Synthesis and characterization of O- and S-bridged perfluoroalkylated metal-free and zinc phthalocyanines

Article abstract of DOI:10.1142/S1088424613500491

The synthesis of tetra and octa perfluoroalkyl substituted zinc and metal free phthalocyanines (ZnPc and H₂Pc) are reported. The compounds 1-5 have been prepared by nucleophilic substitution of 4-nitrophthalonitrile with 1H,1H,2H,2H-perfluorooc

Full text of DOI:10.1142/S1088424613500491

Journal of Porphyrins and Phthalocyanines
J. Porphyrins Phthalocyanines 2013; 17: 555–563
DOI: 10.1142/S1088424613500491
Published at http://www.worldscinet.com/jpp/
Synthesis and characterization of O- and S-bridged
perfluoroalkylated metal-free and zinc phthalocyanines
·
llke Gürola, Gülay Gümüs¸a, Emel Musluog˘lua, Yadigar Arslana and Vefa Ahsen*†a,b◊
a TUBITAK-Marmara Research Center, Materials Institute, PO Box 21, Gebze 41470, Turkey
b Gebze Institute of Technology, Department of Chemistry, PO Box 141, Gebze 41400, Turkey
Dedicated to Professor Özer Bekaroğlu on the occasion of his 80th birthday
Received 9 February 2013
Accepted 24 March 2013
ABSTRACT: The synthesis of tetra and octa perfluoroalkyl substituted zinc and metal free phthalocya-
nines (ZnPc and H2Pc) are reported. The compounds 1–5 have been prepared by nucleophilic substitution
of 4-nitrophthalonitrile with 1H,1H,2H,2H-perfluorooctanethiol, 1H,1H,2H,2H-perfluorodecan-1-ol,
1H,1H-perfluorodecan-1-ol, 1H,1H-perfluorotetradecan-1-ol and 1H,1H-perfluoro-3,6,9-trioxatridecan-
1-ol, respectively. The compounds 6–8 have been prepared by the reaction of 1H,1H,2H,2H-
perfluorodecan-1-ol, 1H,1H-perfluorodecan-1-ol and 1H,1H-perfluoro-3,6,9-trioxatridecan-1-ol with
4,5-dichlororphthalonitrile, respectively. The compound 9 with thia-bridge has been synthesized from
4,5-dichlororphthalonitrile. Zinc and metal free phthalocyanines were obtained from the corresponding
1
phthalonitrile derivatives. All compounds were characterized by using mass, H, 19F NMR, UV-vis
and FT-IR as well as elemental analysis. Tetra substituted Zn(II) phthalocyanines are slightly soluble
only in THF (Compound 4a and 7a are insoluble) but metal free phthalocyanines are not soluble. Octa
substituted Zn(II) and metal free phthalocyanine are soluble in polar solvents such as THF and DMSO.
KEYWORDS: phthalocyanine, fluoroalkyl substituted phthalocyanine, zinc phthalocyanine, free
phthalocyanine, 19F NMR.
few examples of fully characterized phthalocyanines with
INTRODUCTION
electron-withdrawing substituents have been investigated
Phthalocyanines (Pcs) and its derivates have been
[4–6]. The incorporation of fluorine group as substituent
under intensive study for many decades due to their
on phthalocyanines can modify their physical, chemical,
chemical and thermal stability and flexible preparation
and biological properties [7–11]. Phthalocyanines
methods. The practical applications range from the
and their metal complexes have found application in
dyes and pigments industry to TFT displays, laser, solar
different areas of research, such as photoreceptors in
cells, electrophotography, fuel cells, gas sensors, optical
photographic printing [12], thin film organic transistors
data storage and photodynamic therapy [1–3]. The side
[13, 14], photovoltaic cells [15–17]. In the past decade,
substituents (due to their electron donating or electron
a new generation of phthalocyanines containing electron
withdrawing properties) and the central metal ion play
withdrawing substituents such as fluorine have been
crucial role in overall functionality of the Pcs, as they
developed [8, 9]. Those Pcs are of much interest due to
determine solubility and crystal structure. Up to now, a
their high solubility in polar solvents such as acetone or
THF. The electronic properties are also widely affected
by introducing electron donor or acceptor groups.
◊SPP full member in good standing
In this paper, we describe the synthesis and
*Correspondence to: Vefa Ahsen, email: ahsen@gyte.edu.tr,
characterization of the new class of fluoralkylated
metal-free and zinc phthalocyanines and investigated
the effect of different fluorinated alkyl or alkyloxy chain
tel: +90 262-605-3106, fax: +90 262-605-3101
†Current address: Gebze Institute of Technology, Department of
Chemistry, PO Box 141, Gebze 41400, Turkey
Copyright © 2013 World Scientific Publishing Company

·
556
I. GÜROL ET AL.
length effect on the solubility. These phthalocyanines
were prepared starting from 4-nitrophthalonitrile and
4,5-dichlorophthalonitrile with different heteroatoms and
different fluorine containing materials.
692. 1H NMR (acetone-d6): d, ppm 8.04 (1H, d, Jm = 2 Hz
ArH), 7.97 (1H, d, Jo = 8 Hz ArH), 7.87 (1H, dd, Jm = 2
Hz, Jo = 8 Hz ArH), 3.55 (2H, t, S–CH2), 2.75 (2H, m, S–
CH2–CH2). 19F NMR (acetone-d6): d, ppm -82.05 (t, CF3,
3
3
3JFF = 10 Hz), -114.78 (m, CF2–CH2, JFF = 3 Hz, JHF
=
15 Hz), -122.80 (m, CF2–CF2–CH2), -123.78 (m,–CF2-),
-124.14 (m, CF3–CF2–CF2-), -127.12 (m, CF3–CF2, 4JFF =
13 Hz, 3JFF = 3 Hz). Calcd. for C16H7F13N2S (506.28): C
37.96; H 1.39; N 5.53; found C 37.10; H 1.28; N 5.48.
MS (MS-MALDI): m/z (%) 661 [M + DHB]+.
EXPERIMENTAL
Instrumentation and materials
Elemental analyses were obtained using a Thermo
Finnigan Flash 1112 instrument. The infrared spectra
were recorded between 4000–650 cm-1 using a Perkin
Elmer FT-IR System Spectrum BX with an attenuated
total reflection (ATR) accessory featuring a zinc selenide
(ZnSe) crystal. Absorption spectra were recorded with
4-[(3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10, 10-
Heptadecafluorodecyl)oxy]phthalonitrile (2).
Compound 2 was prepared according to the procedure
described for 1. The amounts of reagents employed
and conditions were as follows: 1H,1H,2H,2H-perfluo-
rodecan-1-ol (2 g, 4.3 mmol) dry DMF (6 mL), 4-nitroph-
thalonitrile (0.8 g, 4.3 mmol), anhydrous potassium
carbonate (1.1 g, 7.8 mmol). The product was soluble in
CHCl3, acetone, MeOH, and DMSO.Yield 1.30 g (51%),
mp 100–103 °C. FT-IR: n, cm-1 3092, 2234 (C≡N), 1602,
1564, 1496, 1421, 1296, 1246, 1199 (CF), 1116, 1104
a Schimadzu 2001 UV spectrophotometer. H and 19F
1
NMR spectra were recorded in aceton-d6 solution on
Bruker and Varian 500 MHz spectrometers. Matrix-
assisted laser desorption/ionization time-of-flight mass
spectrometry (MALDI-TOF-MS) measurements were
performed on a Bruker Daltonics MicrOTOF. Positive
ion and linear mode MALDI-TOF MS spectrum of the
compounds were obtained in 2,5-dihydroxy benzoic acid
(DHB) MALDI matrix using nitrogen laser accumulating
50 laser shots.
n-Amyl alcohol and N,N-dimethylformamide (DMF)
were dried according to literature procedures [18].
Zn(CH3COO)2, K2CO3, anhydrous Na2SO4, 1H,1H-per-
fluoro-3,6,9-trioxatridecan-1-ol, 1H,1H-perfluorote-
tradecan-1-ol, 1H,1H,2H,2H-perfluorooctanethiol were
purchased from commercial suppliers. 4-nitrophtha-
lonitrile [19], and 4,5-dichlorophthalonitrile [20] were
synthesized and purified according to the literature
procedures.
1
(C–O), 1057, 1005, 958, 652. H NMR (acetone-d6): d,
ppm 8.01 (1H, d, Jo = 8 Hz ArH), 7.72 (1H, d, Jo = 2 Hz
ArH), 7.54 (1H, dd, Jm = 2 Hz, Jo = 8 Hz ArH), 4.64 (2H,
t, 3JHF = 10 Hz O–CH2–CH2), 2.91 (2H, m, O–CH2–CH2).
19F NMR (acetone-d6): d, ppm -81.60 (t, CF3, 3JFF = 10 Hz),
-113.52 (m, CF2–CH2, 3JFF = 3 Hz, 3JHF = 15 Hz), -122.10
(m, CF2–CF2–CH2, 3JFF = 9 Hz), -122.35 (m, -CF2-, 3JFF
=
8 Hz), -123.18 (m, -CF2-), -123.93 (m, CF3–CF2–CF2),
-126.53 (m, CF3–CF2, 4JFF = 14 Hz, 3JFF = 3 Hz). Calcd.
for C18H7F17N2O (590.23): C 36.63; H 1.19; N 4.74;
found C 36.43; H 1.18; N 4.68. MS (MS-MALDI): m/z
(%) 745 [M + DHB]+.
4-[(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-
Nonadecafluorodecyl)oxy]phthalonitrile (3).
Compound 3 was prepared according to the procedure
described for 1. The amounts of reagents employed and
conditions were as follows: 1H,1H-perfluorodecan-1-ol
(2 g, 4 mmol), dry DMF (5 mL), 4-nitrophthalonitrile
(0.7 g, 4 mmol), anhydrous potassium carbonate (1.0 g,
7.3 mmol). The product was soluble in CHCl3, acetone,
MeOH, and DMSO.Yield 1.30 g (52%), mp 133–135 °C.
FT-IR: n, cm-1 3092, 2232 (C≡N), 1603, 1569, 1495, 1339,
1294, 1194 (CF), 1144, 1123, 1100 (C–O), 1066, 940, 784.
1H NMR (acetone-d6): d, ppm 8.07 (1H, d, Jo = 8 Hz ArH),
7.87 (1H, d, Jo = 2 Hz ArH), 7.66 (1H, dd, Jm = 2 Hz, Jo = 8
Hz ArH), 5.12 (2H, t, 3JHF = 11 Hz O–CH2–CF2). 19F NMR
(acetone-d6): d, ppm -81.60 (t, CF3, 3JFF = 10 Hz), -120.10
Synthesis
4-[(3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluorooctyl)thio]-
phthalonitrile (1). 1H,1H,2H,2H-perfluorooctanethiol
(2.0 g, 5.3 mmol) was dissolved in dry DMF (5 mL) under
argon and 4-nitrophthalonitrile (0.9 g, 5.3 mmol) was
added. After stirring for 10 min, finely ground anhydrous
potassium carbonate (1.3 g, 9.5 mmol) was added in
portions during 2 h with efficient stirring. The reaction
mixture was stirred under argon atmosphere at 60 °C for
48 h. After the solvent was evaporated under reduced
pressure, water (5 mL) was added and the aqueous phase
was extracted with dichloromethane (3 × 10 mL). The
combinedextractsweretreatedfirstwithsodiumcarbonate
solution (5%), then with water and dried over anhydrous
sodium sulfate. Dichloromethane was removed. The pure
product was obtained by crystallization from CHCl3. The
product was soluble in CH2Cl2, CHCl3, acetone, MeOH,
and DMSO. Yield 2.55 g (93%), mp 85–87 °C. FT-IR: n,
cm-1 3048, 2233 (C≡N), 1587, 1548, 1493, 1449, 1392,
1364, 1237, 1186 (CF), 1123, 1083 (C–O), 1070, 956,
4
4
(m, CF3–CF2–CF2, JFF = 13), -122.21 (m, –CF2-, JFF
=
13), -122.34 (m, –CF2-, 3JFF = 9 Hz), -123.16 (m, –CF2-),
-123.43 (m, CF2–CH2), -126.60 (m, CF3–CF2, JFF = 13
4
Hz). Calcd. for C18H5F19N2O (626.21): C 34.52; H 0.80; N
4.47; found C 34.50; H 0.78; N 4.48. MS (MS-MALDI):
m/z (%) 781 [M + DHB]+.
4-[(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,
12,12,13,13,14,14,14-Heptacosafluorotetradecyl)-
oxy]phthalonitrile (4). Compound 4 was prepared
Copyright © 2013 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2013; 17: 556–563

SYNTHESIS AND CHARACTERIZATION OF O- AND S-BRIDGED PERFLUOROALKYLATED
557
according to the procedure described for 1. The amounts
Acetone (10 mL) was added and filtered. The
pure product was obtained by crystallization from
n-hexane. The product was soluble in acetone, MeOH,
and DMSO. Yield 0.80 g (30%), mp 140–143 °C.
FT-IR: n, cm-1 3052, 2236 (C≡N), 1584, 1556, 1503,
1454, 1391, 1373, 1339, 1203 (CF), 1147, 1103, 1069
of reagents employed and conditions were as follows:
1H,1H-perfluorotetradecan-1-ol (2 g, 2.8 mmol), dry
DMF (100 mL), 4-nitrophthalonitrile (0.5 g, 2.8 mmol),
anhydrous potassium carbonate (0.7 g, 5.1 mmol). After
the solvent was evaporated, water (500 mL) was added
and the compound precipitated. The mixture was filtered
off, washed with water then the pure product was obtained
by crystallization from acetone. The product was soluble
in CH2Cl2, CHCl3, acetone, MeOH, and DMSO. Yield
1.84 g (78%), mp 152–155 °C. FT-IR: n, cm-1 3042, 2232
(C≡N), 1603, 1568, 1495, 1355, 1306, 1203, 1184 (CF),
1116, 979, 966, 624. 1H NMR (acetone-d6): d, ppm 8.09
(1H, d, Jo = 8 Hz ArH), 7.87 (1H, d, Jm = 3 Hz ArH), 7.66
(1H, dd, Jo = 8 Hz, Jm = 3 Hz ArH), 5.13 (2H, t, 3JHF = 13
Hz O–CH2–CF2). 19F NMR (acetone-d6): d, ppm -81.60
1
(C–O), 969, 918, 838, 654. H NMR (acetone-d6): d,
ppm 8.27 (1H, s, ArH), 8.07 (1H, s, ArH), 5.21 (2H, t,
3JHF = 11 Hz O–CH2–CF2). 19F NMR (acetone-d6): d, ppm
-81.59 (t, CF3, 3JFF = 10 Hz), -119.78 (m, CF3–CF2–CF2,
3JFF = 13 Hz), -122.20 (m, –CF2-, 4JFF = 13 Hz), -122.34
(m, –CF2-, 3JFF = 9 Hz), -123,16 (m, –CF2-), -123.34 (m,
4
CF2–CH2), -126.64 (m, CF3–CF2, JFF = 13 Hz). Calcd.
for C18H4ClF19N2O (660.66): C 32.72; H 0.61; N 4.24;
found C 32.62; H 0.58; N 4.21. MS (MS-MALDI): m/z
(%) 815 [M + DHB]+.
4
3
(t, CF3, JFF = 10 Hz), -120.03 (m, –CF2-, JFF = 3 Hz,
4-Chloro-5-(2,2-difluoro-2-{1,1,2,2-tetra-
fluoro-2-[1,1,2,2-tetrafluro-2-(nonafluorobutoxy)
ethoxy]ethoxy}ethoxy)phthalonitrile(7).Compound 7
was prepared according to the procedure described for
6. The amounts of reagents employed and conditions
were as follows: 1H,1H-perfluoro-3,6,9-trioxatridecan-
1-ol (2.0 g, 3.6 mmol), dry DMF (5 mL), 4,5-dichloro-
phthalonitrile (0.3 g, 1.8 mmol) and anhydrous potassium
carbonate (1.5 g, 11 mmol). The product was soluble in
CHCl3, acetone, MeOH, and DMSO.Yield 0.89 g (40%),
mp 60–63 °C. FT-IR: n, cm-1 3044, 2237 (C≡N), 1589,
1500, 1392, 1303, 1186 (CF), 1112, 1067 (C–O), 969,
3JHF = 14 Hz), -122.08 (m, –CF2-), -123.15 (m, –CF2-),
-123.44 (m, CF2–CH2), -126.62 (m, CF3–CF2, JFF = 12
4
Hz). Calcd. for C22H5F27N2O (826.25): C 31.98; H 0.61; N
3.39; found C 31.96; H 0.60; N 3.33. MS (MS-MALDI):
m/z (%) 981 [M + DHB]+.
4-(2,2-Difluoro-2-{1,1,2,2-tetrafluoro-2-
[1,1,2,2-tetrafluro-2(nonafluorobutoxy)ethoxy]-
ethoxy}ethoxy) phthalonitrile (5). Compound 5 was
prepared according to the procedure described for 1. The
amounts of reagents employed and conditions were as
follows:1H,1H-perfluoro-3,6,9-trioxatridecan-1-ol(2.0g,
3.6 mmol), dry DMF (5 mL), 4-nitrophthalonitrile (0.64 g,
3.6 mmol) and anhydrous potassium carbonate (0.9 g,
6.6 mmol). The pure product was obtained by crystalli-
zation from n-hexane. The product was soluble in CH2Cl2,
CHCl3, acetone, MeOH, and DMSO. Yield 1.84 g
(75%), mp 33–35 °C. FT-IR: n, cm-1 3040, 2232 (C≡N),
1603, 1468, 1352, 1295, 1215, 1178 (CF), 1096 (C–O),
963, 907, 665. 1H NMR (acetone-d6): d, ppm 8.09 (2H, d,
Jo = 10 Hz ArH), 7.82 (1H, d, Jm = 5 Hz ArH), 7.63 (1H,
dd, Jo = 10 Hz, Jm = 5 Hz ArH), 5.03 (2H, t, 3JHF = 10 Hz
O–CH2–CF2). 19F NMR (acetone-d6): d, ppm -77.82 (m,
1
731. H NMR (acetone-d6): d, ppm 8.28 (1H, s, ArH),
3
8.04 (1H, s, ArH), 5.14 (2H, t, JHF = 10 Hz O–CH2–
CF2). 19F NMR (acetone-d6): d, ppm -77.83 (t, CF2–
4
3
4
CH2, JFF = 9 Hz, JHF = 14 Hz), -81.88 (m, CF3, JFF
=
4
8 Hz), -84.05 (m, CF2–CF2–CF2–O, JFF = 8 Hz), -89.12
(m, O–CF2–CF2), -89.19 (t, –CF2–O, 3JFF = 4 Hz), -89.22
(m, O–CF2-), -89.30 (m, –CF2–O), -89.33 (m, O–CF2-),
4
-89.38 (m, –CF2-), -127.12 (m, CF3–CF2, JFF = 8 Hz).
Calcd. for C18H4ClF19N2O4 (708.66): C 30.51; H 0.57; N
3.95; found C 30.50; H 0.55; N 3.98. MS (MS-MALDI):
m/z (%) 863 [M + DHB]+.
4
CF2–CH2, JFF = 9 Hz, 3JHF = 17 Hz), -81.84 (m, CF3, 4JFF =
4, 5-bis[(3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 8-Tride-
cafluorooctyl)thio]phthalonitrile (8).Compound8 was
prepared according to the procedure described for 6.
1H,1H,2H,2H-perfluorooctanethiol (2.0 g, 5.3 mmol),
dry DMF (5mL), 4,5-dichlorophthalonitrile (0.48g,
2.6 mmol), anhydrous potassium carbonate (2.2 g,
16mmol). The reaction mixture was stirred under argon
atmosphere at 60 °C for 48 h. The solvent was evaporated
under reduced pressure. Water (5 mL) was added and the
aqueous phase was extracted with dichloromethane (3 ×
10 mL). The combined extracts were treated first with
sodium carbonate solution (5%), then with water and
dried over anhydrous sodium sulfate. Dichloromethane
was removed under reduced pressure. The pure product
was obtained by crystallization from CHCl3. The product
was soluble in CH2Cl2, CHCl3, acetone, MeOH, and
DMSO. Yield 2 g (42%), mp 105–109 °C. FT-IR: n,
cm-1 3044, 2232 (C≡N), 1567, 1459, 1439, 1363, 1349,
8 Hz), -84.06 (m, CF2–CF2–CF2–O), -89.10 (m, O–CF2–
CF2), -89.13 (t, –CF2–O, 3JFF = 4 Hz), -89.16 (m, O–CF2-),
-89.20 (m, –CF2–O), -89.22 (m, O–CF2-), -89.40 (m,
–CF2-), -127.10 (m, CF3–CF2, 4JFF = 9 Hz, 3JFF = 4 Hz).
Calcd. for C18H5F19N2O4 (674.22): C 32.07; H 0.75; N
4.15; found C 32.13; H 0.83; N 3.94. MS (MS-MALDI):
m/z (%) 829 [M + DHB]+.
4-Chloro-5-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,
10,10,10-nonadecafluorodecyl)oxy]phthalonitrile(6).
1H,1H-perfluorodecan-1-ol (2 g, 4 mmol) was dissolved
in dry DMF (5 mL) under argon and 4,5-dichloro-
phthalonitrile (0.4 g, 2 mmol) was added. After stirring
for 10 min, finely ground anhydrous potassium carbonate
(1.6 g, 12 mmol) was added in portions during 2 h
with efficient stirring. The reaction mixture was
stirred under argon atmosphere at 70 °C for 72 h.
The solvent was evaporated under reduced pressure.
Copyright © 2013 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2013; 17: 557–563

·
558
I. GÜROL ET AL.
1215, 1182 (CF), 1122, 1097 (C–O), 1073, 963, 642.
1H NMR (acetone-d6): d, ppm 8.04 (2H, s, ArH), 3.58
(4H, t, S–CH2), 2.76 (4H, m, S–CH2–CH2–CF2). 19F
NMR (acetone-d6): d, ppm -82.07 (t, CF3, 3JFF = 10 Hz),
-114.66 (m, CF2–CH2, 3JFF = 4 Hz, 3JHF = 15 Hz), -122.81
(m, CF2–CF2–CH2), -123.80 (m, CF2–CF2), -124.14 (m,
CF2–CF2), -127.12 (m, CF3–CF2, 4JFF = 8 Hz, 3JFF = 3 Hz).
Calcd. for C24H10F26N2S2 (884.44): C 32.59; H 1.14; N
3.17; found C 32.80; H 1.18; N 3.25. MS (MS-MALDI):
m/z (%) 1039 [M + DHB]+.
Compound1a.Compound1(0.5g,1mmol),anhydrous
Zn(CH3COO)2 (0.047 g, 0.25 mmol) and DBU (0.2 mL)
in 5 mL of n-amyl alcohol were heated to 140 °C for 7 h
under argon atmosphere. The reaction mixture was cooled
to room temperature and filtered. The crude product was
refluxed with MeOH, CH2Cl2 and ethylacetate and filtered
off, respectively. Yield 160 mg (77%), mp > 200 °C.
FT-IR: n, cm-1 2980, 1602, 1487, 1442, 1362, 1311, 1222,
1184 (CF), 1119, 1069 (C–O), 952, 911, 740. Calcd. for
C64H28F52N8S4Zn (2090.55): C 36.77; H 1.35; N 5.36;
found C 36.72; H 1.34; N 5.31. MS (MS-MALDI): m/z
(%) 2090.4 [M]+, 1759.4 [M2 - CF3(CF2)5CH]+, 1428.8
M–2[CF3(CF2)5CH]+, 668.92 M–2[CF3(CF2)5CF3(CF2)5
CH2CH2S]+. UV-vis (in THF): lmax, nm (log e) 682 (5.08),
615 (4.34), 357.5 (4.65), 291 (4.33).
Compound 1b. Compound 1 (0.25 g, 0.5 mmol) and
DBU (0.1 mL) in 2 mL of n-amyl alcohol were heated
to 140 °C for 8 h under argon atmosphere. The reaction
mixture was cooled to room temperature and filtered.
The crude product was refluxed with MeOH, CH2Cl2 and
ethylacetate and filtered off. Yield 130 mg (52%), mp >
200 °C. FT-IR: n, cm-1 3292 (NH), 2942, 1606, 1504,
1445, 1363, 1313, 1231, 1184 (CF), 1120, 1070 (C–O),
1011, 954, 741. Calcd. for C64H30F52N8S4 (2027.17):
C 37.92; H 1.49; N 5.53; found C 37.90; H 1.44; N
5.51. MS (MS-MALDI): m/z (%) 2027.1 [M]+, 1751.3
[M – CF3(CF2)4H6]+.
FT-IR: n, cm-1 3292 (NH), 2935, 1614, 1475, 1394,
1327, 1238, 1199 (CF), 1144, 1115, 1098 (C–O), 1008,
928, 826, 744. Calcd. for C72H30F68N8O4Zn (2362.94): C
36.60; H 1.28; N 4.74; found C 36.57; H 1.24; N 4.71.
Compound 3a. Compound 3a was prepared according
to the procedure described for 2a. The amounts of
reagents employed were as follows: compound 3 (0.25 g,
0.4 mmol), anhydrous Zn(CH3COO)2 (0.018 g, 0.11
mmol), DBU (0.07 mL) and n-amyl alcohol (2 mL).
Yield 100 mg (39%), mp > 200 °C. FT-IR: n, cm-1 2942,
1609, 1492, 1393, 1338, 1236, 1194 (CF), 1144, 1116,
1094 (C–O), 946. Calcd. for C72H20F76N8O4Zn (2570.22):
C 33.65; H 0.80; N 4.36; found C 33.62; H 0.78; N 4.31.
MS (MS-MALDI): m/z (%) 2570.1 [M]+. UV-vis (in
THF): lmax, nm (log e) 673 (4.81), 608 (4.11), 349 (4.48),
284 (4.15).
Compound 3b. Compound 3b was prepared according
to the procedure described for 2b. The amounts of
reagents employed were as follows: compound 3 (0.25 g,
0.4 mmol), DBU (0.1 mL) and n-amyl alcohol (1.5 mL).
Yield 10 mg (4%), m.p. > 200 °C. FT-IR: n, cm-1 3353
(NH), 3036, 1614, 1484, 1200, 1176 (CF), 1098 (C–O),
960. Calcd. for C72H22F76N8O4 (2506.64): C 34.50; H 0.9;
N 4.48; found C 34.47; H 0.89; N 4.45.
Compound 4a. Compound 4a was prepared according
to the procedure described for 1a. The amounts of
reagents employed were as follows: compound 4 (0.5 g,
0.6 mmol), anhydrous Zn(CH3COO)2 (0.028 g, 0.15
mmol), DBU (0.1 mL) and n-amyl alcohol (3 mL). Yield
370 mg (72%), mp > 200 °C. FT-IR: n, cm-1 1610, 1488,
1457, 1395, 1340, 1201, 1180 (CF), 1092 (C–O), 1009,
968, 744. Calcd. for C88H20F109N7O4Zn (3375.39): C
31.31; H 0.60; N 2.90; found C 31.29; H 0.57; N 2.91.
MS (MS-MALDI): m/z (%) 3375.1 [M]+.
Compound 4b. Compound 4b was prepared according
to the procedure described for 1b. The amounts of
reagents employed were as follows: compound 4 (0.25 g,
0.3 mmol), DBU (0.1 mL) and n-amyl alcohol (1 mL).
Yield 115 mg (86%), mp > 200 °C. FT-IR: n, cm-1 1616,
1487, 1396, 1351, 1201, 1182 (CF), 1099 (C–O), 1009,
745. Calcd. for C88H22F109N7O4 (3312.01): C 31.91; H
0.67; N 2.96; found C 31.87; H 0.64; N 2.94.
Compound 2a. Compound 2 (0.25 g, 0.4 mmol),
anhydrous Zn(CH3COO)2 (0.020 g, 0.11 mmol) and DBU
(0.1 mL) in 2 mL of n-amyl alcohol were heated to 140 °C
for 7 h under argon atmosphere. The reaction mixture
was cooled to room temperature and filtered. The crude
product was refluxed with MeOH, CH2Cl2 and n-hexane
and filtered off. Yield 85 mg (33%), mp > 200 °C. FT-IR:
n, cm-1 2935, 1609, 1490, 1394, 1339, 1238, 1192 (CF),
1144, 1113, 1090 (C–O), 1056, 946, 743. Calcd. for
C72H28F68N8O4Zn (2426.28): C 35.64; H 1.16; N 4.62;
found C 35.62; H 1.14; N 4.61. MS (MS-MALDI): m/z (%)
2426.9 [M]+, 1980.5 [M – CF3(CF2)7CH2C]+, 659.4 [M –
Compound 5a. Compound 5a was prepared according
totheproceduredescribedfor1a.Theamountsofreagents
employed were as follows: compound 5 (0.5 g, 0.7 mmol),
anhydrous Zn(CH3COO)2 (0.034 g, 0.19 mmol), DBU
(0.15 mL) and n-amyl alcohol (3.7 mL). Yield 100 mg
(21%), mp > 200 °C. FT-IR: n, cm-1 1611, 1491, 1401,
1304, 1186 (CF), 1100 (C–O), 969, 742. Calcd. for
C72H20F76N8O16Zn (2762.23): C 31.31; H 0.73; N 4.06;
found C 31.44; H 1.12; N 3.99. MS (MS-MALDI): m/z
(%) 2762 [M]+. UV-vis (in THF): lmax, nm (log e) 669.5
(4.94), 605 (4.22), 348.5 (4.58), 282 (4.15).
CF3(CF2)7CH2C–3[CF3(CF2)7]-Zn]+. UV-vis (in THF): lmax
,
nm (log e) 673.5 (4.13), 608 (3.47), 350 (3.86), 292 (3.51).
Compound 2b. Compound 2 (0.25 g, 0.4 mmol), and
DBU (0.1 mL) in 1.5 mL of n-amyl alcohol were heated
to 140 °C for 8 h under argon atmosphere. The reaction
mixture was cooled to room temperature and filtered. The
crude product was refluxed with n-hexane, CH2Cl2 and
MeOH and filtered off. Yield 17 mg (7%), mp > 200 °C.
Compound 5b. Compound 5b was prepared according
to the procedure described for 1b. The amounts of
reagents employed were as follows: compound 5 (0.5 g,
0.7 mmol), DBU (0.23 mL) and n-amyl alcohol (2.3 mL).
Copyright © 2013 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2013; 17: 558–563

SYNTHESIS AND CHARACTERIZATION OF O- AND S-BRIDGED PERFLUOROALKYLATED
559
Yield 25 mg (5%), mp > 200 °C. FT-IR: n, cm-1 1615,
1484, 1305, 1202, 1186 (CF), 1095 (C–O), 952, 743.
C72H22F76N8O16 (2698.85): C 32.04; H 0.82; N 4.15;
found C 32.04; H 0.78; N 4.15.
M – [CF3(CF2)5], 1763.5 [M – 3[CF3(CF2)5CH2CH2]–
[Zn–2S–4H–2[CF3(CF2)5CH2]+, 1055.6 [M–6[CF3(CF2)5-
CH2CH2]–[Zn–2S–4H–CF3(CF2)5CH2]+. UV-vis (in THF):
l
max, nm (log e) 697 (4.93), 627 (4.20), 365 (4.51), 310.5
(4.20).
Compound 8b. Compound 8b was prepared according
Compound 6a. Compound 6a was prepared according
totheproceduredescribedfor1a.Theamountsofreagents
employed were as follows: compound 6 (0.15 g, 0.23
mmol), anhydrous Zn(CH3COO)2 (0.041 g, 0.06 mmol),
DBU (0.05 mL) and n-amyl alcohol (1.2 mL).Yield 40 mg
(26%), mp > 200 °C. FT-IR: n, cm-1 2935, 1602, 1475,
1418, 1351, 1201, 1143 (CF), 1104, 1072 (C–O), 976.
Calcd. for C72H16Cl4F76N8O4Zn (2708.04): C 31.93;
H 0.60; N 4.14; found C 31.94; H 0.58; N 4.12. MS
(MS-MALDI): m/z (%) 2708.2 [M]+, 2253.9 [M –
CF3(CF2)7Cl]+, 2152.4 [M – CF3(CF2)72ClZn]+, 1567.7
[M – 2(CF3(CF2)8) – CHO-Zn-3Cl]+. UV-vis (in THF):
to the procedure described for 1b. The amounts of
reagents employed were as follows: compound 8 (0.25 g,
0.3 mmol), DBU (0.06 mL) and n-amyl alcohol (1 mL).
Yield 90 mg (36%), mp > 200 °C. FT-IR: n, cm-1 3292
(NH), 2980, 1597, 1505, 1417, 1401, 1362, 1183 (CF),
1150, 1121, 1072 (C–O), 1014, 955, 749, 708. Calcd.
for C96H42F104N8S8 (3539.98): C 32.57; H 1.20; N 3.17;
found C 32.66; H 1.17; N 3.14. MS (MS-MALDI): m/z
(%) 3539.7 [M]+, 3342.2 [M – CF3(CF2)2CH2CH2]+.
l
max, nm (log e) 670 (4.37), 606.5 (3.77), 353 (4.11),
286.5 (3.92).
RESULT AND DISCUSSION
Compound 6b. Compound 6b was prepared according
to the procedure described for 1b. The amounts of
reagents employed were as follows: compound 6 (0.15 g,
0.23 mmol), DBU (0.05 mL) and n-amyl alcohol (1 mL).
Yield 21 mg (14%), mp > 200 °C. FT-IR: n, cm-1 3292
(NH), 2946, 1610, 1506, 1448, 1388, 1334, 1234,
1199 (CF), 1145, 1079 (C–O), 1019, 977. Calcd. for
C72H16Cl4F76N8O4 (2644.65): C 32.70; H 0.69; N 4.24;
found C 32.69; H 0.67; N 4.22.
Compound 7a. Compound 7a was prepared according
to the procedure described for 1a. The amounts of
reagents employed were as follows: compound 7 (0.25 g,
0.35 mmol), anhydrous Zn(CH3COO)2 (0.017 g, 0.09
mmol), DBU (0.06 mL) and n-amyl alcohol (1.76 mL).
Yield75mg(29%),mp>200°C.FT-IR:n,cm-1 2930,1607,
1490, 1446, 1396, 1304, 1188 (CF), 1140, 1089 (C–O),
953, 742. Calcd. for C72H16Cl4F76N8O16Zn (2899.94):
C 29.82; H 0.55; N 3.86; found C 29.80; H 0.52; N 3.83.
MS (MS-MALDI): m/z (%) 2899 [M]+, 1629.6 [M–
2CF3(CF2)3O (CF2CF2O)2)–CF2CH2 4Cl – Zn]+.
Compound 7b. Compound 7b was prepared according
to the procedure described for 1b. The amounts of
reagents employed were as follows: compound 7 (0.25 g,
0.35 mmol), DBU (0.1 mL) and n-amyl alcohol (1.2 mL).
Yield 70 mg (28%), mp > 200 °C. FT-IR: n, cm-1 3240
(NH), 2935, 1610, 1519, 1448, 1304, 1187 (CF), 1098
(C–O), 1023, 953, 742. Calcd. for C72H18Cl4F76N8O16
(2836.59): C 30.49; H 0.64; N 3.95; found C 30.44; H
0.62; N 3.94.
Compound 8a. Compound 8a was prepared according
to the procedure described for 1a. The amounts of
reagents employed were as follows: compound 8
(0.5 g, 0.5 mmol), anhydrous Zn(CH3COO)2 (0.026 g,
0.14 mmol), DBU (0.1 mL) and n-amyl alcohol (10 mL).
Yield 140 mg (28%), mp > 200 °C. FT-IR: n, cm-1 2980,
1596, 1407, 1366, 1183 (CF), 1172, 1119, 1068 (C–O),
946, 743, 707. Calcd. for C96H40F104N8S8Zn (3603.18):
C 32.00; H 1.12; N 3.11; found C 31.96; H 1.17; N
3.14. MS (MS-MALDI): m/z (%) 3603.8 [M]+, 3284.4.
The compounds 1–5 were prepared by nucleophilic
substitution of nitro group in 4-nitrophthalonitrile with
1H,1H,2H,2H-perfluorooctanethiol, 1H,1H,2H,2H-
perfluorodecan-1-ol, 1H,1H-perfluorodecan-1-ol, 1H,1H-
perfluorotetradecan-1-ol and 1H,1H-perfluoro-3,6,9-
trioxatridecan-1-ol, respectively.Thecompounds6–8were
prepared by the reaction of 1H,1H,2H,2H-perfluorodecan-
1-ol, 1H,1H-perfluorodecan-1-ol and 1H,1H-perfluoro-
3,6,9-trioxatridecan-1-ol with 4,5-dichlororphthalonitrile,
respectively. In addition, the compound 8 was also
prepared similar to the synthesis of compounds 6 and 7.
However, compound 8 with thia-bridge was obtained as
di-substituted dinitrile (Fig. 1). Unfortunately, we were
unable to synthesize the disubstituded dinitrile derivatives
starting from 1H,1H,2H,2H-perfluorodecan-1-ol, 1H,1H-
perfluorodecan-1-ol, 1H,1H-perfluorotetradecan-1-ol
and 1H,1H-perfluoro-3,6,9-trioxatridecan-1-ol.
The zinc(II) phthalocyanines were synthesized
according to the reported methods [21, 22]. Both octa
and tetrasubstituted Zn(II)phthalocyanine reactions
were achieved in anhydrous n-amyl alcohol and
1,5-diazabicyclo [4.3.0]non-5-ene (DBU) as base in the
presenceofanhydrouszincacetateat140°Cunderanargon
atmosphere. All phthalocyanines were obtained by the
cyclotetramerization of mono-susbtituted phthalonitriles
or di-substituted phthalonitrile derivatives. The metal-free
phthalocyanines were obtained directly from the reaction
of compounds 1–8 in n-amyl alcohol at reflux temperature
in the presence of DBU. The new intermediate products
and phthalocyanines were characterized by 1H NMR, 19F
NMR, elemental analysis, and MS. The spectroscopic
data for the newly synthesized compounds were in
accordance to the assigned formulation. The results are
given in the experimental section.
We have observed that the solubility of all
phthalocyanines are affected by the central metal ion.
While all Zn(II) phthalocyanines are soluble in polar
organic solvents such as THF and acetone, all metal-free
Copyright © 2013 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2013; 17: 559–563

·
560
I. GÜROL ET AL.
R
N
N
N
N
Compound
R
M
N
M
N
R
CN
R
N
R
N
1
SCH2CH2(CF2)5CF3
-
CN
2
OCH2CH2(CF2)7CF3
OCH2(CF2)8CF3
-
1-5
3
-
4
OCH2(CF2)12CF3
-
R
5
OCH2CF2(CF2CF2O)2O(CF2)3CF3
OCH2(CF2)8CF3
-
1a-5a
1b-5b
6
-
7
OCH2CF2(CF2CF2O)2O(CF2)3CF3
SCH2CH2(CF2)5CF3
-
Cl
R
8
-
1a
1b
2a
2b
3a
3b
4a
4b
5a
5b
6a
6b
7a
7b
8a
8b
SCH2CH2(CF2)5CF3
Zn
2H
Zn
2H
Zn
2H
Zn
2H
Zn
2H
Zn
2H
Zn
2H
Zn
2H
SCH2CH2(CF2)5CF3
N
N
N
N
N
M
N
R
Cl
CN
CN
Cl
R
OCH2CH2(CF2)7CF3
OCH2CH2(CF2)7CF3
OCH2(CF2)8CF3
N
N
R
Cl
6,7
OCH2(CF2)8CF3
OCH2(CF2)12CF3
Cl
R
OCH2(CF2)12CF3
6a,7a
6b,7b
OCH2CF2(CF2CF2O)2O(CF2)3CF3
OCH2CF2(CF2CF2O)2O(CF2)3CF3
OCH2(CF2)8CF3
R
R
OCH2(CF2)8CF3
N
N
OCH2CF2(CF2CF2O)2O(CF2)3CF3
OCH2CF2(CF2CF2O)2O(CF2)3CF3
SCH2CH2(CF2)5CF3
N
N
N
M
N
R
R
R
R
R
R
CN
N
N
R
CN
SCH2CH2(CF2)5CF3
8
R
8a
8b
Fig. 1. Synthesis routes of substituted phthalocyanine derivatives
phthalocyanines are not soluble. Generally, the solubility
ofperfluoroalkylsubstitutedPcsdependsonthelengthand
the number of fluorinated alkyl chains on the periphery [4,
21, 23]. The increasing number of substituent decreases
the solubility. Thus, octa-substituted derivatives have
less solubility than tetra-substituted ones. Besides, the
bridging atom is also effective on solubility. In the case
of S-, the solubility is better in comparison with O- as
bridging atom.
The IR spectra of the compounds 1–8 clearly indicate
the presence of C≡N groups by the intense stretching
bands around 2234 cm-1. The characteristic C–F bands
of these compounds appeared around 1190 cm-1. In
addition, the characteristic C–O bands of the compounds
5 and 7 were observed as strong peaks at 1096 and
1067 cm-1 respectively. Generally, the phthalocyanine
compounds are prepared by cyclotetramerization of
dinitrile derivatives, the sharp peak for C≡N vibration
disappeared after conversion into phthalocyanines.
Besides, NH stretching bands at around 3290 cm-1 due
to the inner core imino groups are observed for all metal
free phthalocyanines.
The optical spectra of the soluble compounds (1a, 2a,
3a, 5a, 6a, 8a) measured inTHF (1 × 10-5 M) and exhibited
characteristic absorptions in the Q-band region at around
682, 673.5, 673, 669.5, 670 and 697 nm respectively. The
overall UV-vis spectra are given in Fig. 3. In the case of
S-bridged tetra-substituted derivative (1a), the absorption
maximum is blue shifted about10 nm compared to the
O-bridged tetra Pc (2a). We observed a red shift about
Copyright © 2013 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2013; 17: 560–563

SYNTHESIS AND CHARACTERIZATION OF O- AND S-BRIDGED PERFLUOROALKYLATED
561
Fig. 2. 19F NMR spectrum of compound 2
are insoluble, their UV-vis measurements could not be
accomplished.
For the investigation of the aggregation behavior of
the soluble Pcs, their solution at different concentrations
(1 × 10-5, 5 × 10-6 and 1 × 10-6 M) were prepared in
THF. The intensity of the Q-band absorption increased
in parallel with increasing concentration. Beer–Lambert
law was obeyed for all the soluble Pcs. (Fig. 4).
In the 1H NMR spectrum of the compounds 1–5, the
aromatic protons appear between 8.09–7.54 ppm
as double-doublet and doublet due to orto and
meta positions of the hydrogen atoms belonging to
cyano substituted benzene. The aromatic protons of
compounds 6–7 were observed between 8.28–8.04 ppm
as singlet due to the chlorine atoms on the cyano
substituted benzene as peripheral position. In addition,
Fig. 3. UV-vis spectra of zinc phthalocyanines in THF (1 × 10-5 M)
the compound 8 appears as singlet at 8.04 ppm due
to di-substituted dinitrile. The CH2 protons of the
substituent were observed at different ppm because of
their various bridged groups on the side chains. But
the protons of CH2–CH2–CF2 group exhibit around
2.80 ppm as a triplet due to the effect of the fluorine
atoms for all compounds. However, the protons of
O–CH2- or S–CH2- were observed around 5.12 ppm
15 nm when compared the S-bridged tetra (1a) and octa
(8a) Pcs.
Only the compounds 1a, 2a, 3a, 5a, 6a and 8a are
barely soluble in THF (4a and 7a are insoluble) and the
absorption maxima and extinction coefficients are given
in the experimental section. Since the metal-free Pcs
Copyright © 2013 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2013; 17: 561–563

·
562
I. GÜROL ET AL.
CONCLUSION
In this paper, a homologous series with chain lengths
ranging from CF3(CF2)5 to CF3(CF2)12 containing tetra
and octa substituted metal-free and zinc phthalocyanines
were prepared and characterized. By peripherally
functionalizing with fluoroalkyl and fluoroalkyloxy
chains, we obtained O- and S- bridged tetra substituted
phthalocyanines. The length of chain and the number of
the substituent are influential factors for the solubility.
While the Pcs having short fluorinated alkyl chain
are soluble, the newly synthesized perfluoroalkyl and
fluoroalkyloxy substituted Pcs were slightly soluble in
polar solvents such as THF and acetone. In comparison
to the similar alkyl substituted Pcs, the fluorinated ones
have less solubility. Similarly, tetra substituted Pcs
have better solubility than octa derivatives. The optical
spectra of the soluble compounds exhibited characteristic
absorptions in the Q-band region. In the case of S-bridged
Pcs, the absorption maximum is blue shifted compared to
the O-bridged tetra Pcs. We observed a red shift when
compared the S-bridged tetra and octa Pcs. These new
compounds will also be investigated for their chemical
sensor properties against VOCs in air and pesticides in
water.
Acknowledgements
We are grateful to Dr. Bünyamin COŞUT and
Muhiddin ÇERGEL for the measurements of MS and
NMR spectra.
Fig. 4. Aggregation behavior of 1a, 2a and 8a in THF at
different concentrations (1 × 10-5, 5 × 10-6 and 1 × 10-6 M)
REFERENCES
1. Kenney ME and Liu Y. U.S. Pat. Appl. Publ. 2012,
US 20120323164 A1 20121220. Sharman WM and
Van Lier JE. Bioconjugate Chem. 2005; 16: 1166–
1175. Allemann E, Brasseur N, Kudrevich SV,
Madeleine CL and Van Lier J. Int. J. Cancer 1997;
72: 289–294. Boyle RW, Rousseau J, Kudrevich
SV, Obochi M and Van Lier JE. Br. J. Cancer 1996;
73: 49–53.
2. Bouvet M, Parra V and Suisse JM. Eur. Phys. J.
Appl. Phys. 2011; 56: 34103/1–34103/10. Brant P,
Weber DC, Haupt SG, Nohr RS and Wynne KJ.
J. Chem. Soc. Dalton Trans., Inorganic Chemistry
(1972–1999) 1985; 2: 269–274. Tasaltin C, Gurol I,
Harbeck M, Musluoglu E, Ahsen V and Ozturk ZZ.
Sensors and Actuators, B: Chemical 2010; B150:
781–787. Harbeck M, Tasaltin C, Gurol I, Musluo-
glu E, Ahsen V and Ozturk ZZ. Sensors and Actua-
tors, B: Chemical 2010; B150: 616–624.
and 3.55 ppm, respectively. A common feature of the
1H NMR spectra of all Zn(II) phthalocyanines are
broad absorptions when compared to that of the cyano
derivatives because of a mixture of the four possible
structural isomers of tetrasubstituted phthalocyanines
[24, 25], except compound 7a. Since the metal-free
phthalocyanines are not soluble in acetone-d6 and THF-
d8, the 1H NMR spectra of 1b–8b could not be measured.
The 19F NMR spectra of the compounds 1–8 showed
the characteristic peaks of the fluorine atoms of the substi-
tuted groups [26]. For the compound 2, the peaks assigned
to the CF3, CF2–CH2, CF2–CF2–CH2, CF3–CF2–CF2,
CF3–CF2 fragment were observed around -81, -113, -122,
-124 and -126 ppm respectively (Fig. 2). The CF3 signals
apperaed as a multiplet due to JFF and JFF coupling of
the fluorine atoms (3JFF = 3 Hz, 4JFF = 9 Hz, 3JHF = 15 Hz).
The mass spectra of the compounds 1–8 confirmed the
proposed structure. The mass spectra of all ZnPcs intense
singly charged molecular ions were observed in all cases
in the MALDI-TOF spectra with 2,5-dihyroxybenzoic
acid (DHB) as matrix.
3
4
3. Kuder JE. J. Imag. Sci. 1988; 32: 51–59. Cook MJ
and Chambrier I. J. Porphyrins and Phthalocyanines
2011; 15: 149–173. Moreira LM, dos Santos FV,
Lyon JP, Maftoum-Costa M, Pacheco-Soares C and
Silva NS. Australian J. Chem. 2008; 61: 741–754.
Copyright © 2013 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2013; 17: 562–563

SYNTHESIS AND CHARACTERIZATION OF O- AND S-BRIDGED PERFLUOROALKYLATED
563
Bonnett R. Chem. Soc. Rev 1995; 24: 19–33. Spikes
13. Wu W, Zhang H, Wang Y, Ye S, Guo Y, Di C, Yu G,
Zhu D and Liu Y. Adv. Funct. Mater. 2008; 18:
2593–2601.
14. Zhuoyu J, Liwei S, Congyan L, Long W, Jingwei G,
Hong W, Dongmei L and Ming L. IEEE Electron
Device Letters 2012; 33: 1619–1621.
15. Josef BM, Johannes E and Dieter W. PCT Int. Appl.
2012; WO 2012172107 A1 20121220.
16. Tomas TC, Christian C, Anais MM, Bregt V and
Tom A. PCT Int. Appl. 2012; WO 2012146672 A2
20121101.
17. Moritz R, Christian U, Johannes W, Ronny T,
David W, Gregor S, Wolf-Michael G, Dirk H,
Andre W and Jaehyung H. Adv. Funct. Mater. 2011;
21: 3019–3028.
18. Perrin DD and Armarego WLF. Purification of
Laboratory Chemicals, (2nd edn) Pegamon Press:
Oxford, 1989.
19. Young JG and Onyebuagu W. J. Org. Chem. 1990;
55: 2155–2159. Wöhrle D, Eskes M, Shigehara K
and Yamada A. Synthesis 1993; 2: 194–196.
20. Gurol I, Durmus M and Ahsen V. Eur. J. Inorg.
Chem. 2010; 1220–1230.
JD. J. Fluorine Chem. 2002; 113: 161–165. Gao L
and Qian X. J. Porphyrins and Phthalocyanines
2009; 13: 681–690.
4. Özer M, Yılmaz F, Erer H, Kani İ and Bekaroğlu Ö.
Appl. Organomet. Chem. 2009; 23: 55–61. Romero
NC, Guilleme J, Fernandez-Ariza J, Rodriguez-
Morgade MS, Gonzalez-Rodriguez D, Torres T and
Guldi DM. Org. Lett. 2012; 14: 5656–5659. Sugi-
mori T, Horike S, Handa M and Kasuga K. Inorg.
Chim.Acta.1998;278:253–255.EfimovA,SariolaE
and Lemmetyinen H. J. Porphyrins and Phthalo-
cyanines 2009; 13: 1–13.
5. Debnath AK, Kumar A, Samanta S, Prasad R,
Singh A, Chauhan AK, Veerender P, Singh S,
Basu S and Aswal DK. Appl. Phys. Letters 2012;
100: 142104/1-142104/4.
6. Ozcesmeci M, Ecevit OB, Surgun S and Hamuryu-
dan E. Dyes and Pigments 2013; 96: 52–58.
Ozcesmeci M and Hamuryudan E. Dyes and Pig-
ments 2008; 77: 457–461. Koca A, Özkaya AR,
Selçukoğlu M and Hamuryudan E. Electrochimica
Acta. 2007; 52: 2683–2690.
7. Reddy MR, Shibata N, Kondo Y, Nakamura S and
Toru T. Angew. Chem. Int. Ed. 2006; 45: 8163–8166.
8. Yoshiyama H, Shibata N, Sato T, Nakamura S and
Toru T. Chem. Commun. 2008; 7: 1977–1979.
9. Yoshiyama H, Shibata N, Sato T, Nakamura S and
Toru T. Org. Biomol. Chem. 2009; 7: 2265–2269.
10. Kobayashi N, Ogata H, Nonaka N and Luk’yanets
EA. Chemistry — A European Journal 2003; 9:
5123–5134.
21. Gurol I, Gumus G and Ahsen V. Journal of Fluorine
Chemistry 2012; 142: 60–66.
22. Selcukoglu M and Hamuryudan E. Dyes and
Pigments 2007; 74: 17–20.
23. Wei S, Huang D, Li L and Meng Q. Dyes and
Pigments 2003; 56: 1–6.
24. Gurol I, Durmus M, Ahsen V and Nyokong T.
Dalton Transactions 2007: 34: 3782–3791.
25. William R and Dolbier JR. Guide to Fluorine NMR
for Organic Chemists, John Wiley: NewYork, 2009.
11. Kobayashi N, Sasaki N, HigashiY and Osa T. Inorg.
Chem. 1995; 34: 1636–1637.
12. Leznoff CC and Lever ABP. Phthalocyanines:
Properties and Applications, VCH: New York, NY,
1989–1996. McKeown NB. Phthalocyanine Mate-
rials: Synthesis, Structure and Function, Cambridge
University Press: Cambridge, 1998.
Copyright © 2013 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2013; 17: 563–563