Synthesis and characterization of new soluble polyfluorinated seco-porphyrazines

Article abstract of DOI:10.1016/j.inoche.2012.04.002

The synthesis of new polyfluorinated magnesium porphyrazine bearing pentafluorophenyl moieties was achieved by cyclotetramerization of 3,4-bis(pentafluorophenyl)pyrroline-2,5-diimine in the presence of Mg(BuO) ₂. Acid-mediated demetallation of

Full text of DOI:10.1016/j.inoche.2012.04.002

Inorganic Chemistry Communications 21 (2012) 28–31
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Synthesis and characterization of new soluble polyfluorinated seco-porphyrazines
⁎
Selma Kayaköy, Ergün 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:
The synthesis of new polyfluorinated magnesium porphyrazine bearing pentafluorophenyl moieties was achieved
by cyclotetramerization of 3,4-bis(pentafluorophenyl)pyrroline-2,5-diimine in the presence of Mg(BuO)2. Acid-
mediated demetallation of the magnesium porphyrazine resulted in peripheral oxidation of one pyrrole ring to re-
veal the seco-porphyrazine, [2,3,7,8,12,13,17,18-octakis(pentafluorophenyl)-2-seco-2,3-dioxoporphyrazine]. Fur-
ther reaction of that product with copper (II) acetate, zinc (II) acetate and cobalt (II) acetate has led to the
metallated seco-derivatives, [2,3,7,8,12,13,17,18-octakis(pentafluorophenyl)-2-seco-2,3-dioxoporphyrazinato]
M(II) [M = Cu(II), Zn(II), Co(II)]. The spectroscopic and aggregation behavior of all the target porphyrazines
were investigated in different solvents and at different concentrations in chloroform. The compounds were char-
acterized by using many spectroscopic techniques such as FT-IR, 1H NMR, 13C NMR, 19F NMR, UV–vis, mass and
elemental analysis. The porphyrazines were soluble in various organic solvents such as chloroform, dichloro-
methane, pyridine, and THF.
Received 15 February 2012
Accepted 9 April 2012
Available online 19 April 2012
Keywords:
Seco-porphyrazines
Fluorocarbons
Pentafluorophenyl
Zinc
Copper
© 2012 Elsevier B.V. All rights reserved.
Porphyrins (P) and their structural derivatives –phthalocyanines
(Pc) and porphyrazines (Pz)– constitute a distinct class of macrocy-
clic tetrapyrrole systems with unique physical and chemical proper-
ties. Phthalocyanines have received a great deal of interest owing to
their extensive use in a number of applications involving chemical
sensors, electrochromic devices, batteries, semiconductors, catalysts,
and liquid crystals [1,2]. Metallated phthalocyanines (MPcs) are also
currently undergoing clinical trials for use in the photodynamic ther-
apy (PDT) of cancer [3–8]. Because of their chemical diversity, these
compounds, and in particular porphyrins and phthalocyanines, have
been at the focus of multidisciplinary interest for many years. Howev-
er, although the molecular structures of all three types of macrocycles
are very similar, benzo- and especially aza-substitution have a strong
impact on the overall chemical behavior of the corresponding tetra-
pyrrole ligands [9–11].
The porphyrazines have specific optical properties because they have
symmetrical rich 18 π-electron aromatic macrocycle, which can play as a
host to different metal ions in its central cavity. Therefore, they have
been extensively used in optical recording media, photosensors, optical
filters and copy preventing inks. A seco-porphyrazine is defined as a por-
phyrazine in which one of the pyrrole rings has been effectively cut and
replaced by two acyclic substituents attached to the macrocyclic core.
Fluorinated metallated tetrapyrrole compounds currently receive a
great deal of attention because of their interesting electron transfer,
photosensitizing properties, along with magnetic and thermal character-
istics [12–17]. The presence of pentafluorophenyl groups on the
macrocycle ring can increase the catalytic activity and stability [18].
Fluoro-substituted tetrapyrrole compounds are known for their high
solubility, even in polar, aprotic solvents. The increased solubility may
be due to fluorine, which has the highest electronegativity of all ele-
ments [19].
Our group has been heavily interested in the preparation of new
soluble porphyrazine derivatives. Among these, Pzs with peripheral
functional groups such as 3,5-bis(trifluoromethyl)benzylthio [20] and
3-thiopropylpentafluorobenzoate [21] can be cited. Recently, we have
synthesized novel seco-porphyrazines substituted with 1-naphthyl [22],
o-tolyl and p-tolyl [23], 4-tert-butylphenyl [24], 4-biphenyl [25], and
3,5-bis(trifluoromethyl)phenyl [26] groups on the peripheral positions
as encountered by Barrett, Hoffman and coworkers, with peripheral
amino derivatives [27–30].
In the present paper, octasubstituted symmetric magnesium porphyr-
azine (3), unsymmetrical metal-free seco-porphyrazine (4), and metal-
lated seco-porphyrazines (5–7) containing polyfluorophenyl groups on
the periphery were synthesized. Magnesium porphyrazine was prepared
by a direct cyclotetramerization of 3,4-bis(pentafluorophenyl)pyrroline-
2,5-diimine (2) in the presence of Mg(BuO)2. Even though the first step
of this process to obtain 3 has been actualized in the requested direction,
demetallation to metal-free compound leads to an oxidized 4 as encoun-
tered by Nie et al. [31] with peripheral amino derivatives. Together with
further metallated products (5–7), these new soluble complexes were
characterized by elemental analysis, together with FT-IR, 1H NMR, 13C
NMR, 19F NMR, UV–vis, and mass spectral data.
3, 4 and 5–7 with eight pentafluorophenyl groups bound to
the periphery are 2,3-bis(pentafluorophenyl)dinitrile derivative
(1) [32] which was obtained by oxidative coupling of penta-
fluorophenylacetonitrile in the presence of I2. The solid product
⁎
Corresponding author. Tel.: +90 212 866 33 00; fax: +90 212 866 34 02.
E-mail address: egonca@fatih.edu.tr (E. Gonca).
1387-7003/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.inoche.2012.04.002

S. Kayaköy, E. Gonca / Inorganic Chemistry Communications 21 (2012) 28–31
29
(1) was obtained in a yield of 64% (Scheme 1). It was a mixture of maleo
and fumaronitriles and the latter was present in higher ratio as
expected from the presence of pentafluorophenyl substituents. The
product was brown colored and was very soluble in chloroform,
dichloromethane and acetone, but insoluble in n-hexane. Its reluctance
to turn into porphyrazine under the usual conditions (i.e. Mg(OR)2 in
refluxing n-propanol or n-butanol) points out the lower ratio of the
maleonitrile component. This problem was solved by activation of the
fumaronitrile derivative to the corresponding diiminopyrroline deriva-
tive (2) [33] which cyclizes quite easily to porphyrazine at reflux tem-
perature of n-propanol or n-butanol [34]. In order to convert the
diiminopyrroline derivative (2) into porphyrazine, we have made use
of its template reaction in the presence of magnesium butanolate,
which is the typical method generally applied in cyclotetramerization
of these tetrapyrrole derivatives [35–37]. The dark blue octakis(penta-
fluorophenyl)porphyrazinatomagnesium (3) [38] was soluble in chlo-
roform, dichloromethane, acetone, THF and pyridine (Fig. 1). The
conversion of 3 to metal-free seco-porphyrazine derivative (4) [39]
was achieved by treatment with trifluoroacetic acid followed by neu-
tralization with ammonia and aqueous precipitation. The purity of the
product could be raised by dissolving the crude substance in minimum
amount of chloroform and then reprecipitating it by dropwise addition
of the solution to n-hexane. Further reaction of 4 with copper (II) acetate,
zinc (II) acetate and cobalt (II) acetate has led to the metallated seco-
derivatives, [2,3,7,8,12,13,17,18-octakis(pentafluorophenyl)-2-seco-2,3-
dioxoporphyrazinato] M(II) [M = Cu(II), Zn(II), Co(II)] (5–7) [40–42]
(Scheme 1) (Fig. 2).
Fig. 1. [2,3,7,8,12,13,17,18-octakis(pentafluorophenyl)porphyrazinato]Mg(II) (3).
1H NMR investigations of 2 and 4 provide the characteristic chem-
ical shifts for the structures as expected. The N\H protons of 2 were
also identified in the 1H NMR spectrum with a broad singlet peak at
δ=4.80 ppm, presenting the diiminopyrroline derivative. 1H NMR
spectrum of 4 showed chemical shift belonging to metal-free por-
phyrazine ring protons (broad singlet) at −1.35 ppm [45,46].
In the 13C NMR spectra of diamagnetic porphyrazines 3, 4 and 6,
six different single chemical shifts for carbon atoms were clearly
seen.
The newly synthesized compounds were characterized by using
standard spectral methods (FT-IR, UV–vis, mass, 1H, 13C and 19F
NMR) in addition to elemental analysis. Spectral investigations for
all new products were consistent with the assigned structures.
Elemental analysis results correspond closely with the calculated
values for (1–7) (Table 1).
In the FT-IR spectrum of 2,3-bis(pentafluorophenyl)dinitrile deriva-
tive (1), the characteristic stretching vibration of C`N is observed at
2218 cm−1, the aromatic C_C peak is at 1610 cm−1 and the stretching
vibrations of C\F are at 1346, 1166 and 1125 cm−1. In the FT-IR spec-
trum of 3,4-bis(pentafluorophenyl)pyrroline-2,5-diimine (2), stretching
vibration of N\H is observed at 3330 cm−1, the aromatic C_C peak is
at 1610 cm−1 and the characteristic C\F peaks are at 1344, 1184,
1123 cm−1 [20,21,26,43,44]. In the FT-IR spectrum of 3 the N\H groups
19F NMR spectroscopy has been a very useful technique for inves-
tigating the fluorinated compound. 19F NMR spectrum of 6 showed
three different peaks at −142.8 ppm, −152.3 ppm and −161.9 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 the five fluorine atoms attached to the aromatic
ring [47,48]. Integration of the peaks gave a 2:1:2 ratio as expected.
in the inner core show absorption at 3335 cm−1
.
Scheme 1. (i) NaOMe, MeOH, I2; (ii) NH3, cat Na, Ethylene glycol; (iii) Mg turnings, I2, n-BuOH; (iv) CF3CO2H; (v) EtOH and Cu(OAc)2, Zn(OAc)2, or Co(OAc)2.

30
S. Kayaköy, E. Gonca / Inorganic Chemistry Communications 21 (2012) 28–31
Table 2
UV–vis data for the porphyrazines (3–7) in chloroform.
Compound
λ/nm (log ε/dm3 mol−1 cm−1
)
3
4
5
6
7
356 (4.91)
348 (4.93)
360 (4.98)
376 (4.98)
368 (4.95)
668 (4.88)
620 (4.58)
676 (4.79)
680 (4.91)
672 (4.89)
696 (4.61)
7 (1×10−5 M) in solvents of different polarities (chloroform, dichloro-
methane, pyridine, and THF) are given in Fig. 5. There is almost no differ-
ence with respect to the changes in the nature of the solvent.
The substitution of polyfluorinated groups into the peripheral
position of symmetrical porphyrazine and unsymmetrical seco-
porphyrazines informs high solubility in organic solvents such as
chloroform, dichloromethane, pyridine, and THF. The solubility of
3 in chloroform, DCM, THF, and acetone was determined as 44, 54,
60, and 63 mg/mL, respectively. But, it was not soluble in methanol.
The increased solubility might be because of the higher solubility of
pentafluorophenyl substituents in organic polar solvents. When the
polarities of the solvents are increased, the solubility of complexes
also increases as expected [19–21,26,46–48,50].
Fig. 2. [2,3,7,8,12,13,17,18-octakis(pentafluorophenyl)-2-seco-2,3-dioxoporphyrazine]
and metal derivatives [M = 2H, Cu(II), Zn(II) or Co(II)] (4–7).
The spectral properties of the novel magnesium, metal-free seco-
porphyrazine and metallated seco-porphyrazines (M = Cu, Zn, Co)
with eight pentafluorophenyl substituents at the periphery have
been presented in this work. The 40 peripheral fluorine atoms in
the structure increase the solubility of the complexes in halogenated
solvents, acetone and THF. Fluorinated metallated porphyrazines
have currently been receiving a great deal of attention due to their in-
teresting electron transport characteristics [12,51]. While unsubsti-
tuted tetrapyrrole compounds exhibit p-type behavior due to the
doping with electron accepting molecules, thin films of some metal
hexadecafluoro-tetrapyrrole compounds exhibit n-type behavior.
These properties resulted in a number of studies aiming at different
applications like photovoltaic cells, rectifying junction and gas sen-
sors. Also, fluorocarbons display enhanced hydrophobicity, chemical
resistance and thermal stability in comparison to their hydrocarbon
counterparts [43,52]. Consequently, porphyrazines reported here
can be proposed as active compounds for catalytic and photosensor
applications in homogeneous media [17,18,53].
In addition to these supportive results for the structures, mass
spectrometry results of pentafluorophenyl substituted porphyrazines
(3–7) gave the characteristic molecular ion peaks, at m/z: 1664.1
[M]+, 1674.2 [M]+, 1736.8 [M]+, 1738.7 [M]+ and 1731.1 [M]+, re-
spectively, confirming the proposed structures.
The most revealing data for tetrapyrrole systems are obtained by
their electronic spectra in solution. In the electronic absorption spec-
tra of the complexes (3, 5–7), Q bands were observed at 668, 676,
680, and 672 nm, respectively in chloroform. A second intense and
broad π–π* transition in the range 356–376 nm which is called
Soret or B band is also a characteristic band as expected for tetrapyr-
roles (Table 2). As a consequence of the change in the symmetry of
porphyrazine core (3) from D4h to C2v, the electronic absorption spec-
tra of 4 display a split in the Q band at 620 and 696 nm [49]. UV–vis
spectra of 5–7 in chloroform are shown in Fig. 3.
The aggregation behavior of porphyrazines in solution, which can
be followed effectively by absorption studies, is a good indication of
the interactions between the aromatic macrocycles of the porphyra-
zines. The aggregation behavior of 5 was investigated at different con-
centrations in chloroform (Fig. 4). In chloroform, as the concentration
was increased, the intensity of the Q-band absorption increased in paral-
lel, and there were no new bands because of the aggregated ones [50]. It is
seen that the Beer–Lambert law was obeyed for compound 5 for concen-
trations ranging from 3×10−5 to 2.5×10−6 mol dm−3 (Fig. 4). And also
the aggregation treatments of 5 were worked in dichloromethane at dif-
Acknowledgment
This work is supported by the Scientific Research Fund of Fatih
University under the project number P50021102_B.
ferent concentrations ranging from 3×10−5 to 2.5×10−6 mol dm−3
.
There were only slight differences in B and Q bands as nm and because
of the aggregated ones there were no new bands. UV–vis spectra of
Table 1
Elemental analysis results of 1–7.a
Compound
C
H
N
1
2
3
4
5
6
7
46.76 (46.85)
44.90 (44.98)
46.25 (46.17)
45.78 (45.90)
44.18 (44.27)
44.11 (44.23)
44.28 (44.39)
6.90 (6.83)
9.77 (9.84)
6.80 (6.73)
6.81 (6.69)
6.57 (6.45)
6.33 (6.45)
6.59 (6.47)
0.83 (0.71)
0.16 (0.12)
a
Required values are given in parentheses.
Fig. 3. UV–vis spectra of 5–7 in chloroform.

S. Kayaköy, E. Gonca / Inorganic Chemistry Communications 21 (2012) 28–31
31
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[32] Experimental data for compound 1: Yield: 1.65 g (64%). FT-IR, νmax/(cm−1):
2218 (C`N), 1662, 1614 (C_C, aromatic), 1575, 1512, 1465, 1380, 1340, 1275,
1161, 1119, 1055, 936, 902, 844, 706, 675, 588. 13C NMR (δ, ppm): 107.5, 118.5,
121.6, 137.4, 142.7, 143.3. 19F NMR (δ, ppm): −144.6 (o-fluoro), −154.4 (p-fluoro),
Fig. 4. UV–vis spectra of 5 in chloroform at various concentrations.
−163.6 (m-fluoro). MS (ESI) m/z: 410.9 [M]+
.
[33] Experimental data for compound 2: Yield: 0.31 g (48%). FT-IR, νmax/(cm−1):
3330 (N\H), 1664, 1610 (C_C, aromatic), 1570, 1515, 1467, 1382, 1346, 1272,
1166, 1125, 1063, 942, 908, 842, 708, 671, 586. 1H NMR (δ, ppm): 4.80 (br s,
3H, NH). 13C NMR (δ, ppm): 107.5, 125.3, 137.4, 142.2, 143.3, 164.3. 19F NMR
(δ, ppm): −144.8 (o-fluoro), −154.5 (p-fluoro), −163.8 (m-fluoro). MS (ESI)
m/z: 427.8 [M]+
.
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[38] Experimental data for compound 3: Yield: 117 mg (56%). FT-IR, νmax/(cm−1):
1660, 1610 (C_C, aromatic), 1572, 1518, 1461, 1386, 1341, 1278, 1161, 1118,
1052, 936, 906, 843, 708, 671, 586. 13C NMR (δ, ppm): 107.2, 118.8, 121.1,
137.8, 142.3, 143.7. 19F NMR (δ, ppm): −142.7 (o-fluoro), −152.5 (p-fluoro),
−161.6 (m-fluoro). MS (ESI) m/z: 1664.1 [M]+
.
[39] Experimental data for compound 4: Yield: 114 mg (68%). FT-IR, νmax/(cm−1):
3335 (N\H), 1722 (C_O), 1664, 1614 (C_C, aromatic), 1585, 1509, 1414,
1344, 1302, 1271, 1184, 1123, 1066, 906, 842, 705, 686, 582. 1H NMR (δ, ppm):
−1.35 (br s, 2H, NH). 13C NMR (δ, ppm): 107.4, 118.7, 121.3, 137.6, 142.1,
143.5. 19F NMR (δ, ppm): −141.5 (o-fluoro), −152.3 (p-fluoro), −161.8 (m-fluoro).
Fig. 5. UV–vis spectra of 7 in various solvents.
MS (ESI) m/z: 1674.2 [M]+
.
[40] Experimental data for compound 5: Yield: 94 mg (54%). FT-IR, νmax/(cm−1):
1720 (C_O), 1666, 1614 (C_C, aromatic), 1580, 1512, 1415, 1348, 1305, 1274,
References
1188, 1126, 1075, 904, 840, 705, 685, 582. MS (ESI) m/z: 1736.8 [M]+
.
[41] Experimental data for compound 6: Yield: 129 mg (74%). FT-IR, νmax/(cm−1):
1718 (C_O), 1662, 1608 (C_C, aromatic), 1585, 1502, 1408, 1344, 1309, 1272,
1184, 1126, 1066, 903, 847, 703, 686, 582. 13C NMR (δ, ppm): 107.4, 118.6,
121.4, 137.6, 142.5, 143.8. 19F NMR (δ, ppm): −142.8 (o-fluoro), −152.3 (p-
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