Highly symmetrical polyfluorinated porphyrazines

Article abstract of DOI:10.1016/j.jfluchem.2013.02.012

By cyclotetramerization of 2,3-bis[2-fluoro-5-(trifluoromethyl)benzylthio] maleonitrile in the presence of magnesium butanolate, magnesium porphyrazinate carrying eight (2-fluoro-5-(trifluoromethyl)benzylthio) functional groups on the periphery positions

Full text of DOI:10.1016/j.jfluchem.2013.02.012

Journal of Fluorine Chemistry 149 (2013) 65–71
Contents lists available at SciVerse ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
Highly symmetrical polyfluorinated porphyrazines
1
,
Erg u¨ n Gonca *
Fatih University, Department of Chemistry, TR 34500 B u¨ y u¨ k c¸ ekmece, I˙stanbul, Turkey
A R T I C L E I N F O
A B S T R A C T
Article history:
By cyclotetramerization of 2,3-bis[2-fluoro-5-(trifluoromethyl)benzylthio] maleonitrile in the presence
of magnesium butanolate, magnesium porphyrazinate carrying eight (2-fluoro-5-(trifluoromethyl)-
benzylthio) functional groups on the periphery positions has been synthesized. Conversion of the
magnesium porphyrazinate into the metal-free derivative was achieved by treatment with
trifluoroacetic acid. Further reaction of this product with different metal (II) acetates have led to the
metallo porphyrazines. Then, chloro-octakis [2-fluoro-5-(trifluoromethyl)benzylthio] porphyrazinato
iron (III) (FePzCl) was prepared by the reaction of metal-free porphyrazine with iron (II) acetate and
Received 16 November 2012
Received in revised form 13 February 2013
Accepted 13 February 2013
Available online 19 February 2013
Keywords:
2
-Fluoro-5-(trifluoromethyl)benzyl
further treatment with HCl solution. The monomeric bisaxial complex FePz(py)
complex [FePz(pyz)] were formed as stable complexes by reacting FePzCl with pyridine or pyrazine,
respectively. These novel complexes were characterized by elemental analysis, together with FT-IR,
2
as well as the bridged
bromide
Pyridine
n
1
H
Pyrazine
13
19
Shish kebab type olygomer
Bisaxial complex
NMR, C NMR, F NMR, UV–vis and mass spectral data.
ß 2013 Elsevier B.V. All rights reserved.
1
9
F NMR spectroscopy
1
. Introduction
phthalocyanines. The porphyrazines also often display a vastly
increased solubility in organic solvents compared with their
phthalocyanine counterparts. Thus, porphyrazines maintain a
unique position in the family of tetrapyrrolic macrocycles, and
their straightforward synthesis, coupled with their tuneable
electronic and optical properties, renders them exciting candidates
for a whole range of applications [9–14].
Tetraazaporphyrins, or porphyrazines as they are more
commonly known, are part of a family of aromatic, tetrapyrrolic
ring systems that can be divided into two distinct categories,
namely porphyrins and tetraazaporphyrins, in which meso
nitrogen atoms replace the methine groups. The latter can be
further divided into porphyrazines (Pz), and phthalocyanines (Pc),
which contain benzenoid rings fused to the macrocyclic periphery.
Due to their unique electronic and optical properties, potential
applications of tetraazaporphyrins include biomedical agents,
chemical sensors, liquid crystals, non-linear optics, Langmuir–
Blodgett films, and ladder polymers, to name but a few [1–8].
In recent years, porphyrazines that bear a range of carbon and
heteroatomic substituents fused directly to the macrocyclic
periphery have gained increasing attention. This is due to the
strong correlation between the nature of the substituent, and the
electronic and optical properties of the macrocyclic ring system,
coupled with the relative ease of their synthetic preparation. In
comparison to the other family members, analogous derivatives
are virtually inaccessible for the porphyrins, and direct fusion of
The addition of fluorine atoms to biologically active compounds
modulates their physical–chemical and pharmacological proper-
ties [15]. These conversions allow their use in many therapeutic
studies, including treatment of bacterial and fungal infections,
cancer, cardiovascular and central nervous system diseases
[16,17]. Many porphyrinoids having peripheral fluorine atoms
and groups show potential for photodynamic therapy due to their
enhanced stability, high level of singlet oxygen production,
lipophilicity, and selective accumulation in tumor cells [18–21].
However, it has been demonstrated that porphyrins with fluorine
1
9
atoms can be applied in in vivo imaging using F NMR [19,22].
Recently, we synthesized and characterized some fluorinated
tetrapyrroles, such as porphyrazines and phthalocyanines, which
display potential applications in biology and medicine [23–30].
In our previous paper, we have reported the synthesis,
structural and spectral properties of symmetric metallo-porphyr-
azines [23]. In this study, our aim has been to design new
molecules with polyfluoro-substituents, enhancing their solubility
in common organic solvents. We report the synthesis, and
characterization of new readily soluble metallo-porphyrazines
with up to 32 fluorine-containing substituents on the periphery for
the first time, and we also report on the effects of the substituents
heteroatomic substituents onto the porphyrazine
results in a pronounced effect compared with the substitution
of an equivalent group onto the benzenoid rings of the
b-positions
*
Tel.: +90 212 8663300/2066; fax: +90 212 866 34 02.
E-mail address: egonca@fatih.edu.tr
Tel.: +90 212 8662066.
1
0022-1139/$ – see front matter ß 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jfluchem.2013.02.012

6
6
E. Gonca / Journal of Fluorine Chemistry 149 (2013) 65–71
F3C
F3C
NC
NC
S
S
CN
CN
SNa
SNa
Br
F
F
(i)
(ii)
+
F3C
F
(
iii)
(iv)
3
4
5 - 7
H; (iv) EtOH and Co(OAc)
Scheme 1. (i) MeOH; (ii) Mg turnings, I
2
, n-BuOH; (iii) CF
3
CO
2
2 2 2
, Cu(OAc) , or Zn(OAc) .
on the spectroscopic properties of the porphyrazine complexes in
different solvents. In addition, we report novel soluble iron
porphyrazine derivatives with eight 2-fluoro-5-(trifluoromethyl)-
benzylthio substituents appending to the periphery positions.
Chloro {octakis [2-fluoro-5-(trifluoromethyl)benzylthio] porphyr-
azinato} iron (III) (8) was prepared by the reaction of metal-free
porphyrazine with iron (II) acetate and further treatment with HCl
been obtained from 2,3-dinitrile derivative (1) with desired
substituents. Alkylation of 1 with 2-fluoro-5-(trifluoromethyl)-
benzyl bromide in MeOH gave 2,3-bis[2-fluoro-5-(trifluoro-
methyl)benzylthio]maleonitrile (2) which was in cis-form and
3 2 2
easily soluble in CHCl , CH Cl , and acetone. The orange colored
product, 2, was obtained in 84% yield (Scheme 1). Cyclic
tetramerization of 2 can be performed by several ways. However,
the yield of the reaction is strongly dependent on the substituents
on the benzene rings and the central metal atom. The presence of
bulky electron-donating S-groups is expected to enhance the
chemical stability and optical properties of porphyrazines [31].
solution. The monomeric bisaxial complex [FePz(py)
2
] (9) as well
as the bridged complex [FePz(pyz)] (10) were formed as stable
n
complexes by reacting 8 with pyridine or pyrazine, respectively. By
using different spectroscopic methods such as elemental analysis,
1
13
19
FT-IR, H NMR, C NMR, F NMR, UV–vis and mass spectrometry,
novel compounds have been characterized.
Cyclotetramerization of 2 into octakis(2-fluoro-5-(trifluoro-
methyl)benzylthio) porphyrazinato magnesium (3) was realized
by making use of the template effect of magnesium ions. The
optimum condition was to accomplish the reaction in n-BuOH at
reflux temperature for 12 h (Scheme 1) [32–34]. 3 was very soluble
in most of the common solvents except MeOH and EtOH (Fig. 1).
The conversion of 3 into to the metal-free porphyrazine (4) was
2
. Results and discussion
The synthesis of the novel compounds (2-10) is shown in
Schemes 1 and 2. Peripherally substituted porphyrazines have
3
F C
F3C
CF
3
CF3
F
F
F
F
3
F C
CF
3
3
F C
CF
3
S
S
S
S
N
N
S
S
S
S
S
S
S
S
F
F
N
N
N
N
F
F
NH
N
N
i
N
M
N
Cl
N
Fe
N
N
F
F
F
F
N
H
N
3
F C
S
S
F
CF3
3
F C
S
S
CF
3
F
F
F
F
3
C
CF3
F
3
C
CF3
H Pz (4)
2
FePzCl (8)
ii
iii
[
FePz(py) ] (9)
[FePz(pyz)] (10)
2
n
2
Scheme 2. Synthesis route to new compounds: (i) Fe(OAc) , HOAc, HCl; (ii) pyridine; (iii) pyrazine.

E. Gonca / Journal of Fluorine Chemistry 149 (2013) 65–71
67
F C
3
CF3
F
F
N
F C
CF3
F C
3
3
CF3
F
F
S
S
F C
CF3
3
N
S
S
N
S
S
S
S
S
S
F
F
F
F
N
N
N
N
HN
N
N
N
Fe
N
N
M
N
F
F
NH
S
S
F
F
N
F C
3
S
S
F
CF3
F
N
F C
CF3
3
F C
3
N
S
F
S
CF3
F
F C
CF3
3
Fig. 2. Bis(pyridine){octakis [2-fluoro-5-(trifluoromethyl)benzylthio]porphyrazinato}
iron (II) [FePz(py) ] (9).
2
M = Mg (3); 2H (4); Co (5); Cu (6); Zn (7).
6
4
v
82 nm as a single intense absorption) [38,39] to C symmetry,
Fig. 1. Octakis [2-fluoro-5-(trifluoromethyl)benzylthio] substituted porphyrazines
3-7).
resulting in an intense band at 588 nm together with two others at
44 and 680 nm [37]. This Q band absorption was appearing as
(
5
two peaks at 622 and 678 nm in the case of metal-free
porphyrazine with D2h symmetry [38,39].
3 2
achieved by the treatment with CF CO H. The spectroscopic data
have clearly indicated the change of the structure from 3 to 4.
Further reaction of 4 with cobalt (II) acetate, copper (II) acetate,
and zinc (II) acetate has led to the metallo porphyrazines (M = Co,
Cu, Zn) (5-7) (Fig. 1).
It is not factual to reduce 8 to the divalent state in non-donating
solvents, but the behavior of
8 with pyridine at ambient
temperature results in the octahedrally coordinated FePz(py)
2
complex (9) (Fig. 2) [35]. Its formation may be efficiently followed
by the differences in the color of the solution and also approved by
the electronic spectrum, which encloses a single and intense Q
band absorption at 592 nm, typical of D4h symmetry.
Iron insertion into 4 was carried out in acetic acid using
anhydrous iron (II) acetate as the metal salt (Scheme 2) [35,36].
Although the reaction was carried out under inert atmosphere,
trace amounts of oxygen led to Fe (III) derivatives. Further
exposure to air was almost inevitable during the work-up
procedures, so the product was treated with dilute HCl solution
in order to convert all of the trivalent iron products into FePzCl.
Tetrapyrroles having transition metal ion, e.g. iron (II), in the
centre are of important property while they form ‘‘shish kebab’’
type axially coordinated bridged complexes with bidentate
coordinating ligands. 8 can be easily reduced to axially coordinated
9 in the presence of ligands such as pyridine. We have prepared
bridged systems with pyz and an axially coordinated monomer
with pyridine (Scheme 2). While pyridine can react with 8 in
benzene solutions, we accomplish the reaction with pyz only in
melted excess ligand and the product is a bridged system (not
bisaxially coordinated monomer) (Fig. 3).
À1
The band at 1089 cm in the FT-IR spectrum of 8 can be assigned
to the contribution of axial ligands to CN-skeleton vibrations as
encountered in octaphenyltetraazaporphyrins [37]. Another
consequence of the presence of the axial chloride ligand is the
changes occurring in the Q-band absorption from an MPz
derivative of D4h symmetry (e.g. MgPz where Q band is at
F C
3
F C
3
F C
3
CF3
CF3
CF3
F
F
F
F
F
F
F C
F C
3
F C
3
3
CF3
CF3
CF3
S
S
S
S
S
S
N
N
N
S
S
S
S
S
S
F
F
F
NH
N
F
F
NH
N
F
F
NH
N
F
F
N
N
N
N
N
Fe
Fe
N
N
Fe
N
N
N
F
F
F
N
N
N
HN
N
HN
N
HN
N
S
S
S
S
S
S
F C
F C
F C
3
3
3
S
F
S
S
F
S
F
S
S
CF3
CF3
CF3
F
F
F
F C
F C
F C
3
3
3
CF3
CF3
CF3
Fig. 3.
m
-Pyrazine{octakis [2-fluoro-5-(trifluoromethyl)benzylthio]porphyrazinato} iron (II) [FePz(pyz)] (10).
n

6
8
E. Gonca / Journal of Fluorine Chemistry 149 (2013) 65–71
All new compounds were characterized by using many
1
13
19
spectroscopic techniques such as FT-IR, H NMR, C NMR,
F
NMR, UV–vis, mass and elemental analysis. The spectroscopic data
of desired products were in accordance with the assigned
structures.
Elemental analyses agree closely with the values calculated for
(
2-10).
In the FT-IR spectrum of 2 stretching vibration of CBN is
À1
observed at 2222 cm , the aromatic and aliphatic C–H peaks are
around 2870-3070 cm , aromatic C 55 C stretching vibrations are at
1
1
vibration around 2222 cm
absorption of the inner core of 4 was observed around 3310 cm
À1
À1
À1
650 cm
and C–F stretching vibrations are around 1352-
116 cm . After the conversion of 2 into 3, the sharp CBN
À1
disappeared. The N–H stretching
À1
.
FT-IR spectra of all porphyrazines derivatives (3-10) showed the
À1
aromatic C–H stretching vibration peaks around 3075-3030 cm
,
the aliphatic C–H stretching vibration peaks around 2975-
À1
À1
2
850 cm , the aromatic C 55 C peaks around 1675-1650 cm
,
À1
and C–F stretching vibrations are around 1350-1120 cm . In the
Fig. 4. UV–vis spectrum of 8 in chloroform.
À1
FT-IR spectrum of 9, the newly appearing band at 1588 cm and
À1
1
225 cm are likely to be due to the breathing mode of axial
pyridine groups.
The NMR investigations of porphyrazines have provided the
1
characteristic chemical shifts for the structures expected. In the H
NMR spectra of 2,3-bis(2-fluoro-5-(trifluoromethyl)benzylthio)-
maleonitrile (2) four types of protons are clearly seen: Three dd
around 7.68-7.35 ppm corresponding to aromatic protons, a
2
singlet at 4.66 ppm belonging to S–CH . The NH protons in the
inner core of the metal-free porphyrazine (4) are also very well
1
characterized by the H NMR which shows a peak at
d
= À1.25 ppm
as a result of the 18 -electron system of the porphyrazine ring
p
1
[
23–30,40,41]. The H NMR spectra of 9 and 10 indicate an
octahedrally coordinated Fe (II) complex. The chemical shift values
of the axially coordinated ligands have been extensively affected
by the 18-
p
electrons of the porphyrazine core, i.e. the peaks at
.59, 7.75 and 7.38 ppm in free pyridine have been shifted to 6.84,
.75 and 2.35 ppm, respectively, after binding axially to form
. Similarly, there is only a single peak at 2.26 ppm for
pyrazine protons in the bridged structure [FePz(pyz)] [42–44]. In
the C NMR spectra of porphyrazines 3, 4 and 6, ten different
8
4
FePz(py)
2
n
13
Fig. 5. UV–vis spectra of 9 in various solvents.
19
single chemical shifts for carbon atoms are clearly seen. F NMR
spectroscopy has been a very useful technique for investigating the
19
fluorinated compound.
F NMR spectrum of 3 showed two
Table 1. There is almost no difference with respect to the changes
in the nature of the solvent.
different peaks at À144.8 ppm (o-fluoro) and À63.40 ppm.
In addition to these verifying results for the structures, the mass
spectra of compounds (3-9) gave the characteristic molecular ion
The Q bands, appearing at 592 and 625 nm in the UV–visible
2 n
spectrum of FePz(py) (9) or [FePz(pyz)] (10), confirm the
+
+
+
+
peaks at m/z: 2002.9 [M] , 1979.2 [M] , 2036.3 [M] , 2041.8 [M] ,
2
coordination of the pyridine and pyrazine ligands to the metal
ion. UV–vis spectrum of 8 in chloroform is shown in Fig. 4. UV–vis
spectra of 9 in various solvents are shown in Fig. 5.
+
+
+
043.8 [M] , 2069.8[M] , and 2191.1 [M] respectively, confirming
the proposed structures.
UV–vis spectral data of 3, 5-7 in solvents of different polarity
acetone, chloroform, THF and dichloromethane) are given in
When a bidentate ligand such as pyrazine is used instead of
pyridine, similar changes occur in the oxidation state of the metal
ion. In addition, bidentate ligands form a bridge between the metal
centers and form a shish kebab type olygomer [45,46]. In the
electronic spectrum of 10, the Q band absorption at 625 nm has
been shifted to longer wavelength (ca. 33 nm) when compared
with the monomeric structure (9) obtained with pyridine. There is
also a shoulder around 710 nm in the electronic spectra after
oligomer formation.
(
Table 1
a
UV–vis data for the porphyrazines (3, 5-7) in different solvents.
Compound
(CH
3
)
2
CO
CHCl
3
THF
3.80 (4.93)
2 2
CH Cl
3
385 (4.96)
83 (4.95)
3.84 (4.94)
682 (4.93)
383 (4.92)
681 (4.91)
6
677 (4.93)
5
6
340 (4.73)
67 (4.80)
343 (4.70)
670 (4.77)
341 (4.69)
668 (4.76)
346 (4.65)
673 (4.73)
6
3. Conclusions
353 (4.96)
84 (5.01)
356 (4.92)
687 (4.99)
358 (4.92)
689 (4.98)
359 (4.90)
690 (4.96)
In this present work, we have described the synthesis, the
spectral properties and the preparation of novel soluble poly-
fluorinated porphyrazine derivatives. The monomeric bisaxial
complex FePz(py)
type olygomer, [FePz(pyz)]
6
7
341 (4.91)
80 (4.96)
346 (4.89)
685 (4.93)
345 (4.87)
686 (4.92)
347 (4.85)
687 (4.90)
6
2
as well as the bridged complex, shish kebab
were formed as stable complexes by
a
3
À1
À1
l
max/nm (log
e
/dm mol cm ).
n

E. Gonca / Journal of Fluorine Chemistry 149 (2013) 65–71
69
À1
nmax/cm : 3074-3038 (CH, aromatic), 2956-2864
reacting FePzCl with pyridine or pyrazine, respectively. Solubility
of metallo porphyrazines in common solvents is enhanced.
Consequently, we might conclude that the Fe(II)Pz macrocycle
reacts in excess liquid pyrazine to form exclusively a polymeric
compound as is the case for most tetraaza annulenes.
(82%). FT-IR,
(CH, aliphatic), 1662 (C 55 C, aromatic), 1510, 1410, 1345, 1308,
1272, 1188, 1120, 1060, 908, 842, 712, 688, 569. UV–vis (CHCl
3
)
À5
3
À1 À1
(1 Â 10 M)
l
max (nm) (log
, ppm): 7.66 (dd, 8H, Ar–H), 7.48 (dd, 8H, Ar–H),
e/dm mol cm ): 384 (4.94), 682
1
(4.93). H NMR (
d
1
3
7
.32 (dd, 8H, Ar–H), 4.62 (s, 16H, S–CH
113.9, 115.2, 116.3, 124.4, 125.5, 126.2, 127.4, 127.8, 163.4.
NMR (
, ppm): À144.8 (o-fluoro), À63.40. MS (ESI) m/z: 2002.9
[M] . Calcd. for C80 32Mg: C 48.00; H 2.01; N 5.60; S 12.81.
2
). C NMR (d, ppm): 33.4,
19
4
. Experimental
F
d
+
IR spectra were recorded on a Perkin Elmer Spectrum One FT-IR
40 8 8
H N S F
(
ATR sampling accessory) spectrophotometer, electronic spectra
Found: C 48.12; H 2.12; N 5.48; S 12.70.
1
13
19
on a Unicam UV2 spectrophotometer. H NMR, C NMR and
F
NMR spectra, were taken in CDCl solutions at 400.000, 100.577
3
4.3. {2,3,7,8,12,13,17,18-Octakis[2-fluoro-5-
2
1
23
and 376.308 MHz, respectively, recorded on a Bruker Ultra Shield
(trifluoromethyl)benzylthio] H , H porphyrazine} (4)
1
Plus 400 MHz spectrometer. Chemical shifts refer to TMS ( H NMR
13
19
and
C NMR) and fluorotrichloromethane ( F NMR) as the
3 (100 mg, 0.05 mmol) was dissolved in the minimum amount
internal standards. Mass spectra were recorded on a Bruker
Daltonics Micro-TOF and MALDI-TOF mass spectrometer using the
electrospray ionisation (ESI) method. The instrument was operated
in positive ion mode. Elemental analyses were recorded on a
Thermo Scientific 2000 instrument. All starting materials were
purchased from major suppliers and used without any further
purification. The homogeneity of the products was tested in each
step by TLC.
of CF
the reaction mixture was added to ice drop by drop and neutralized
with 25% NH solution, precipitation occurred and it was filtered.
The precipitate was extracted into the CHCl and the CHCl
solution was extracted with water twice. After drying over
anhydrous Na SO , the solvent was evaporated to obtain a violet
colored metal-free porphyrazine. 4 was obtained by column
chromatography (SiO , MeOH:CHCl , 1:30, v/v). Yield: 67 mg
max/cm : 3310 (N–H), 3075-3032 (CH, aromatic),
2938-2855 (CH, aliphatic), 1668 (C 55 C, aromatic), 1508, 1410,
3
CO
2
H (ꢀ4 mL) and stirred for 3 h at room temperature. When
3
3
3
2
4
2
3
À1
The disodium salt of dithiomaleonitrile (1) was prepared
according to the previously reported procedures [47].
(68%). FT-IR, n
1
350, 1308, 1275, 1182, 1122, 1064, 902, 842, 702, 686, 580. UV–
À5
3
À1
À1
4.1. Synthesis of 2,3-bis[2-fluoro-5-
vis (CHCl
3
) (1 Â 10 M)
l
max (nm) (log
e
/dm mol cm ): 350
, ppm): 7.64 (dd, 8H, Ar–
),
d, ppm): 33.5, 113.6, 115.0, 116.5,
1
(trifluoromethyl)benzylthio]maleonitrile (2)
(4.82), 622 (4.24), 678 (4.32). H NMR (d
H), 7.46 (dd, 8H, Ar–H), 7.34 (dd, 8H, Ar–H), 4.64 (s, 16H, S–CH
2
1
3
Disodium salt of dithiomaleonitrile (1) (1.12 g, 6.00 mmol) was
À1.25 (br s, 2H, NH). C NMR (
124.6, 125.2, 126.4, 127.1, 127.5, 163.6. F NMR (
(o-fluoro), À63.42. MS (ESI) m/z: 1979.2 [M] . Calcd. for
32: C 48.54; H 2.14; N 5.66; S 12.96. Found: C
1
9
mixed with 2-fluoro-5-(trifluoromethyl)benzyl bromide (3.86 g,
5.0 mmol) in methanol (50 mL) and refluxed under nitrogen for
about 18 h. After evaporation of MeOH, the remaining oil product
was treated with CHCl to remove insoluble salts by filtration. The
CHCl solution was extracted several times with 15% Na SO
solution and then dried over anhydrous Na SO overnight. When
CHCl was evaporated the colored product was dissolved in a
d
, ppm): À144.6
+
1
80 42 8 8
C H N S F
3
48.41; H 2.25; N 5.52; S 12.82.
3
2
4
2
4
4.4. General procedure for metallo porphyrazines (5-7)
3
minimum amount of chloroform and then added drop wise into
cold n-hexane to precipitate the product, which was filtered off and
dried in vacuum. The orange colored product was very soluble in
4 (99 mg, 0.05 mmol) in CHCl
metal salt [Co(OAc) (89 mg, 0.5 mmol), Cu(OAc)
0.5 mmol), or Zn(OAc) (92 mg, 0.5 mmol)] in EtOH (15 mL) and
3
(10 mL) was stirred with the
2
2
(91 mg,
2
CHCl
3
, CH
2
Cl
2
, and acetone, but insoluble in n-hexane. Yield: 1.30 g
refluxed under nitrogen for about 6 h. Then, the precipitate
composed of the crude product and the excess metal salt were
À1
(
(
84%). FT-IR,
n
max/cm : 3070-3035 (CH, aromatic), 2988-2870
CH, aliphatic), 2222 (CBN), 1665, 1650 (C 55 C, aromatic), 1502,
416, 1352, 1305, 1277, 1184, 1116, 1057, 903, 848, 707, 683, 565.
H NMR (d, ppm): 7.68 (dd, 2H, Ar–H), 7.46 (dd, 2H, Ar–H), 7.35 (dd,
3
filtered. The precipitate was treated with CHCl and the insoluble
1
1
metal salts were removed by filtration. The filtrate was reduced to
minimum volume under reduced pressure and then added into n-
hexane (150 mL) drop by drop to realize the precipitation. Finally,
pure porphyrazine derivatives (5-7) were obtained by column
13
2
H, Ar–H), 4.66 (s, 4H, S–CH
2
). C NMR (d, ppm): 33.2, 113.7,
19
1
15.4, 116.0, 124.2, 125.3, 126.4, 127.2, 127.4, 163.7. F NMR (
d
,
+
ppm): À144.5 (o-fluoro), À63.44. MS (ESI) m/z: 494.9 [M] . Calcd.
for C20 : C 48.59; H 2.04; N 5.67; S 12.97. Found: C 48.70;
H 2.11; N 5.56; S 12.85.
chromatography (SiO
2 3
, MeOH:CHCl , 1:50, v/v).
10 2 2 8
H N S F
4.4.1. {2,3,7,8,12,13,17,18-Octakis[2-fluoro-5-
(
trifluoromethyl)benzylthio] porphyrazinato} Co(II) (5)
À1
4.2. {2,3,7,8,12,13,17,18-Octakis[2-fluoro-5-
Yield: 61 mg (60%). FT-IR,
nmax/cm : 3072-3032 (CH, aromat-
(trifluoromethyl)benzylthio] porphyrazinato} Mg(II) (3)
ic), 2946-2860 (CH, aliphatic), 1666 (C 55 C, aromatic), 1504, 1412,
1
342, 1312, 1278, 1184, 1124, 1062, 904, 846, 716, 684, 565. UV–
À5
3
À1 À1
Mg turnings (6 mg, 0.25 mmol) and a small I
refluxed in n-BuOH (20 mL) for about 8 h to obtain Mg(BuO)
bis(2-fluoro-5-(trifluoromethyl)benzylthio) maleonitrile
2
crystal were
vis (CHCl
3
) (1 Â 10 M)
lmax (nm) (log e/dm mol cm ): 343
+
2
. 2,3-
(4.70), 670 (4.77). MS (ESI) m/z: 2036.3 [M] . Calcd. for
(2)
80 40 8 8
C H N S F32Co: C 47.18; H 1.98; N 5.50; S 12.60. Found: C
(247 mg, 0.50 mmol) was added to this solution and the mixture
47.29; H 1.89; N 5.62; S 12.47.
was refluxed for about 12 h. The colored product was filtered,
washed with ethanol and water and dried in a vacuum. The crude
4.4.2. {2,3,7,8,12,13,17,18-Octakis[2-fluoro-5-
product was dissolved in CHCl
3
and filtered. The CHCl
3
solution
(trifluoromethyl)benzylthio] porphyrazinato} Cu(II) (6)
À1
was dried over anhydrous Na SO
2
4
. When CHCl was evaporated,
3
Yield: 49 mg (48%). FT-IR,
nmax/cm : 3070-3035 (CH, aromat-
the dark green colored product was obtained. Purification of the
product was accomplished by column chromatography with silica
ic), 2926-2855 (CH, aliphatic), 1660 (C 55 C, aromatic), 1502, 1410,
1344, 1315, 1275, 1180, 1128, 1060, 908, 842, 718, 688, 560. UV–
À5
3
À1 À1
+
gel using MeOH/CHCl
3
(1:50) as eluent. 3 was soluble in CHCl
3
,
vis (CHCl
3
) (1 Â 10 M)
lmax (nm) (log e/dm mol cm ): 356
CH Cl , acetone and THF, but insoluble in n-hexane. Yield: 205 mg
2
2
(4.92), 687 (4.99). MS (ESI) m/z: 2041.8 [M] . Calcd. for

7
0
E. Gonca / Journal of Fluorine Chemistry 149 (2013) 65–71
C
80
H
40
N
8
S
8
F
32Cu: C 47.07; H 1.98; N 5.49; S 12.57. Found: C 47.17;
60 8C for 5 h. The excess pyrazine was sublimed under high
vacuum for 8 h. Yield: 61 mg (58%). FT-IR, nmax/cm : 3072-3030
À1
H 2.09; N 5.38; S 12.69.
(
CH, aromatic), 2975-2865 (CH, aliphatic), 1675 (C 55 C, aromatic),
À1
4.4.3. {2,3,7,8,12,13,17,18-Octakis[2-fluoro-5-
1504, 1446, 1348, 1269, 1184, 1118, 1055, 889, 735 cm . UV–vis
(CHCl
À5
3
À1
À1
(
trifluoromethyl)benzylthio] porphyrazinato} Zn(II) (7)
3
) (1 Â 10 M)
l
max (nm) (log
e
/dm mol cm ): 370
, ppm): 7.70 (dd, 8H, Ar–
),
, ppm): À144.6 (o-fluoro), À63.46.
(2113.65) : C 47.73; H 2.10; N 6.63;
À1
1
Yield: 65 mg (64%). FT-IR,
nmax/cm : 3075-3030 (CH, aromat-
(4.85), 625 (4.64), 710 (4.18). H NMR (d
H), 7.50 (dd, 8H, Ar–H), 7.33 (dd, 8H, Ar–H), 4.60 (s, 16H, S–CH
2
ic), 2938-2854 (CH, aliphatic), 1664 (C 55 C, aromatic), 1508, 1410,
1
9
1
344, 1314, 1276, 1188, 1126, 1065, 910, 845, 712, 690, 562. UV–
2.26 (s, 4H, pyz-H). F NMR (
Calcd. for (C84 32Fe)
d
À5
3
À1
À1
vis (CHCl
3
) (1 Â 10 M)
l
max (nm) (log
e
/dm mol cm ): 346
H
44
N S
10 8
F
n
n
1
(4.89), 685 (4.93). H NMR (
d
, ppm): 7.68 (dd, 8H, Ar–H), 7.44 (dd,
S 12.14. Found: C 47.85; H 2.22; N 6.50; S 12.02.
13
8
2
H, Ar–H), 7.36 (dd, 8H, Ar–H), 4.68 (s, 16H, S–CH ). C NMR (d,
ppm): 33.2, 113.7, 115.4, 116.5, 124.7, 125.3, 126.4, 127.4, 127.6,
Acknowledgements
19
1
0
1
63.6. F NMR (
d
, ppm): À144.6 (o-fluoro), À63.44. MS (ESI) m/z:
43.8 [M] . Calcd. for C80 32Zn: C 47.03; H 1.97; N 5.48; S
2.56. Found: C 47.15; H 1.85; N 5.60; S 12.44.
+
40 8 8
H N S F
This work was supported by the Scientific Research Fund of
Fatih University under the project number P50011204_B.
4
.5. Chloro {octakis [2-fluoro-5-(trifluoromethyl)benzylthio]
Appendix A. Supplementary data
porphyrazinato} iron (III) (FePzCl) (8)
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.jfluchem.2013.
2
A mixture of 4 (95 mg, 0.0478 mmol) and Fe(OAc) (416 mg,
.39 mmol) in HOAc (20 mL) was heated at 120 8C for 24 h under
nitrogen. The reaction was monitored continuously for the presence
of metal-free porphyrazine by UV–vis spectroscopy. After comple-
tion of the reaction, the mixture was filtered and HOAc was
evaporated under reduced pressure. The residue was dissolved in
2
02.012.
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3
2
1
l
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À1
À1
1
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e
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d,
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.84 (m, py-H ), 4.75 (m, py-H ), 4.64 (s, 16H, S–CH ), 2.35 (m, py-H ).
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[
1