Synthesis and characterization of novel fluoroether-substituted phthalocyanines

Article abstract of DOI:10.1016/j.jfluchem.2012.06.023

The synthesis of 1H,1H-nonafluoro-3,6-dioxaheptan-1-ol with 4-nitrophthalonitrile and 4,5-dichlorophthalonitrile in the presence of K ₂CO₃ leads to the formation of 4-{2,2-difluoro-2-[1,1,2,2- tetrafluoro-2-(trifluoromethoxy)ethoxy]e

Full text of DOI:10.1016/j.jfluchem.2012.06.023

Journal of Fluorine Chemistry 142 (2012) 60–66
Contents lists available at SciVerse ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
Synthesis and characterization of novel fluoroether-substituted phthalocyanines
a
a
a,b,
˙
*
Ilke Gu¨rol , Gu¨lay Gu¨mu¨s¸ , Vefa Ahsen
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
A R T I C L E I N F O
A B S T R A C T
Article history:
The synthesis of 1H,1H-nonafluoro-3,6-dioxaheptan-1-ol with 4-nitrophthalonitrile and 4,5-
dichlorophthalonitrile in the presence of K2CO3 leads to the formation of 4-{2,2-difluoro-2-[1,
1,2,2-tetrafluoro-2-(trifluoromethoxy)ethoxy]ethoxy}phthalonitrile (1), 4-chloro-5-{2,2-difluoro-2-
[1,1,2,2-tetrafluoro-2-(trifluoromethoxy)ethoxy] ethoxy}-phthalonitrile (2), and 4,5-bis{2,2-difluoro-
2-[1,1,2,2-tetrafluoro-2-(trifluoromethoxy)ethoxy]ethoxy}phthalonitrile (3), respectively. Metal free
phthalocyanines were synthesized by tetramerization of the phthalonitriles in 2-(dimethylami-
no)ethanol while metallophthalocyanines were prepared in the presence of zinc, cobalt or nickel salts.
The new compounds were characterized by elemental analysis, IR, 1H, and 19F NMR and UV–Vis
spectroscopy as well as mass spectrometry. The fluoroether substituted Pcs are best soluble in polar
solvents such as acetone and THF.
Received 30 March 2012
Received in revised form 18 June 2012
Accepted 19 June 2012
Available online 28 June 2012
Keywords:
Phthalocyanine
Fluoroether
19F NMR
19F COSY
Crown Copyright ß 2012 Published by Elsevier B.V. All rights reserved.
1. Introduction
solubility in polar solvents such as acetone or THF. The electronic
properties are widely affected by introducing electron donor or
Phthalocyanines and their metal complexes have found
application in different areas of research, such as photoreceptors
in photographic printing [1], thin film organic transistors [2],
photovoltaic cells [3], liquid crystals [4–6], photodynamic therapy
[7–12], light-emitting diodes [13] and chemical sensors [14–20].
Phthalocyanines are among the most widely used chemically
sensitive coating materials in chemical sensors [21] and suitable
for detecting volatile organic compounds (VOCs) in gas and liquid
phase [22].
The physico-chemical properties of phthalocyanines can be
modified in a wide range through chemical modifications made to
the Pc core structure. For example, the solubility in organic solvents
is increasedby the introduction of bulkyor longchain alkyloralkoxy
groups to the periphery of the macrocycle. Tetra substituted Pcs are
commonly found to exhibit a higher solubility than the octa
substituted ones [23–25]. The formation of constitutional isomers
during synthesis of the tetra substituted phthalocyanines leads to
the higher solubility of these systems [26].
acceptor groups, as well. While unsubstituted phthalocyanines
exhibit p-type behavior MePcF16 shows n-type behavior due to the
electron withdrawing properties of the strongly electronegative
fluorine atoms directly attached to the Pc core [30–34]. Phthalo-
cyanines with electron donating or electron withdrawing sub-
stituents were studied in photovoltaic cells or gas sensors [35–38].
Furthermore, the properties of phthalocyanines are influenced not
only by the nature of the substituents (electron donating or
electron withdrawing) on the phthalocyanine and substitution
pattern (tetra, octa, peripheral, non-peripheral), but also by the
nature of the metal ion complex.
In this paper, we present for the first time the synthesis and
characterization of phthalocyanines substituted with fluoroethers
as electron withdrawing substituents. Aggregation properties of
the phthalocyanine derivatives in different solvents and at
different concentrations in chloroform are also presented.
2. Result and discussion
In the past decade, a new generation of phthalocyanines
with fluorinated, electron withdrawing substituents has been
developed [27–29]. These Pcs are of much interest due to their high
The compound 1 was prepared by nucleophilic substitution of
the nitro group in 4-nitrophthalonitrile with 1H,1H-nonafluoro-3,6-
dioxaheptan-1-ol. The compounds 2 and 3 were both prepared by
the reaction of 1H,1H-nonafluoro-3,6-dioxaheptan-1-ol with 4,5-
dichlorophthalonitrile (Fig. 1). They were separated from the same
reactionmixture, buttheyieldratioofthetwoproductswasfoundto
change with reaction temperature. In case of a reaction temperature
of near 95 8C compound 3 was obtained in higher yields than 2.
* Corresponding author at: Gebze Institute of Technology, Department of
Chemistry, PO Box 141, Gebze, 41400, Turkey.
Tel.: +902626053106; fax: +902626053101.
E-mail address: ahsen@gyte.edu.tr (V. Ahsen).
0022-1139/$ – see front matter. Crown Copyright ß 2012 Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jfluchem.2012.06.023

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I. Gu¨rol et al. / Journal of Fluorine Chemistry 142 (2012) 60–66
61
Fig. 1. Synthesis routes of substituted phthalocyanine derivatives.
Fig. 2. 19F COSY spectrum of compound 3.

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62
All the phthalocyanines were obtained by the cyclotetramer-
absence of the inner –NH band (3300 cmÀ1) (characteristic for
H2Pc) confirms the metallic Pc structure.
ization of a phthalonitrile and synthesized according to reported
methods [39–46]. The synthesis of both the octa and tetra
substituted metal phthalocyanines (1a–3a, 1b–3b, 1d–3d) was
achieved in anhydrous amyl alcohol using 1,8-diazabicy-
In the 1H NMR spectrum of 1 the aromatic protons appeared at
d
8.08 (d), 7.85 (d) and 7.66 (dd). The CH2 protons of the substituent
group were observed at 5.06 ppm as a triplet due to the effect of the
fluorine atoms. The spectra of 2 and 3 were observed as expected in
accordance with the proposed structure. The tetrasubstituted
phthalocyanines were obtained as a mixture of the four possible
structural isomers. For this reason, the 1H NMR spectra of 1a and 2a
have broad bands [48,49].
The coupling between hydrogen–fluorine and fluorine–fluorine
atoms make the interpretation of the 19F NMR spectra difficult. For
this reason, the 19F NMR peaks of compound 3 are assigned based
on a 19F COSY experiment (Fig. 2). The signals along the diagonal
reflect the normal 19F spectrum. The cross peaks provide the
necessary information for peak assignment. In general, each cross
peak represents a correlation due to either three or four bond F–F
coupling. The observed cross peaks indicate the following
correlations: CF3 with O–CF2 and CF2–O with O–CF2CH2. In the
19F COSY spectrum of compound 3 no 3JFF correlation was observed
[50].
clo[5.4.0]undec-7-ene (DBU) as
a base in the presence of
anhydrous zinc(II) acetate, cobalt(II) chloride or nickel(II) chloride,
respectively, at 140 8C under an argon atmosphere (Fig. 1). The
metal free phthalocyanines 1c, 2c and 3c were obtained directly by
refluxing 1, 2 or 3 in 2-(dimethyl-amino)ethanol. The new
intermediate products and phthalocyanines were characterized
by 1H NMR, 19F NMR, FT-IR, and UV–vis spectrometry, elemental
analysis, and MS. The spectroscopic data for the newly synthesized
compounds were consistent with the assigned formulation. The
results are given in the Section 4.
Purification of all the studied phthalocyanines was done by
column chromatography over silica gel using THF or acetone as
eluents.
We have observed that the solubility of the perfluoroethoxy
phthalocyanines is affected by both the central metal ion and the
number of substituents. While 1a and 1b are soluble in non-
polar organic solvents (e.g. chloroform), 2a, 3a, 2b and 3b show
high solubility only in polar organic solvents such as THF,
acetone, and DMSO. 1c–3c and 1d–3d are not soluble in
chloroform, THF, acetone, and DMSO. Generally, fluoroalkyl
substituted compounds are known to have high solubility in
polar solvents [47].
The spectra of the compounds 1, 2 and
3 showed the
characteristic peaks of the nine fluorine atoms of the substituent
groups. The peaks assigned to the CF3, CF2CH2, CF3–O–CF2–CF2–O,
CF3–O–CF2 fragment were observed at
d
À56.21, À78.08, À89.21,
and À91.59 ppm (Fig. 3), respectively. The CF3 signals appeared as
a triplet due to 4JFF coupling of the fluorine atoms (4JFF = 9 Hz). The
CF2–CH2 signals are split as a multiplet due to 4JFF and 3JHF coupling
(9 Hz and 13 Hz, respectively). Area integration of the four
observed peaks yielded the expected 3:2:2:2 ratio. 19F NMR
spectra of the phthalocyanines feature the same characteristic
chemical shifts as for compound 3.
The IR spectra of the compounds 1, 2, and 3 clearly indicate the
presence of CBB N groups by the intense stretching bands around
2235 cmÀ1. The characteristic C–F bands of 1, 2 and 3 appeared at
1180 cmÀ1
.
Generally, while the phthalocyanines are prepared by cyclote-
tramerization of substituted phthalonitriles, generally the imide
occurred and observed as the characteristic band at around
1700 cmÀ1 in IR absorptions. The absence of this band is attributed
to the purity of the phthalocyanine which supports the informa-
tion observed from the thin layer chromatography (TLC). The
In addition to these positive results supporting the expected
chemical structures the mass spectra of compounds 1, 2 and 3 gave
the characteristic molecular ion peaks at m/z 408 [M]+, 442 [M]+,
688 [M]+ respectively, as a second confirmation. Concerning the
phthalocyanines intense singly charged molecular ions peaks were
Fig. 3. 19F NMR spectrum of compound 3.

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63
Fig. 4. Positive ion MALDI-MS spectrum of 1c obtained in DHB matrix.
Fig. 5. UV–vis spectra of 1a in CHCl3 at different concentrations: 1 Â 10À4, 5 Â 10À5
,
Fig. 6. UV–vis spectra of 1a in different solvents: acetone (-), THF (–), chloroform
(. . .).
1 Â 10À5, 5 Â 10À6, 1 Â 10À6 M.
observed in all cases in the MALDI-TOF spectra with 2,5-dihydroxy
benzoic acid (DHB) as matrix. The positive ion MALDI-MS
spectrum of 1c is given in Fig. 4.
(659 nm) due to the difference of substitution pattern. The Q band
positions of the perfluoroethoxy substituted MPcs result from the
electron withdrawing effect of the fluorine atoms in the
substituents. The Q bands of other compounds were comparable
to those of the compounds 1b and 3b.
In order to investigate the photophysical properties of the
synthesized compounds, UV–vis absorption spectra were
recorded. The phthalocyanines exhibit typical spectra with two
strong absorption regions. One of them is the so-called Soret Band
(B Band) in the UV region at around 300–350 nm and the other is
the Q band in the visible region at 600–700 nm. The UV–vis spectra
of the phthalocyanine complexes 1a, 1b, 2a, 2b, 3a, 3b exhibited
characteristic absorptions in the Q-band region at around 671, 659,
670, 658, 667, 655 nm in THF, respectively. The absorption
maximum is blue-shifted about 12 nm (e.g. from 671 nm for 1a
to 659 nm for 1b in THF) and absorption coefficient becomes lower
(from 4.90 for 1a to 4.65 for 1b) as the result of the change in the
central metal ion. Their Q band wavelengths were attributed to the
Furthermore, the aggregation behavior of 1a was investigated
at different concentrations in chloroform (Fig. 5). The intensity of
the Q band absorption increased in parallel with increasing
concentration. The Lambert–Beer law was obeyed for compound
1a for concentrations ranging from 1 Â 10À4 to 1 Â 10À6 M.
In addition, the visible absorption spectra illustrating the
aggregation behavior of phthalocyanines in various solvents are
shown in Fig. 6. In THF an intense absorption band at 670 nm and a
shoulder around 605 nm are observed. The low-energy band has
been attributed to unaggregated phthalocyanine and the high-
energy shoulder to aggregated species [1,36]. On the contrary to
the results in THF and acetone, in apolar solvents such as
chloroform the high energy band around 674 nm was not observed
in the spectra, which has been assigned to the non aggregated
p–
p* transition from the HOMO to the LUMO of the Pc2À ring. The Q
band of the octa substituted Pc (3b) (655 nm) is shifted to lower
wavelengths compared with that of the tetra substituted Pc (1b)

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64
phthalocyanine species as encountered in a number of soluble
phthalocyanines [51,52].
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.
3. Conclusion
Yield: 1.9 g (66%), m.p. 55–57 8C. FT-IR (cmÀ1): 3096, 2235
(CBB N), 1603, 1568, 1495, 1458, 1435, 1276, 1254, 1179 (CF), 1140,
In this paper, we have prepared and characterized Zn(II), Ni(II),
Co(II) and 2H phthalocyanine complexes substituted with 1H,1H-
nonafluoro-3,6-dioxaheptan-1-ol in tetra and octa positions for the
first time. The presented spectroscopic and analytical results
confirm that all compounds have their proposed structures.
Fluorine atoms in the structure increase the solubility of the
complexes in acetone and THF. We also studied the aggregation
behavior of the new complexes 1a, 1b, 2a, 2b, 3a, and 3b in
different solvents and also of 1a at different concentrations in
chloroform. The substituted complexes showed similar typical
aggregation behavior. However, tetra and octa fluoroxy substitu-
tion of phthalocyanines have proved to be an extremely efficient
way to diminish aggregation among the planar molecules. The Q-
band positions of the fluoroxy substituted MPcs result from the
balance of some factors, such as the electron-withdrawing effect of
the fluorine atoms in the substituents and the number (4 or 8) of
the substituents on the Pc ring.
1078 (CO), 964. 1H NMR (Acetone d6):
d
, ppm 8.08 (1H, d, ArH), 7.85
(1H, d, ArH), 7.66 (1H, dd, ArH), 5.06 (2H, t, CH2). 19F NMR (acetone
4
5
d6):
d
, ppm À56.10 (t, CF3, JFF = 9 Hz, JFF = 1.8 Hz), À78.82 (m,
4
3
4
CF2–CH2, JFF = 9 Hz, JHF = 13 Hz), À89.12 (m, CF2–O, JFF = 9 Hz),
À91.52 (q, 2F, O–CF2, 4JFF = 9 Hz). Calc. for C13H5F9N2O3 (408.17): C
38.25; H 1.23; N 6.86; Found: C 37.53; H 1.18; N 6.69. MS (EI): m/z
(%): 408 [M]+.
4.2.2. 4-Chloro-5-{2,2-difluoro-2-[1,1,2,2-tetrafluoro-2-
(trifluoromethoxy)ethoxy] ethoxy}phthalonitrile (2)
1H,1H-nonafluoro-3,6-dioxaheptan-1-ol (1.0 g, 3.6 mmol) was
dissolved in absolute DMF (5 mL) under argon and 4,5-dichlor-
ophthalonitrile (0.71 g, 3.6 mmol) was added. After stirring for
10 min finely ground anhydrous potassium carbonate (2.94 g,
21.0 mmol) was added in portions during 2 h with efficient
stirring. The reaction mixture was stirred under argon atmosphere
at 70 8C for 72 h. The solvent was evaporated under reduced
pressure. Water (5 mL) was added and the aqueous phase was
extracted with dichloromethane (3 Â 10 cm3). 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 procedure. The
product was purified by column chromatography on silica gel
using n-hexan/dichloromethane (1:1) as the eluent. The product is
soluble in CH2Cl2, CHCl3, acetone, MeOH and DMSO.
The sensor properties of these new compounds will be the
subject of our future study.
4. Experimental
4.1. Characterization methods and chemicals
Elemental analyses were obtained using a Thermo Finnigan
Flash 1112 instrument. Infrared spectra were recorded on a Perkin
Elmer FT-IR System Spectrum BX. 1H and 19F NMR spectra were
recorded in THF-d8 solution on Bruker and Varian 500 MHz
spectrometers. Absorption spectra in the UV–visible region were
recorded with a Shimadzu 2001 UV spectrophotometer. The mass
spectra were acquired with a Bruker Daltonics MicrOTOF mass
spectrometer equipped with an electro spray ionization (ESI)
source. The instrument was operated in positive ion mode using a
m/z range of 50–3000. The capillary voltage of the ion source was
set at 6000 V and the capillary exit at 190 V. The nebulizer gas flow
1 bar and drying gas flow 8 mL minÀ1. Positive ion and linear mode
MALDI-TOF MS spectra of the compounds were obtained in 2,5-
dihydroxy benzoic acid as matrix using nitrogen laser accumulat-
ing 50 laser shots.
Yield: 0.83 g (52%), m.p. 41–43 8C. FT-IR (cmÀ1): 3048,
2235(CN), 1584, 1498, 1448, 1392, 1272, 1182 (CF), 1064
(CO), 969. 1H NMR (acetone d6):
d
, ppm 8.06 (1H, s, ArH), 7.84
(1H, s, ArH), 4.94 (1H, t, ArH). 19F NMR (acetone d6):
d
, ppm
4
5
À56.11 (t, CF3, JFF = 9 Hz, JFF = 1.5 Hz), À77.85 (m, CF2–CH2,
3
4
4JFF = 9 Hz, JHF = 13 Hz) À89.17 (m, CF2–O, JFF = 13 Hz), À91.54
4
(q, 2F, O–CF2, JFF = 9 Hz). Calc. for C13H4ClF9N2O3 (442.62): C
35.28; H 0.91; N 6.33; Found: C 35.12; H 0.87; N 6.14. MS (EI):
m/z (%): 442 [M]+.
4.2.3. 4,5-Bis{2,2-difluoro-2-[1,1,2,2-tetrafluoro-2-
(trifluoromethoxy)ethoxy]ethoxy} phthalonitrile (3)
1H,1H-nonafluoro-3,6-dioxaheptan-1-ol (4.0 g, 14.2 mmol)
was dissolved in absolute DMF (5 mL) under argon and 4,5-
dichlorophthalonitrile (1.3 g, 7.1 mmol) was added. After stirring
for 10 min, finely ground anhydrous potassium carbonate (3.70 g,
27.0 mmol) was added in portions during 2 h with efficient
stirring. The reaction mixture was stirred under argon atmosphere
at 95 8C for 72 h. The solvent was evaporated under reduced
pressure. Water (5 mL) was added and the aqueous phase was
extracted with dichloromethane (3 mL Â 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
product was purified by column chromatography on silica gel
using n-hexan/dichloromethane (1:1) as the eluent. The product
was soluble in CH2Cl2, CHCl3, acetone, MeOH, and DMSO.
Yield: 1.30 g (27%), m.p. 69–70 8C. FT-IR (cmÀ1): 3048,
2235(CN), 1588, 1499, 1452, 1390, 1272, 1215, 1182 (CF), 1137,
n-amyl alcohol and dimethylformamide (DMF) were dried
according to literature procedures [53]. NiCl2, Zn(CH3COO)2, CoCl2,
K2CO3, Na2CO3, anhydrous Na2SO4, THF-d8, acetone-d6 and 1H,1H-
nonafluoro-3,6-dioxaheptan-1-ol were purchased from commer-
cial suppliers. 4-nitrophthalonitrile [54], 4,5-dichlorophthaloni-
trile [55] were synthesized and purified according to the literature
procedures.
4.2. Synthesis
4.2.1. 4-{2,2-Difluoro-2-[1,1,2,2-tetrafluoro-2-
(trifluoromethoxy)ethoxy]ethoxy} phthalonitrile (1)
1H,1H-nonafluoro-3,6-dioxaheptan-1-ol (2.0 g, 7.1 mmol) was
dissolved in absolute DMF (5 mL) under argon and 4-nitrophtha-
lonitrile (1.2 g, 7.1 mmol) was added. After stirring for 10 min,
finely ground anhydrous potassium carbonate (1.77 g, 13.0 mmol)
was added in portions during 2 h with efficient stirring. The
reaction mixture was stirred under argon atmosphere at 60 8C for
72 h. The solvent was evaporated under reduced pressure. Water
(5 mL) was added and the aqueous phase was extracted with
dichloromethane (3 mL Â 10 mL). The combined extracts were
treated first with sodium carbonate solution (5%), then with water
1096 (CO), 972. 1H NMR (acetone d6):
d, ppm 7.90 (2H, s, ArH), 5.04
(4H, t, CH2). 19F NMR (acetone d6):
d
, ppm À56.21 (t, CF3,
4
3
4JFF = 9 Hz), À78.08 (m, CF2–CH2, JFF = 9 Hz, JHF = 13 Hz), À89.21
(m, CF2–O, 4JFF = 13 Hz), À91.59 (q, 2F, O–CF2, 4JFF = 9 Hz). Calc. for
C18H6F18N2O6 (688.23): C 31.41; H 0.88; N 4.07; Found: C 31.33; H
0.89; N 4.01. MS (MS-EI): m/z (%): 688 [M]+.

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65
4.2.4. Compound 1a
4.2.9. Compound 2b
Compound 1 (0.5 g, 1.22 mmol) and anhydrous Zn(CH3COO)2
(0.056 g, 0.31 mmol), and 0.2 mL DBU in 5 mL n-amyl alcohol were
heated to 140 8C for 7 h under an argon atmosphere in a round-
bottomed flask. The resulting green crude product was cooled and
filtered. The crude product was purified by passing through a silica
gel column using acetone and THF as eluents.
Compound 2b was prepared according to the procedure
described for 2a. The amounts of reagents employed were as
follows: 2 (0.3 g, 0.68 mmol) and anhydrous cobalt(II) chloride
(0.022 g, 0.17 mmol) in 2 mL ethylene glycol.
Yield: 120 mg (38%), m.p. > 200 8C. FT-IR (cmÀ1): 2933, 1608,
1526, 1446, 1405, 1218, 1177(CF), 1137, 1072 (CO), 962. 19F NMR
4
Yield: 250 mg (48%), m.p. > 200 8C. FT-IR (cmÀ1): 2960, 1609,
1488, 1396, 1339, 1221, 1178(CF), 1100(CO), 968. 1H NMR (THF
(THF d8):
d
, ppm À54.25 (t, 12F, CF3, JFF = 9 Hz), À75.21 (m, 8F,
4
3
CF2–CH2, JFF = 9 Hz, JHF = 13 Hz), À86.77 (m, 8F, CF2–O,
4
d8):
d
, ppm 8.79 (4H, b, ArH), 8.44 (4H, b, ArH), 7.65 (4H, b, ArH),
4JFF = 9 Hz), À89.23 (m, 8F, O–CF2, JFF = 9 Hz). Calc. for C52H16
5.08 (8H, t, CH2). 19F NMR (THF d8):
d
, ppm À54.33 (p, 12F, CF3,
Cl4F36N8O12Co (1829.45): C 34.14; H 0.88; N 6.13; Found: C 34.13;
4JFF = 9 Hz), À75.80 (m, 8F, CF2–CH2, JFF = 9 Hz, JHF = 13 Hz),
H 0.80; N 6.09. UV–vis (THF): lmax/nm (log e): 336 (4.63), 658
4
3
4
À87.05 (m, 8F, CF2–O, JFF = 9 Hz), À89.50 (m, 8F, O–CF2,
(4.75). MS (MS-MALDI): m/z (%): 1829 [M]+.
4JFF = 9 Hz). Calc. for C52H20F36N8O12Zn (1698.09): C 36.78; H
1.19; N 6.60; Found: C 36.75; H 1.13; N 6.60. UV–vis (THF): lmax
/
4.2.10. Compound 2c
nm (log
[M]+.
e
): 349 (4.55), 671 (4.90). MS (MS-MALDI): m/z (%): 1698
Compound 2c was prepared according to the procedure
described for 2a. The amounts of reagents employed were as
follows: 2 (0.25 g, 0.56 mmol) in 1 mL 2-(dimethyl-amino)ethanol.
Yield: 14 mg (6%), m.p. > 200 8C. FT-IR (cmÀ1): 3048, 2936,
1610, 1447, 1392, 1221, 1180 (CF), 1100 (CO), 1020, 970. Calc. for
4.2.5. Compound 1b
Compound 1b was prepared according to the procedure
described for 1a. The amounts of reagents employed were as
follows: 1 (0.5 g, 1.22 mmol) and anhydrous cobalt(II) chloride
(0.04 g, 0.31 mmol) in 3 mL ethylene glycol.
C
52H18Cl4F36N8O12 (1772.51): C 35.24; H 1.02; N 6.32; Found: C
29.28; H 1.50; N 5.11. MS (MS-MALDI): m/z (%): 1772 [M]+.
Yield: 130 mg (25%), m.p. 194 8C. FT-IR (cmÀ1): 2949, 1612,
4.2.11. Compound 2d
1480, 1410, 1222, 1178 (CF), 1100 (CO), 968. 19F NMR (THF d8):
d
,
Compound 2d was prepared according to the procedure
described for 2a. The amounts of reagents employed were as
follows: 2 (0.4 g, 0.9 mmol), anhydrous nickel(II) chloride (0.029 g,
0.22 mmol) and 0.2 mL DBU in 4 mL n-amyl alcohol.
Yield: 60 mg (15%), m.p. > 200 8C. FT-IR (cmÀ1): 3047, 2947,
1608, 1447, 1392, 1221, 1180(CF), 1100 (CO), 1020, 970. Calc. for
4
ppm À54.44 (p, 12F, CF3, JFF = 9 Hz), À75.93 (m, 8F, CF2–CH2,
4JFF = 9 Hz, 3JHF = 13 Hz), À87.30 (m, 8F, CF2–O, 4JFF = 9 Hz), À89.73
(m, 8F, O–CF2, 4JFF = 9 Hz). Calc. for C52H20F36N8O12Co (1691.94): C
36.92; H 1.19; N 6.62; Found: C 36.86; H 1.18; N 6.60. UV–vis
(THF): lmax/nm (log e): 330 (4.49), 659 (4.65). MS (MS-MALDI): m/
z (%): 1691 [M]+.
C52H16Cl4F36N8O12Ni (1829.18): C 34.14; H 0.88; N 6.13; Found: C
34.12; H 0.84; N 5.98. MS (MS-MALDI): m/z (%): 1829 [M]+.
4.2.6. Compound 1c
Compound 1c was prepared according to the procedure
described for 1a. The amounts of reagents employed and
conditions were as follows: 1 (0.5 g, 1.22 mmol) in 1 mL dry 2-
(dimethyl-amino)ethanol at 175 8C.
4.2.12. Compound 3a
Compound 3a was prepared according to the procedure
described for 2a. The amounts of reagents employed were as
follows: 3 (0.4 g, 0.58 mmol), anhydrous zinc(II) acetate (0.027 g,
0.15 mmol) and 0.2 mL DBU in 5 mL n-amylalcohol.
Yield: 130 mg (31%), m.p. > 200 8C. FT-IR (cmÀ1): 2963, 1612,
1493, 1454, 1341, 1224, 1178 (CF), 1070 (CO), 962. 1H NMR (THF
Yield: 160 mg (32%), m.p. > 200 8C. FT-IR (cmÀ1): 3046, 2963,
1615, 1483, 1222, 1180 (CF), 1100 (CO), 969. Calc. for
C
52H22F36N8O12 (1634.72): C 38.21; H 1.36; N 6.85; Found: C
37.52; H 1.28; N 6.22. MS (MS-MALDI): m/z (%): 1634 [M]+.
d8):
d
, ppm 9.12 (8H, s, ArH), 5.44 (16H, s, CH2). 19F NMR (THF d8):
d
,
4
ppm À54.56 (m, 24F, CF3, JFF = 9 Hz), À76.91 (m, 16F, CF2–CH2),
À87.30 (m, 16F, CF2–O), À89.73 (m, 16F, O–CF2). Calc. for
C72H24F72N8O24Zn (2818.33): C 30.68; H 0.86; N 3.98; Found: C
4.2.7. Compound 1d
Compound 1d was prepared according to the procedure
described for 1a. The amounts of reagents employed were as
30.62; H 0.85; N 3.97. UV–vis (THF): lmax/nm (log e): 355 (4.24),
follows:
1
(0.3 g, 0.73 mmol), anhydrous nickel(II) chloride
667 (5.05). MS (MS-MALDI): m/z (%): 2818 [M]+.
(0.024 g, 0.18 mmol), and 0.2 mL DBU in 4 mL n-amyl alcohol.
Yield: 95 mg (31%), m.p. > 200 8C. FT-IR (cmÀ1): 2935, 1611,
1470, 1224, 1175 (CF), 1109 (CO), 967. Calc. for C52H20F36N8O12Ni
(1691.40): C 36.92; H 1.19; N 6.62; Found: C 36.73; H 1.16; N 6.58.
MS (MS-MALDI): m/z (%): 1691 [M]+.
4.2.13. Compound 3b
Compound 3b was prepared according to the procedure
described for 3a. The amounts of reagents employed were as
follows: 3 (0.4 g, 0.58 mmol) and anhydrous cobalt(II) chloride
(0.019 g, 0.15 mmol) in 3 mL ethylene glycol.
4.2.8. Compound 2a
Yield: 55 mg (14%), m.p. > 200 8C. FT-IR (cmÀ1): 2932, 1609,
Compound 2a was prepared according to the procedure
described for 1a. The amounts of reagents employed were as
follows: 2 (0.5 g, 1.13 mmol), anhydrous zinc(II) acetate (0.055 g,
0.27 mmol), and 0.2 mL DBU in 5 mL n-amylalcohol.
Yield: 210 mg (42%), m.p. > 200 8C. FT-IR (cmÀ1): 2952, 1607,
1487, 1440, 1391, 1220, 1178 (CF), 1138, 1068 (CO), 968. 1H NMR
1472, 1430, 1224, 1180 (CF), 1100 (CO), 962. 19F NMR (THF d8):
d
,
4
ppm À56.32 (m, 24F, CF3, JFF = 9 Hz), À78.48 (m, 16F, CF2–CH2),
À89.07 (m, 16F, CF2–O), À91.35 (m, 16F, O–CF2). Calc. for
C72H24F72N8O24Co (2811.88): C 30.75; H 0.86; N 3.99; Found: C
30.39; H 0.80; N 3.95. UV–vis (THF): lmax/nm (log e): 335 (4.62),
655 (4.76). MS (MS-MALDI): m/z (%): 2811 [M]+.
(THF d8):
d, ppm 8.96 (4H, s, ArH), 8.54 (4H, s, ArH), 5.40 (8H, s,
4
CH2). 19F NMR (THF d8):
d
, ppm À54.40 (m, 12F, CF3, JFF = 9 Hz),
4.2.14. Compound 3c
4
3
À76.16 (m, 8F, CF2–CH2, JFF = 9 Hz, JHF = 13 Hz), À87.35 (m, 8F,
Compound 3c was prepared according to the procedure
described for 3a. The amounts of reagents employed were as
follows: 3 (0.25 g, 0.36 mmol) in 1 mL 2-(dimethyl-amino)ethanol.
Yield: 30 mg (12%), m.p. > 200 8C. FT-IR (cmÀ1): 3048, 2956,
1612, 1499, 1451, 1225, 1180 (CF), 1136, 1096 (CO), 972. Calc. for
4
4
CF2–O, JFF = 9 Hz), À89.51 (m, 8F, O–CF2, JFF = 9 Hz). Calc. for
C52H16Cl4F36N8O12Zn (1835.91): C 34.02; H 0.88; N 6.10; Found: C
34.05; H 0.86; N 6.03. UV–vis (THF):
lmax/nm (log e): 354 (4.67),
670 (5.04). MS (MS-MALDI): m/z (%): 1835 [M]+.

˙
I. Gu¨rol et al. / Journal of Fluorine Chemistry 142 (2012) 60–66
66
¨
¨
[22] (a) Z.Z. Oztu¨ rk, R. Zhou, V. Ahsen, O. Bekarog˘lu, W. Go¨pel, Sensors and Actuators B
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C72H26F72N8O24 (2754.90): C 31.39; H 0.95; N 4.07; Found: C
31.28; H 0.97; N 3.98. MS (MS-MALDI): m/z (%): 2754 [M]+.
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Compound 3d was prepared according to the procedure
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3 (0.4 g, 0.58 mmol), anhydrous nickel(II) chloride
(0.019 g, 0.15 mmol), and 0.2 mL DBU in 4 mL n-amyl alcohol.
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