Synthesis and characterization of novel polyfluorinated porphyrazines

Article abstract of DOI:10.1016/j.jfluchem.2012.04.013

By cyclotetramerization of 2,3-bis(2,3,4,5,6-pentafluorobenzylthio) maleonitrile in the presence of magnesium butanolate, magnesium porphyrazinate carrying eight (2,3,4,5,6-pentafluorobenzylthio) functional groups on the periphery positions has been synth

Full text of DOI:10.1016/j.jfluchem.2012.04.013

Journal of Fluorine Chemistry 140 (2012) 54–58
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Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
Synthesis and characterization of novel polyfluorinated porphyrazines
*
Neriman Ag˘gu¨n, Ergu¨n Gonca
Department of Chemistry, Fatih University, TR34500 B. Cekmece, Istanbul, 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(2,3,4,5,6-pentafluorobenzylthio)maleonitrile in the presence of
magnesium butanolate, magnesium porphyrazinate carrying eight (2,3,4,5,6-pentafluorobenzylthio)
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 copper(II) acetate, zinc(II) acetate and cobalt(II) acetate have led to
the metallo derivatives [M = Cu(II), Zn(II), Co(II)]. These novel complexes were characterized by
elemental analysis, together with FT-IR, 1H NMR, 13C NMR, 19F NMR, UV–vis, and mass spectral data.
ß 2012 Elsevier B.V. All rights reserved.
Received 27 December 2011
Received in revised form 19 January 2012
Accepted 23 April 2012
Available online 30 April 2012
Keywords:
2,3,4,5,6-Pentafluorobenzylthio
Porphyrazine
19F NMR spectroscopy
Magnesium
Copper
1. Introduction
Porphyrazines are considerably less studied than phthalocya-
nines. There have been several positive properties of porphyr-
Porphyrazines and their structural analogs belong to a wide
class of macro heterocyclic tetrapyrrole systems that are constitu-
tionally tetra-aza analogues of porphyrins. These porphyrins are of
considerable interest because their representatives are compo-
nents of the most important natural compounds (hemoglobin,
myoglobin, cytochromes, chlorophylls, and others) and are
included in such living processes including cell respiration,
photosynthesis, and electron transport. Recently, heteroatomic
substitutions directly fusing to the macrocyclic periphery have
brought an increasing consideration to the porphyrazine works [1–
5]. Relative ease of their synthetic preparation, and also the strong
correlation between the nature of the substituent and the
electronic and optical properties of the macro cyclic ring system
play roles on this recent interest. Comparing to the phthalocyanine
analogues, direct fusion of heteroatomic substituents onto the
azines, specifically those closest to synthetic analogs of
phthalocyanines and their high stability against oxidation
favoring their use in wide practical application as dyes and
pigments. Porphyrazines have found several applications in new
areas such as bleachable dyes in laser technique, discotic liquid
crystals, constituents of electrochromic and electrophotographic
materials, radiation protectors, gas sensors, catalysts of several
methods (in particular, electrochemical), antimicrobial drugs, in
luminescent diagnostics and photodynamic therapy of cancer
tumors [7–12].
The main problem limiting applications of porphyrazines (Pzs)
in many areas is still their limited solubility. Their solubility can be
increased, on the other hand, by introducing electron-withdrawing
(–F, –Cl, –Br) and electron-donating (–NH2, Ar–S–, RO–, RS–) bulky
or long chain alkyl groups into the peripheral places [13–17]. The
formation of constitutional isomers and the higher dipole moment
of the tetra-substituted Pzs resulting from the unsymmetrical
grouping of the substituents on the periphery leads to higher
solubility of Pzs in many organic solvents [18].
Metallo-porphyrazines substituted with fluorine atoms are
currently receiving a great deal of attention because of their high
thermal stability, hydrophobicity, lipophobicity and chemical
resistance; they also have interesting electron-transporting
characteristics [19]. By placing stronger electron-withdrawing
fluorine atoms on the Pz ring results in both the valence and
conduction band energies being further lowered. Thus, MPzFn (n:
number of fluorine atoms) exhibits n-type behavior, while
unsubstituted porphyrazines have p-type because of doping with
electron accepting molecules [20]. These unexpected properties of
porphyrazine b-positions results in an evident effect; on the other
hand, there is no such available analogous derivatives for the
porphyrins. In comparison to the phthalocyanine counterparts, the
porphyrazines also often display an extensively increased solubili-
ty in organic solvents. Thus, they maintain a unique position
among the tetrapyrrolic macrocycles, and their straightforward
synthesis coupled with their tunable electronic and optical
properties, renders them exciting candidates for a whole range
of applications [6].
* Corresponding author. Tel.: +90 212 866 33 00; fax: +90 212 866 34 02.
E-mail address: egonca@fatih.edu.tr (E. Gonca).
0022-1139/$ – see front matter ß 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jfluchem.2012.04.013

N. Ag˘gu¨n, E. Gonca / Journal of Fluorine Chemistry 140 (2012) 54–58
55
MPzFn have led scientists to expose their chemistry to be used in a
number of different industrial applications [21].
reaction in n-butanol at reflux temperature for 12 h (Scheme 1).
Octakis(2,3,4,5,6-pentafluorobenzylthio) porphyrazinato magne-
sium (3) was very soluble in most of the common solvents except
methanol and ethanol (Fig. 1). The conversion of 3 into 4 was
achieved by the treatment with relatively strong acids (e.g.
trifluoroacetic acid). The mass spectral results have clearly
indicated the change of the structure from magnesium porphyr-
azinate (3) to the metal-free porphyrazine (4). Further reaction of 4
with copper(II) acetate, zinc(II) acetate and cobalt(II) acetate has
led to the metal porphyrazinates (M = Cu, Zn, Co) (5–7) (Fig. 1).
All new compounds were characterized by using many
spectroscopic techniques such as FT-IR, 1H NMR, 13C NMR, 19F
NMR, UV–vis, mass and elemental analysis. The spectroscopic data
of desired products were in accordance with the assigned
structures.
Our group has been deeply interested in the preparation of
novel soluble porphyrazine derivatives. Among these, we have
synthesized novel seco-porphyrazines substituted with 1-naphthyl
[22], o-tolyl and p-tolyl [23], 4-tertbutylphenyl [24] and 4-
biphenyl groups [25] on the peripheral positions, as encountered
by Barrett, Hoffman and coworkers with peripheral amino
derivatives [26]. Recently, we have also synthesized Pzs with
peripheral functional groups such as quaternizable amino groups
[27], crown ethers [28], ferrocenes [29], triphenylphosphine [30],
4-tert-buthylphenylthio [31], o-tolylthio and p-tolylthio [32],
tosylaminoethylthio [33], 3-methylbutylthio [34], 1-naphthyl-
methylthio [35] and 9-anthracenylmethylthio [36] units can be
cited.
In our previous study, we have reported the synthesis,
structural and spectral properties of symmetric metallo-porphyr-
azines [37]. In this step, our aim has been to design new molecules
with polyfluoro-substituents, enhancing their solubility in com-
mon solvents and at the same time prohibiting their aggregation.
We report herein the synthesis, and characterization of new
readily soluble metallo-porphyrazines with up to 40 fluorine-
containing substituents on the periphery for the first time, and we
also report on the effects of the substituents on the spectroscopic
and aggregation properties of the porphyrazines derivatives in
different solvents and at different concentrations in chloroform. By
using different spectroscopic methods such as elemental analysis,
FT-IR, 1H NMR, 19F NMR, UV–vis. and mass spectrometry, new
compounds have been characterized.
Elemental analyses agree closely with the values calculated for
(2–7).
In the FT-IR spectrum of 2,3-bis(2,3,4,5,6-pentafluoroben-
zylthio)maleonitrile (2) stretching vibration of CꢀN is observed
at 2220 cmꢁ1
, the aliphatic C–H peaks are around 2985–
2855 cmꢁ1, aromatic C55C stretching vibrations are at 1650 cmꢁ1
and C–F stretching vibrations are around 1355–1114 cmꢁ1. After
the conversion of dinitrile derivative (2) to porphyrazine (3), the
sharp CꢀN vibration around 2220 cmꢁ1 disappeared. The N–H
stretching absorption of the inner core of the metal-free
porphyrazine (4) was observed around 3290 cmꢁ1. FT-IR spectra
of all porphyrazines derivatives (3–7) showed the aliphatic C–H
peaks are in the range of 2988–2850 cmꢁ1 and the aromatic C55C
peak is at 1615–1648 cmꢁ1
.
1H NMR investigations of porphyrazines have provided the
characteristic chemical shifts for the structures expected. In the
1H-NMR spectra of 2,3-bis(2,3,4,5,6-pentafluorobenzylthio)ma-
leonitrile (2) one type of proton is clearly seen: a singlet at
4.66 ppm for methylene protons. The NH protons in the inner core
of the metal-free porphyrazine (4) are also very well characterized
2. Results and discussion
As proposed by Linstead, unsaturated 1,2-dinitrile derivative
should be prepared as the starting material [38,39]. Disodium salt
of dithiomaleonitrile (1) obtained from simple reactants sodium
cyanide and carbondisulfide in two steps was referred as the
starting point. Alkylation of disodium salt of maleonitrile with
2,3,4,5,6-pentafluorobenzyl bromide in methanol gave 2,3-
bis(2,3,4,5,6-pentafluorobenzylthio)maleonitrile (2) which was
in cis-form and easily soluble in chloroform, dichloromethane
and acetone (Scheme 1). The orange colored product (2) was
obtained in 58% yield. The presence of bulky electron-donating S-
groups is expected to enhance the chemical stability and optical
properties of porphyrazines [27,40,41]. Cyclotetramerization of
2,3-bis(2,3,4,5,6-pentafluorobenzylthio)maleonitrile into por-
phyrazine was realized by making use of the template effect of
magnesium ions. The optimum condition was to accomplish the
by the 1H NMR which shows a peak at
the 18 -electron system of the porphyrazine ring [27–
d
= ꢁ1.10 ppm as a result of
p
29,33,35,42].
In the 13C NMR spectra of diamagnetic porphyrazines 3, 4 and 6,
seven different single chemical shifts for carbon atoms are clearly
seen.
19F NMR spectroscopy has been a very useful technique for
investigating the fluorinated compound. 19F NMR spectrum of
MgPz (3) showed three different peaks at ꢁ142.4 ppm,
ꢁ152.6 ppm and ꢁ161.6 ppm, respectively, relative to the fluorine
atoms in the ortho, para and meta positions of the phenyl
substituents and the spectrum showed the expected signals of
Scheme 1. (i) Methanol; (ii) Mg turnings, I2, n-BuOH; (iii) CF3CO2H; (iv) EtOH and Cu(OAc)2, Zn(OAc)2, or Co(OAc)2.

56
N. Ag˘gu¨n, E. Gonca / Journal of Fluorine Chemistry 140 (2012) 54–58
Fig. 1. Octakis (2,3,4,5,6-pentafluorobenzylthio) substituted porphyrazines (3–7).
the five fluorine atoms attached to the aromatic ring. Integration of
the peaks gave a 2:1:2 ratio as expected.
tion increased in parallel, and there were no new bands because of
the aggregated ones [34]. It is seen that the Beer-Lambert law was
In addition to these verifying results for the structures, the mass
spectra of compounds (3–7) gave the characteristic molecular ion
peaks at m/z: 2033.9 [M]+, 2011.8 [M]+, 2072.1 [M]+, 2074.2 [M]+
and 2068.8 [M]+, respectively, confirming the proposed structures.
The UV–vis spectra of the porphyrazine complexes exhibited
characteristic of absorptions in the Q-band region at around 664–
680 nm for MPzs (3, 5–7) in chloroform, attributed to the
corrected for compound 3 for concentrations ranging from
2 ꢂ 10ꢁ5 to 5 ꢂ 10ꢁ6 mol dmꢁ3 (Fig. 3). And also the aggregation
treatments of 3 were worked in different solvents such as DCM,
THF and acetone at different concentrations ranging from 2 ꢂ 10ꢁ5
to 5 ꢂ 10ꢁ6 mol dmꢁ3. There were only slight differences in B and
Q bands as nm and because of the aggregated ones there were no
new bands.
p
!
p*transition from the HOMO to the LUMO of the Pzꢁ2 ring,
and in the B band region (UV region) at around 340–356 nm in
chloroform, arising from the deeper
p*transitions (Table 1)
It is expected that the substitution of polyfluorinated groups
into the peripheral position of porphyrazines imparts high
solubility in organic solvents such as chloroform, dichloro-
methane, and acetone. The increased solubility might be because
p
!
[42,43]. The presence of an electron donating group on the
periphery causes a bathochromic shift on Q bands. For metal-free
derivative (4), Q band is split into two peaks at 654 and 712 nm as a
consequence of the change in the symmetry of porphyrazine core
from D4h (in the case of metallo derivatives) to D2h. UV–vis spectra
of 4–7 in chloroform are shown in Fig. 2.
Aggregation, which is usually described as a coplanar associa-
tion, is dependent on the concentration, type of the solvent, type of
the substituents, complexed metal ions and temperature [44–46].
The aggregation treatment of
3 was worked at different
concentrations in chloroform (Fig. 3). In chloroform, as the
concentration was increased, the intensity of the Q-band absorp-
Table 1
UV–vis data for the porphyrazines in chloroform.
Compound
l/nm (log e )
/dm3 molꢁ1 cmꢁ1
3
4
5
6
7
356 (4.97)
338 (4.77)
340 (4.95)
352 (4.91)
346 (4.83)
664 (4.93)
654 (4.47)
678 (4.99)
680 (4.97)
674 (4.88)
712 (4.50)
Fig. 2. UV–vis spectra of 4–7 in chloroform.

N. Ag˘gu¨n, E. Gonca / Journal of Fluorine Chemistry 140 (2012) 54–58
57
cold n-hexane to precipitate the product, which was filtered off and
dried in vacuum. The orange colored product was very soluble in
chloroform, dichloromethane and acetone, but insoluble in n-
hexane. Yield: 2.29 g (76%). FT-IR, n
max/(cmꢁ1): 2985–2872 (CH,
aliphatic), 2220 (CꢀN), 1665, 1650 (C55C, aromatic), 1593, 1512,
1418, 1355, 1308, 1274, 1182, 1114, 1055, 903, 846, 705, 681, 555.
1H NMR (
d
, ppm): 4.66 (s, 4H, S-CH2). 13C NMR (
d
, ppm): 18.6,
113.7, 113.9, 115.5, 137.2, 137.4, 141.8. 19F NMR (
d
, ppm): ꢁ144.6
(o-fluoro), ꢁ154.4 (p-fluoro), ꢁ163.6 (m-fluoro). MS (ESI) m/z:
502.9 [M]+. Calcd. for C18H4N2S2F10: C 43.04; H 0.80; N 5.58; S
12.77. Found: C 43.11; H 0.86; N 5.52; S 12.65.
3.2. [2,3,7,8,12,13,17,18-octakis(2,3,4,5,6-pentafluorobenzylthio)
porphyrazinato] Mg(II) (3)
Mg turnings (6 mg, 0.25 mmol) and a small I2 crystal were
refluxed in n-BuOH (20.0 mL) for about 8 h to obtain Mg(BuO)2.
2,3-Bis(2,3,4,5,6-pentafluorobenzylthio)maleonitrile (2) (251 mg,
0.50 mmol) was added to this solution and the mixture was
refluxed for about 12 h. The colored product was filtered, washed
with ethanol and water and dried in a vacuum. The crude product
was dissolved in CHCl3 and filtered. The CHCl3 solution was dried
over anhydrous Na2SO4. When CHCl3 was evaporated, the dark
green colored product was obtained. Purification of the product
was accomplished by column chromatography with silica gel using
methanol/chloroform (1:20) as eluent. 3 was soluble in chloro-
form, dichloromethane, acetone and THF, but insoluble in n-
Fig. 3. UV–vis spectra of 3 in chloroform at various concentrations.
of the higher solubility of pentafluorobenzyl-substituted groups in
organic polar solvents. The solubility of 3 in chloroform, DCM, THF,
and acetone was determined as 45, 55, 61, and 63 mg/mL,
respectively. When the polarities of the solvents are increasing,
the solubility of 3 is also increasing as anticipated.
In our previous paper [32], non-fluorinated groups into the
peripheral position such as o-tolyl and p-tolyl groups were
synthesized and the solubility of MgPz in chloroform, DCM, THF,
and acetone was determined as 29, 35, 38, and 39 mg/mL,
respectively. As a result of these solubility data of fluorinated
and non-fluorinated counterparts, it is clear that the main effect of
solubility is due to fluorinated groups.
hexane. Yield: 198 mg (78%). FT-IR,
aliphatic), 1660, 1615 (C55C, aromatic), 1595, 1515, 1415, 1358,
1310, 1276, 1180, 1112, 1058, 905, 848, 702, 680, 553. 1H NMR (
ppm): 4.62 (s, 16H, S-CH2). 13C NMR (
, ppm) 18.9, 113.4, 114.0,
115.8, 137.0, 137.4, 141.5. 19F NMR (
n
max/(cmꢁ1): 2988–2850 (CH,
d
,
d
d
, ppm): ꢁ142.4 (o-fluoro),
ꢁ152.6 (p-fluoro), ꢁ161.6 (m-fluoro). MS (ESI) m/z: 2033.9 [M]+.
Calcd. for C72H16N8S8F40Mg: C 42.52; H 0.79; N 5.51; S 12.61.
Found: C 42.61; H 0.86; N 5.44; S 12.73.
3. Experimental
IR spectra were recorded on a Perkin Elmer Spectrum One FT-IR
(ATR sampling accessory) spectrophotometer, electronic spectra
on a Unicam UV2 spectrophotometer. Elemental analyses were
recorded on a Thermo Scientific 2000 instrument. 1H NMR, 13C
NMR and 19F NMR spectra, were taken in CDCl3 solutions at
400.000, 100.577 and 376.308 MHz, respectively, recorded on a
Bruker Ultra Shield Plus 400 MHz spectrometer. Chemical shifts
refer to TMS (1H NMR and 13C NMR) and fluorotrichloromethane
3.3. [2,3,7,8,12,13,17,18-octakis(2,3,4,5,6-pentafluorobenzylthio)
H21, H23 porphyrazine] (4)
3 (102 mg, 0.05 mmol) was dissolved in the minimum amount
of trifluoroaceticacid (ꢃ4.00 mL) and stirred for 3 h at room
temperature. When the reaction mixture was added to ice drop by
drop and neutralized with 25% ammonia solution, precipitation
occurred and it was filtered. The precipitate was extracted into the
chloroform and the chloroform solution was extracted with water
twice. After drying over anhydrous Na2SO4, the solvent was
evaporated to obtain a violet colored metal-free porphyrazine. 4
was obtained by column chromatography (SiO2, CH3OH:CHCl3,
(
19F NMR) as the internal standards. Mass spectra were recorded
on a Bruker Daltonics Micro-TOF and MALDI-TOF mass spectrom-
eter using the electrospray ionisation (ESI) method. The instru-
ment was operated in positive ion mode. 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.
1:50, v/v). Yield: 67 mg (66%). FT-IR,
n
max/(cmꢁ1): 3295 (N–H),
2987–2855 (CH, aliphatic), 1662, 1622 (C55C, aromatic), 1598,
1512, 1413, 1356, 1314, 1278, 1182, 1114, 1059, 906, 849, 705,
The disodium salt of dithiomaleonitrile (1) was prepared
according to the previously reported procedures [38].
683, 556. 1H NMR (
d
, ppm): 4.62 (s, 4H, S-CH2), ꢁ1.10 (br s, 2H,
NH). 13C NMR (
141.6. 19F NMR (
d, ppm): 18.8, 113.6, 113.9, 115.6, 137.2, 137.4,
d
, ppm): ꢁ142.3 (o-fluoro), ꢁ151.3 (p-fluoro),
3.1. Synthesis of 2,3-bis(2,3,4,5,6-pentafluorobenzylthio)maleonitrile
(2)
ꢁ154.4 (m-fluoro). MS (ESI) m/z: 2011.8 [M]+. Calcd. for
C
72H18N8S8F40: C 42.99; H 0.80; N 5.57; S 12.75. Found: C
42.89; H 0.75; N 5.64; S 12.62.
Disodium salt of dithiomaleonitrile (1) (1.12 g, 6.00 mmol) was
mixed with (2,3,4,5,6-pentafluorobenzyl bromide) (3.92 g,
15.0 mmol) in methanol (50.0 mL) and refluxed under nitrogen
for about 18 h. After evaporation of MeOH, the remaining oil
product was treated with CHCl3 to remove insoluble salts by
filtration. The CHCl3 solution was extracted several times with 15%
Na2SO4 solution and then dried over anhydrous Na2SO4 overnight.
When CHCl3 was evaporated the colored product was dissolved in
a minimum amount of chloroform and then added drop-wise into
3.4. General procedure for metallo porphyrazines (5–7)
4 (101 mg, 0.05 mmol) in CHCl3 (10.0 mL) was stirred with the
metal salt [Cu(OAc)2 (91 mg, 0.5 mmol), Zn(OAc)2 (92 mg,
0.5 mmol) or Co(OAc)2 (89 mg, 0.5 mmol)] in ethanol (15.0 mL)
and refluxed under nitrogen for about 6 h. Then, the precipitate
composed of the crude product and the excess metal salt were
filtered. The precipitate was treated with CHCl3 and the insoluble

58
N. Ag˘gu¨n, E. Gonca / Journal of Fluorine Chemistry 140 (2012) 54–58
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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
chromatography (SiO2, CH3OH: CHCl3, 1:20, v/v).
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3.4.1. [2,3,7,8,12,13,17,18-octakis(2,3,4,5,6-pentafluorobenzylthio)
porphyrazinato] Cu(II) (5)
Yield: 46 mg (44%). FT-IR,
n
max/(cmꢁ1): 2985–2852 (CH,
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aliphatic), 1664, 1648 (C55C, aromatic), 1592, 1518, 1412, 1355,
1315, 1274, 1185, 1114, 1056, 902, 846, 704, 682, 550. MS (ESI) m/
z: 2072.1 [M]+. Calcd. for C72H16N8S8F40Cu: C 41.72; H 0.78; N 5.41;
S 12.37. Found: C 41.81; H 0.84; N 5.35; S 12.48.
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3.4.2. [2,3,7,8,12,13,17,18-octakis(2,3,4,5,6-pentafluorobenzylthio)
porphyrazinato] Zn(II) (6)
Yield: 50 mg (48%). FT-IR,
aliphatic), 1665, 1636 (C55C, aromatic), 1598, 1512, 1410, 1355,
1310, 1274, 1184, 1110, 1056, 902, 846, 703, 681, 554. 1H NMR (
ppm): 4.64 (s, 16H, S-CH2). 13C NMR (
, ppm) 18.9, 113.4, 114.0,
115.8, 137.0, 137.4, 141.5. 19F NMR (
n
max/(cmꢁ1): 2985–2858 (CH,
d
,
d
d
, ppm): ꢁ142.8 (o-fluoro),
ꢁ152.4 (p-fluoro), ꢁ161.4 (m-fluoro). MS (ESI) m/z: 2074.2 [M]+.
Calcd. for C72H16N8S8F40Zn: C 41.68; H 0.78; N 5.40; S 12.36.
Found: C 41.61; H 0.85; N 5.48; S 12.23.
¨
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3.4.3. [2,3,7,8,12,13,17,18-octakis(2,3,4,5,6-pentafluorobenzylthio)
porphyrazinato] Co(II) (7)
¨
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Yield: 54 mg (52%). FT-IR,
n
max/(cmꢁ1): 2986–2850 (CH,
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aliphatic), 1666, 1644 (C55C, aromatic), 1590, 1514, 1410, 1353,
1312, 1276, 1180, 1112, 1058, 900, 844, 702, 684, 554. MS (ESI) m/
z: 2068.8 [M]+. Calcd. for C72H16N8S8F40Co: C 41.81; H 0.78; N 5.42;
S 12.40. Found: C 41.89; H 0.84; N 5.36; S 12.51.
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This work was supported by the Scientific Research Fund of
Fatih University under the project number P50021103_B.
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