in DMF. As can be seen from Fig. 6, there
1.0
(a)
(b)
(c)
(d)
(e)
(f)
0.8
0.6
0.4
0.2
0.0
300
450
600
Wavelength (nm)
750
Fig. 6. Changes in the visible spectra of (a) (5) in DMF (C = 1.2 ꢃ 10ꢁ5 mol/L) after
the addition of (b) 0.2 mL, (c) 0.4 mL, (d) 0.6 mL, (e) 0.8 mL, (f) 1.0 mL methanol.
0.7
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
(a)
(b)
(c)
(d)
(e)
(f)
0.6
(a)
(b)
0.5
0.4
0.3
0.2
0.1
0.0
(c)
(d)
(e)
(e)
(f)
400
500
600
Wavelength (nm)
700
800
400
500
600
700
800
Wavelength (nm)
Fig. 7. Changes in the visible spectra of (a) (5) in DMF (C = 1.0 ꢃ 10ꢁ5 mol/L) after
addition of (b) 0.2 mL, (c) 0.4 mL, (d) 0.6 mL, (e) 0.8 mL, (f) 1.0 mL 0.001 M AgNO3 in
methanol.
Fig. 9. Changes in the visible spectra of (a) (5) in DMF (C = 1.0 ꢃ 10ꢁ5 mol/L) after
addition of (b) 0.2 mL, (c) 0.4 mL, (d) 0.6 mL, (e) 0.8 mL, (f) 1.0 mL 0.1 M Pb(NO3)2 in
methanol.
0.7
(a)
1.00
(b)
(a)
(b)
(c)
(d)
(e)
0.6
0.5
0.4
0.3
0.2
0.1
0.0
(c)
(d)
(e)
(f)
0.75
(g)
(f)
0.50
0.25
0.00
400
500
600
700
800
400
500
600
700
800
Wavelength (nm)
Wavelength (nm)
Fig. 8. Changes in the visible spectra of (a) (5) in DMF (C = 1.0 ꢃ 10ꢁ5 mol/L) after
addition of (b) 0.2 mL, (c) 0.4 mL, (d) 0.6 mL, (e) 0.8 mL, (f) 1.0 mL 0.1 M Hg(NO3)2 in
methanol.
Fig. 10. Changes in the visible spectra of (a) (5) in DMF (C = 1.0 ꢃ 10ꢁ5 mol/L) after
addition of (b) 0.2 mL, (c) 0.4 mL, (d) 0.6 mL, (e) 0.8 mL, (f) 1.0 mL (g) 1.2 mL 0.1 M
Cd(NO3)2 in methanol.

Ç. Yag˘cı, A. Bilgin / Polyhedron 51 (2013) 142–155
151
of the dilution effect. When Ag+ solutions in methanol were added
to a solution of compound (5) in DMF, with the increase in the
amount of Ag+, the intensity of the main Q band of (5) decreased
with a slight shift of 2 nm (705–703 nm). On the other hand, the
shoulder at 669 nm and the Q band at 634 nm were displaced with
a new broadened band at 657 nm, Fig. 7. In the case of Hg2+ solu-
tions in methanol, the Q band of (5) was broadened and blue
shifted by ꢀ5 nm as a result of aggregation, Fig. 8. This behavior
can be attributed to the aggregation phenomena. Dimerization of
the phthalocyanine units by intermolecular complexation through
peripheral dithia groups with Ag+ and Hg2+ ions forms sandwich
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
DMF
Pyridine
type complexes arising from p-stacking interactions, which causes
the new absorption band. The new bands can be ascribed to the
presence of dimeric and oligomeric phthalocyanine species
[20b,43]. Further addition of AgNO3 or Hg(NO3)2 did not change
the spectrum.
400
500
600
700
800
Wavelength (nm)
Fig. 11. Changes in the visible spectra of (5) (C = 1 ꢃ 10ꢁ5 mol/L) in different
solvents.
On the other hand, when Pb2+, Fig. 9, and Cd2+, Fig. 10, solutions
in methanol were added, the intensity of the Q absorption bands at
705 and 634 nm decreased gradually without any shift. There was
no change in the visible spectrum of (5) with the addition of Pb2+
and Cd2+ ions. In addition to the dilution effect, this behaviour in
the visible spectrum may be attributed to very weak or no coordi-
nation of the peripheral S atoms to the Pb2+ and Cd2+ ions [44]. The
aggregation behavior of the zinc(II) phthalocyanine compound (5)
was also investigated in different solvents, such as DMF and pyri-
dine. There is a blue shift in the case of DMF due to the polar char-
acter of the solvent, Fig. 11 [45].
600
500
0.7
0.6
0.5
400
0.4
0.3
0.2
0.1
0.0
Absorption
300
200
100
0
Emission
Excitation
The absorption, excitation and emission spectra of compound
(5) were studied and are given in Fig. 12. The excitation spectrum
was similar to the absorption spectrum and both were mirror
images of the fluorescent spectrum in THF. The proximity of the
wavelength of the Q-band absorption to the Q-band maxima of
the excitation spectrum for compound (5) suggests that the nucle-
ar configurations of the ground and excited states are similar and
are not affected by excitation in THF [46]. Fluorescence emission
peak was observed at k = 710 nm.
600
650
700
750
800
Wavelength (nm)
Fig. 12. Changes in the absorption, excitation and emission spectra of compound
(5) in THF (C = 1 ꢃ 10ꢁ5 M). Excitation wavelength = 671nm.
In order to investigate the interaction of (5) with Ag+ and Pd2+
ions, complexes (9) and (10) were prepared (Scheme 2). As can
be seen in Figs. 13 and 14, the UV–Vis spectra of complexes (9)
was a decrease in the intensities of the Q bands without any shifts
in wavelength in the visible absorption spectra of (5) with an in-
crease of the methanol amount. This decrease could be the result
HO
OH
Y
X
M
'
X
M
S
'
S
S
Y
OH
HO
S
N
9: AgNO3, DMF-H2O
Ar(g), Reflux, 40%
N
N
N
N
ZnPc
M
N
N
5
10: Na2[PdCl4], DMF-H2O
Ar(g), Reflux, 67%
N
S
S
OH
HO
M
X
'
Y
S
X
M
Y
'
S
OH
HO
Compound
M
M'
X
Y
-
9
Zn Ag+ NO3
-
-
-
10
Zn Pd2+ Cl
Cl
Scheme 2. Synthesis of compounds (9) and (10).

152
Ç. Yag˘cı, A. Bilgin / Polyhedron 51 (2013) 142–155
0.5
0.4
0.3
0.2
0.1
0.0
(5)
(9)
400
500
600
700
800
Wavelength
Fig. 13. UV–Vis spectra of compounds (5) and (9) in DMF (C = 6 ꢃ 10ꢁ6 M).
and (10) are similar to those of compound (5), except for broaden-
ing. These broadened bands can be attributed to the interaction of
the thio groups with the different sized cations [18,44,47]. Figs. 13
and 14 show the UV–Vis spectra of compounds (9) and (10), as Ag+
and Pd2+ complexes of compound (5) respectively, whereas Fig. 7
indicates the interaction of (5) with Ag+ ions as a solution in
DMF. The visible spectra of the titration of (5) with an AgNO3 solu-
tion and the isolated complex (9) are expected to be similar, but as
can be seen in Fig. 13 they are not very similar. This can be attrib-
uted to the difference of the working conditions whilst recording
the spectra.
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
(5)
(10)
3.3. Conductivity measurements
400
500
600
700
800
The AC electrical conductivities of the metal free and metall-
ophthalocyanines were measured in air atmosphere and under
vacuum in the sandwich form covered with silver paste to form
electrodes. The capacitance and the dielectric loss factor of each
sample were measured between 1 kHz and 1 MHz frequency and
300–400 K using an LCR meter. The AC conductivity values at dif-
ferent frequencies were calculated using the dielectric permittivity
and the dielectric loss factor according to the given equations, and
the results are given in Table 1.
Wavelength
Fig. 14. UV–Vis spectra of compounds (5) and (10) in DMF (C = 1 ꢃ 10ꢁ5 M).
(4)
4.0x10-6
-5
6.0x10
(5)
(6)
(7)
(8)
2.0x10-6
-5
5.0x10
0.0
102
103
104
-5
4.0x10
e0erA
C ¼
-5
d
3.0x10
-5
2.0x10
rAC ¼ 2
pfeoer tan d
-5
where C is the capacitance of the sample,
e
0 is the permittivity of air,
1.0x10
A is the surface area of the sample, d is the thickness of the sample,
0.0
103
er is the dielectric permittivity of the sample, f is the frequency and
tan d is the dielectric loss [48]. According to Table 1, the AC electri-
cal conductivity values correspond to those of semi-conductive
materials, encountered in most of the substituted phthalocyanines
[49]. The AC conductivity values obtained under air conditions were
higher than those of under vacuum, probably due to absorbed oxy-
104
105
106
log f (Hz)
Fig. 15. The frequency versus AC conductivity of compounds (4)–(8) at 300 K
(Inset: Plot of frequency versus concentration).

Ç. Yag˘cı, A. Bilgin / Polyhedron 51 (2013) 142–155
153
Table 1
The AC conductivity values of (4)–(10) at different frequencies.
Compound
Pellet thickness (mm)
Conductivity (S mꢁ1
)
1 kHz
In air
10 kHz
In air
1 MHz
In air
In vacuum
In vacuum
In vacuum
4
5
6
7
8
9
10
0.457
0.600
0.677
0.600
0.617
0.524
0.571
3.62 ꢃ 10ꢁ6
3.72 ꢃ 10ꢁ8
9.24 ꢃ 10ꢁ8
2.44 ꢃ 10ꢁ8
5.97 ꢃ 10ꢁ6
8.98 ꢃ 10ꢁ9
7.14 ꢃ 10ꢁ9
2.13 ꢃ 10ꢁ6
1.20 ꢃ 10ꢁ8
1.57 ꢃ 10ꢁ7
5.67 ꢃ 10ꢁ9
7.23 ꢃ 10ꢁ7
7.65 ꢃ 10ꢁ9
1.86 ꢃ 10ꢁ9
6.46 ꢃ 10ꢁ6
1.79 ꢃ 10ꢁ7
4.49 ꢃ 10ꢁ7
1.81 ꢃ 10ꢁ7
1.08 ꢃ 10ꢁ5
8.81 ꢃ 10ꢁ8
3.6 ꢃ 10ꢁ8
4.84 ꢃ 10ꢁ6
1.12 ꢃ 10ꢁ7
5.53 ꢃ 10ꢁ7
6.93 ꢃ 10ꢁ8
2.07 ꢃ 10ꢁ6
8.16 ꢃ 10ꢁ8
2.40 ꢃ 10ꢁ8
8.71 ꢃ 10ꢁ5
2.72 ꢃ 10ꢁ5
4.44 ꢃ 10ꢁ5
1.34 ꢃ 10ꢁ5
1.31 ꢃ 10ꢁ4
7.19 ꢃ 10ꢁ6
5.67 ꢃ 10ꢁ6
5.87 ꢃ 10ꢁ5
1.47 ꢃ 10ꢁ5
3.03 ꢃ 10ꢁ5
8.04 ꢃ 10ꢁ6
4.23 ꢃ 10ꢁ5
6.91 ꢃ 10ꢁ6
2.38 ꢃ 10ꢁ6
gen from the air atmosphere. There is not a significant change in the
conductivity values after complexation of the S-donors with the
Ag(I) and Pd(II) ions in case of the compounds (9) and (10) [50].
The frequency versus AC conductivity graph was plotted at 300 K
and is given in Fig. 15. The AC conductivity values of the complexes
are not strongly frequency dependent at lower frequencies and do
not show a clear variation. On the other hand, at higher frequencies,
above about 105 Hz, the AC conductivity shows a strong frequency
dependence and there is a significant increase with frequency
[20c,51]. The AC conductivity values of the phthalocyanine com-
pounds versus temperature at 1 and 10 kHz are given in Fig. 16.
The temperature dependent increase in the AC conductivity can
be attributed to the increase in free volume and thermal mobility
of the charge carriers. It is shown in Fig. 16 that only the conductiv-
ity of compound 5 reduces with increasing temperature at higher
frequency. This phenomenon is inconsistent with the classical the-
ory of conductivity. It may be related to its polarization under a
mutative electric field [52].
1 kHz
(10 kHz)
1.4x10-6
9.0x10-7
3.2x10-6
2.4x10-6
(8)
7.5x10-8
7.0x10-8
7.2x10-9
6.0x10-9
(7)
(6)
2.4x10-7
1.6x10-7
7.0x10-7
6.0x10-7
1.1x10-7
1.5x10-8
1.2x10-8
1.0x10-7
1.0x10-5
(5)
(4)
3.6x10-6
2.4x10-6
5.0x10-6
300 320 340 360 380 400
300 320 340 360 380 400
Temperature (K)
Temperature (K)
Fig. 16. Temperature versus AC conductivity values of compounds (4)–(8) at 1 and
10 kHz.
2
4
6
8
(
4)
5)
6)
7)
8)
(
(
(
(
0
100
200
300
400
Temperature (oC)
Fig. 17. The DSC Thermograms of (4)–(8).

154
Ç. Yag˘cı, A. Bilgin / Polyhedron 51 (2013) 142–155
Table 2
resulting in a clear broadening of the UV–Vis spectra. The excita-
Thermal properties of phthalocyanines (4)–(10).
tion and emission spectra of compound (5) were also studied in
THF and were found to be similar to the absorption spectrum of
(5). The electrical conductivities of the compounds were measured
in air and vacuum atmosphere at room temperature and were
found to be ꢀ10ꢁ9–10ꢁ5 S mꢁ1. The dependence of the AC conduc-
tivity on the frequency and temperature were also evaluated. The
metal free and the Zn(II), Ni(II) and Co(II) metallophthalocyanines
showed good thermal stability under the working conditions,
whilst the Cu(II) phthalocyanine (7) was the most rapidly degraded
metallophthalocyanine. Polymerization of the appropriate mono-
mers with the terminal hydroxyl functionalized groups of phthalo-
cyanine as an initiator, prepared in this work, will be discussed in
future studies.
Compound Dissꢁociation of
Initial
decomposition
temperature (°C)
Main decomposition
temperature (°C)
NO3 Tmax (°C)
4
–
346
390
351
333
348
325
338
378
426
374
368
379
359
371
5
–
6
–
7
–
8
–
9
10
227
–
3.4. DSC measurements
Thermal properties of the metal free (4) and metallophthalocy-
anines (5)–(8) were investigated by DSC (Fig. 17). DSC measure-
ments were performed on raw materials with a scanning rate of
10 °C/min between ꢁ4 and 440 °C. DSC curves exhibit both endo-
thermic and exothermic changes for all the phthalocyanines in
the region investigated [53]. All the metal free and metallophthalo-
cyanines show a broad endothermic peak between 50 and 125 °C
attributed to the desorption of alcohol and water during the prep-
aration or the desorption of adsorbed humidity or air gases during
the storage of the phthalocyanine complexes [20c,54]. Compound
(5) exhibits a broad melting point at 337 °C, whereas compound
(6) exhibits a sharp melting point at 305 °C. The DSC curves of
the compounds (4) and (7)–(10) do not show melting points. There
is a significant exothermic peak indicating oxidation right before
the decomposition effect for compounds (5) and (7), but this exo-
thermic peak is not very significant in the other compounds. The
DSC thermogram of (9) showed an endothermic peak at 227 °C
which may be due to the dissociation of nitrate groups. The ther-
mal stabilities of (9) and (10) were lower than that of compound
(5). The thermal history study did not show any heat flow effects
during the second heating to 440 °C. The initial decomposition
effect decreased in the order (5) > (6) > (8) > (4) > (10) > (7) > (9)
(Table 2). The thermal stabilities of (9) and (10) indicate that the
Ag+ and Pd2+ ions are rather weakly bound to the peripheral dithia
atoms [55]. The Cu-containing metallophthalocyanine (7) was the
most rapidly degraded metallophthalocyanine, while Zn-, Ni- and
Co-containing metallophthalocyanines showed good thermal
stability under the working conditions. These results are in good
agreement with the literature data [20a,56].
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 the DSC and conductivity
measurements.
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