Synthesis, structural and spectral properties of novel octakis(3,5-bis- trifluoromethyl-benzylthio) substituted porphyrazine derivatives

Article abstract of DOI:10.1016/j.jfluchem.2010.09.002

[Octakis(3,5-bis-trifluoromethyl-benzylthio)porphyrazinato] magnesium carrying eight (3,5-bis-trifluoromethyl-benzylthio) groups on the peripheral positions have been synthesized by cyclotetramerization of 1,2-bis(3,5-bis- trifluoromethyl-benzylthio)maleonitrile in the presence of magnesium butanolate. Its demetalation by the treatment with trifluoroacetic acid resulted in the metal-free derivative. 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.

Full text of DOI:10.1016/j.jfluchem.2010.09.002

Journal of Fluorine Chemistry 131 (2010) 1322–1326
Contents lists available at ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
Synthesis, structural and spectral properties of novel
octakis(3,5-bis-trifluoromethyl-benzylthio) substituted porphyrazine derivatives
*
Didar Koc¸ak, 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:
[Octakis(3,5-bis-trifluoromethyl-benzylthio)porphyrazinato] magnesium carrying eight (3,5-bis-tri-
fluoromethyl-benzylthio) groups on the peripheral positions have been synthesized by cyclotetramer-
ization of 1,2-bis(3,5-bis-trifluoromethyl-benzylthio)maleonitrile in the presence of magnesium
butanolate. Its demetalation by the treatment with trifluoroacetic acid resulted in the metal-free
derivative. 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 2010 Elsevier B.V. All rights reserved.
Received 29 July 2010
Received in revised form 2 September 2010
Accepted 4 September 2010
Available online 21 September 2010
Keywords:
3,5-Bis-trifluoromethyl-benzylthio
Porphyrazine
19F NMR spectroscopy
Zinc
Cobalt
1. Introduction
Starting with eight alkylthio substituents appending to
porphyrazine derivatives by Hoffman and co-workers [13], in
Peripherally functionalized porphyrazines (tetraazaporphyr-
ins) and related macrocycles have been a subject of great interest
due to various high synthetic possibilities, numerous technological
applications, and biological importance in coordination chemistry
[1–4]. Porphyrazines may be considered to be structural hybrids of
the well-studied porphyrins and phthalocyanines. As such, they
provide an excellent opportunity to explore the subtle effects of
ligand structure on the properties of coordinated metal ions in
porphyrinic complexes. In addition, tetraazaporphyrins reveal
various unique properties (optical, electrochemical, and catalytic)
which make them of interest in their own right [5–7].
When symmetrical octakis functionalization of the main core is
demanded, planar tetrapyrrole derivatives with eight peripheral
positions are the common starting substances [8–10]. The metal
ions that have been incorporated into porphyrazine centrally and
peripherally express new ways to induce, modify and control
molecular properties [11,12]. It is well-known that there are long-
range interactions between different parts of the molecule because
which the presence of soft S donor atoms perform an important
function in affecting the solid-state interactions, a large series of
derivatives with physical and chemical properties comparable to
those of phthalocyanines have been assigned. Metalloporphyr-
azines have also been investigated to show optical limiting effects
comparable with phthalocyanines and naphthalocyanine deriva-
tives [14]. Substitution of various units on the peripheral positions
of porphyrazines has been performed either starting with an
unsaturated dinitrile precursor with this unit attached at the
beginning (e.g., dimethylaminoethylthio [13], tosylaminoethylthio
[15]) or a porphyrazine that has been prepared at first with reactive
functional groups and then additional groups (e.g., ferrocene [16],
benzo-15-crown-5 [9,10], pyridine [17]) that have been incorpo-
rated by further condensation reactions.
More recently our group has been mainly interested in the
preparation of new soluble phthalocyanine and porphyrazine
derivatives. Among these, phthalocyanines with fused to or
attached through bridges to macrocyclic structures and porphyr-
azines with long chains or functional groups such as quaternizable
amino groups [18], crown ethers [19], ferrocenes [20], triphenyl-
phosphine [21], 4-tert-buthylphenylthio [22] and tosylami-
noethylthio [23] can be cited. Moreover, we have synthesized
novel seco-porphyrazines substituted with (1-naphthyl) [24], (4-
biphenyl) groups [25] on the peripheral positions as encountered
by Barrett and co-workers, with peripheral amino derivatives [26].
We have also reported new porphyrazines with bulky electron rich
of the diffuse nature of porphyrazine’s
p electronic structure. Thus,
the electronic and magnetic properties of these molecular
compounds should be very reactive to the nature of substituent
ions and peripheral complexes.
* 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 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2010.09.002

[
D. Koc¸ak, E. Gonca / Journal of Fluorine Chemistry 131 (2010) 1322–1326
1323
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.
substituents such as 1-naphthylmethylthio [27], 9-anthracenyl-
methylthio units [28].
(3b). Further reaction of this product with copper(II) acetate,
zinc(II) acetate and cobalt(II) acetate has led to the metal
porphyrazinates (M = Cu, Zn, Co) (3c–3e) (Fig. 1).
All new compounds were identified through several spectro-
scopic techniques such as FT-IR, 1H NMR, 19F NMR, 13C NMR,
UV–vis, mass and elemental analysis. The spectroscopic data of
desired products were in accordance with the assigned
structures.
Fluorinated metallo tetrapyrrol compounds form a class of
coordination compounds which have currently been receiving a
great deal of attention owing to their interesting electron transport
characteristics [29–31]. Furthermore, fluorocarbons display en-
hanced thermal stability, hydrophobicity, chemical resistance, and
lipophobicity in comparison to their hydrocarbon counterparts
[32,33].
Elemental analyses correspond closely with the values calcu-
lated for (2, 3a–3e) (Table 1).
In this study, we have synthesized novel soluble porphyrazines
with eight (3,5-bis-trifluoromethyl-benzylthio) substituents
appended to the peripheral positions. Magnesium porphyrazinate
has been synthesized for the first time by cyclotetramerization of
1,2-bis(3,5-bis-trifluoromethyl-benzylthio)maleonitrile in the
presence of magnesium butanolate. The conversion of magnesium
porphyrazinate into the metal-free derivative was achieved by the
treatment with relatively strong acids (e.g., trifluoroacetic acid).
Further reaction of this product with copper(II) acetate, zinc(II)
acetate and cobalt(II) acetate has led to the metal porphyrazinates
(M = Cu, Zn, Co). These novel compounds have been characterized
In the FT-IR spectrum of 1,2-bis(3,5-bis-trifluoromethyl-ben-
zylthio)maleonitrile (2) stretching vibration of CBB N is observed at
2227 cmꢀ1, the aromatic and aliphatic C–H peaks are around
2865–3085 cmꢀ1 and the aromatic C55C peak is at 1619 cmꢀ1
.
These values comply with those reported in the literature for
similar compounds [27]. After the conversion of dinitrile derivative
(2) to porphyrazine (3a), the sharp CBB N vibration around
2227 cmꢀ1 disappeared. The N–H stretching absorption of the
inner core of the metal-free porphyrazine (3b) was observed
around 3330 cmꢀ1. FT-IR spectra of all porphyrazines derivatives
(3a–3e) showed the aromatic and aliphatic C–H peaks are in the
range 2850–3085 cmꢀ1 and the aromatic C55C peak is at 1605–
1667 cmꢀ1 [27].
by elemental analysis, together with FT-IR, 1H NMR, 13C NMR, 19
NMR, UV–vis and mass spectral data.
F
2. Results and discussion
The N–H protons of the metal-free porphyrazine (3b) were also
identified in the 1H NMR spectrum with a broad peak at
The starting material for these novel porphyrazine structures
with eight (3,5-bis-trifluoromethyl-benzylthio) units bound to the
periphery through flexible methylthio chains is 1,2-bis(3,5-bis-
trifluoromethyl-benzylthio)maleonitrile (2) which was obtained
from the disodium salt of dithiomaleonitrile (1) and 3,5-bis(tri-
fluoromethyl)benzyl chloride (Scheme 1). The orange colored
product (2) was obtained in 58% yield. The presence of electron-
donating S-groups is expected to give porphyrazines absorbing
electromagnetic radiation just in the same range as phthalocya-
nines [18,35,36]. The conversion of 1,2-bis(3,5-bis-trifluoro-
methyl-benzylthio)maleonitrile into porphyrazine was achieved
by the template effect of magnesium butanolate (Scheme 1). The
cyclotetramerization gave the blue-green [octakis(3,5-bis-trifluor-
omethyl-benzylthio) porphyrazinato]magnesium (3a) (Fig. 1). It is
soluble in chloroform, dichloromethane, toluene and acetone, but
insoluble in polar hydrocarbon solvents such as n-hexane. The
conversion of 3a into 3b 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 porphyrazinate (3a) to the demetalated porphyrazine
d
= ꢀ0.95 ppm, presenting the typical shielding of inner core
protons, which is a common feature of the 1H NMR spectra of
metal-free porphyrazines [15,18–20,23,27]. In the 1H NMR spectra
of diamagnetic porphyrazines 3a, 3b and 3d, three different types
of protons are clearly seen: two singlets around 7–8 ppm
corresponding to aromatic protons and a singlet at 4.65 ppm
(3a), 5.12 ppm (3b) or 4.86 ppm (3d) for methylene protons. The
ratio of the integral values 3:2 also confirms the proposed
structure. In the 13C NMR spectra of diamagnetic porphyrazines
3a, 3b and 3d, eight different single chemical shifts for carbon
atoms are clearly seen. 19F NMR spectra of diamagnetic porphyr-
azines 3a, 3b and 3d show a single chemical shift for trifluor-
omethyl groups at ꢀ63.44, ꢀ63.42 and ꢀ63.40 ppm, respectively.
Electronic spectra were very useful to establish the structure of
the porphyrazines (3a–3e). UV–vis spectra of porphyrazine core
are dominated by two intense bands, the Q-band around 670 nm
and the B-band in the near UV region around 350 nm, both
correlated to
p
!
p* transitions [12,15]. The presence of an
electron-donating group on the periphery causes a bathochromic
shift on Q-bands. UV–vis spectra of metalloporphyrazines (3a, 3c–

[
D. Koc¸ak, E. Gonca / Journal of Fluorine Chemistry 131 (2010) 1322–1326
Fig. 1. Octakis (3,5-bis-trifluoromethyl-benzylthio) substituted porphyrazines.
Table 1
3. Experimental
Elemental analyses results of 2 and 3a–3e.a
IR spectra were recorded on a Perkin Elmer Spectrum One FT-IR
(ATR sampling accessory) spectrophotometer, electronic spectra on
Compound
C
H
N
2
44.57 (44.45)
44.15 (44.00)
44.55 (44.41)
43.18 (43.29)
43.38 (43.26)
43.50 (43.38)
1.82 (1.70)
1.80 (1.68)
1.91 (1.78)
1.74 (1.65)
1.76 (1.65)
1.54 (1.65)
4.60 (4.71)
4.53 (4.66)
4.61 (4.71)
4.70 (4.59)
4.47 (4.59)
4.71 (4.60)
a
Unicam UV2 spectrophotometer. Elemental analyses were
3a
3b
3c
3d
3e
recorded on a Thermo Finnigan Flash EA 1112 instrument. 1H
NMR, 13CNMR and 19F NMRspectra, weretakeninCDCl3 solutionsat
400,000, 100,577 and 376,308 MHz, respectively, recorded on a
Bruker Ultra Shield Plus 400 MHz spectrometer. Chemical shifts
a
refertoTMS(1HNMRand13CNMR)andfluorotrichloromethane(19
F
Required values are given in parentheses.
NMR) as the 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. All starting materials were purchased
Table 2
UV–vis data for the porphyrazines in chloroform.
Compound
l (/nm) (log e )
/dm3 molꢀ1 cmꢀ1
[i(g._2)TD$FIG]
3a
3b
3c
3d
3e
378 (4.71)
336 (4.65)
364 (4.64)
348 (4.40)
344 (4.33)
668 (4.70)
652 (4.45)
664 (4.49)
680 (4.36)
678 (4.38)
715 (4.48)
3e in CHCl3) prepared in the present work exhibited intense single
Q-band absorptions around 668–680 nm and B bands in the near
UV region around 344–378 nm (Table 2). For metal-free derivative
(3b), Q-band is split into two peaks at 652 and 715 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 3a and 3b in chloroform are shown in Fig. 2. An absorbance vs.
concentration study indicated that due to (3,5-bis-trifluoromethyl-
benzylthio) units, the aspect of the UV–vis spectrum of the free
ligand in Fig. 2, with broad and low intensity Q-bands does not
exclude the presence of aggregation. UV–vis spectra of 3c in
solvents of different polarity (dichloromethane, ethanol, chloro-
form and pyridine) are given in Fig. 3. There is almost no difference
with respect to the changes in the nature of the solvent.
Fig. 2. UV–vis spectra of 3a and 3b in chloroform.

[
D. Koc¸ak, E. Gonca / Journal of Fluorine Chemistry 131 (2010) 1322–1326
1325
7.35 (s, 16H, Ar–H), 4.65 (s, 16H, CH2–S). 13C NMR (
d
, ppm) 40.0,
113.4, 115.6, 121.6, 124.6, 129.1, 131.2, 140.2. 19F NMR (
d, ppm)
ꢀ63.44. MS (ESI): (m/z): 2402.5 [M]+.
3.3. [2,3,7,8,12,13,17,18- Octakis(3,5-bis-trifluoromethyl-benzylthio)
H
21, H23 porphyrazine] (3b)
3a (120 mg, 0.05 mmol) was dissolved in the minimum amount
of trifluoroaceticacid (ꢁ4.00 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. 3b
was obtained by column chromatography (SiO2, CH3OH:CHCl3,
1:30, v/v). Yield: 76 mg (64%). FT-IR,
n
max/(cmꢀ1): 3330 (N–H),
3070–3030 (CH, aromatic), 2930–2850 (CH, aliphatic), 1660, 1612
(C55C, aromatic), 1584, 1508, 1412, 1348, 1304, 1278, 1186, 1124,
Fig. 3. UV–vis spectra of 3c in various solvents.
1066, 903, 844, 704, 686, 582. 1H NMR (
d, ppm) 7.66 (s, 8H, Ar–H),
from major suppliers and used without any further purification. The
homogeneity of the products was tested in each step by TLC.
The disodium salt of dithiomaleonitrile (1) was prepared
according to the previously reported procedures [34].
7.33 (s, 16H, Ar–H), 5.12 (s, 16H, CH2–S), ꢀ0.95 (br s, 2H, NH). 13
C
NMR (
d, ppm) 40.2, 113.2, 115.4, 121.7, 124.5, 129.0, 131.3, 140.4.
19F NMR (
d
, ppm) ꢀ63.42. MS (ESI): (m/z): 2379.1 [M]+.
3.4. General procedure for metalloporphyrazines (3c–3e)
3.1. Synthesis of 2,3-bis(3,5-bis-trifluoromethyl-
benzylthio)maleonitrile (2)
3b (119 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 4 h. Then, the precipitate
composed of the crude product and the excess metal salt was
filtered. The precipitate was treated with CHCl3 and the insoluble
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 (3c–3e) were obtained by column
chromatography (SiO2, CH3OH:CHCl3, 1:50, v/v).
Disodium salt of dithiomaleonitrile (1) (1.12 g, 6.00 mmol) was
mixed with 3,5-bis(trifluoromethyl)benzyl chloride (3.94 g,
15.0 mmol) in methanol (50.0 mL) and refluxed under nitrogen
for about 18 h. When MeOH was evaporated, the remaining
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.
After evaporation of the solvent the colored product was extracted
with refluxing n-hexane to remove any excess 3,5-bis(trifluor-
omethyl)benzyl chloride. The product was an orange colored and
was very soluble in chloroform, dichloromethane and acetone, but
3.4.1. [2,3,7,8,12,13,17,18-Octakis(3,5-bis-trifluoromethyl-
insoluble in n-hexane. Yield: 2.07 g (58%). FT-IR,
3085–3040 (CH, aromatic), 2935–2865 (CH, aliphatic), 2227
n
max/(cmꢀ1):
benzylthio) porphyrazinato] Cu(II) (3c)
Yield: 51 mg (42%). FT-IR, n
max/(cmꢀ1): 3070–3030 (CH,
(CBB N), 1667, 1619 (C55C, aromatic), 1590, 1510, 1412, 1350,
aromatic), 2920–2850 (CH, aliphatic), 1660, 1605 (C55C, aromatic),
1584, 1508, 1408, 1346, 1302, 1275, 1184, 1122, 1066, 906, 846,
706, 682, 586. MS (ESI): (m/z): 2441.9 [M]+.
1303, 1276, 1180, 1118, 1059, 901, 845, 705, 681, 585. 1H NMR (
d
,
ppm) 7.58 (s, 2H, Ar–H), 7.32 (s, 4H, Ar–H), 4.68 (s, 4H, S–CH2). 13
C
NMR (
d, ppm) 40.2, 113.7, 115.8, 121.8, 124.5, 129.2, 131.0, 140.4.
19F NMR (
d
, ppm) ꢀ63.40. MS (ESI): (m/z): 594.9 [M]+.
3.4.2. [2,3,7,8,12,13,17,18-Octakis(3,5-bis-trifluoromethyl-
benzylthio) porphyrazinato] Zn(II) (3d)
3.2. [2,3,7,8,12,13,17,18-Octakis(3,5-bis-trifluoromethyl-benzylthio)
Yield: 46 mg (38%). FT-IR, n
max/(cmꢀ1): 3075–3035 (CH,
porphyrazinato] Mg(II) (3a)
aromatic), 2928–2852 (CH, aliphatic), 1662, 1606 (C55C, aromatic),
1580, 1502, 1408, 1344, 1302, 1275, 1182, 1122, 1066, 905, 848,
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.
706, 685, 588. 1H NMR (
d
, ppm) 7.65 (s, 8H, Ar–H), 7.33 (s, 16H, Ar–
, ppm) 40.0, 113.3, 115.8, 121.4,
, ppm) ꢀ63.40. MS (ESI): (m/
H), 4.86 (s, 16H, CH2–S). 13C NMR (
d
1,2-Bis(3,5-bis-trifluoromethyl-benzylthio)maleonitrile
(2)
124.6, 129.0, 131.1, 140.1. 19F NMR (
d
(297 mg, 0.50 mmol) was added to this solution and the mixture
was refluxed for about 12 h. The dark green 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 the solvent was
z): 2443.6 [M]+.
3.4.3. [2,3,7,8,12,13,17,18-Octakis(3,5-bis-trifluoromethyl-
benzylthio) porphyrazinato] Co(II) (3e)
Yield: 55 mg (45%). FT-IR,
n
max/(cmꢀ1): 3072–3032 (CH,
evaporated,
a
colored product was obtained. Finally, pure
aromatic), 2928–2857 (CH, aliphatic), 1664, 1608 (C55C, aromatic),
1582, 1503, 1408, 1344, 1300, 1275, 1184, 1122, 1066, 903, 846,
708, 682, 584. MS (ESI): (m/z): 2436.1 [M]+.
porphyrazine was obtained by column chromatography (SiO2,
CH3OH:CHCl3, 1:50, v/v). The blue-green colored product was
soluble in chloroform, dichloromethane, acetone and toluene, but
n
max/(cmꢀ1):
Acknowledgement
insoluble in n-hexane. Yield: 219 mg (73%). FT-IR,
3075–3035 (CH, aromatic), 2925–2855 (CH, aliphatic), 1665, 1608
(C55C, aromatic), 1580, 1505, 1408, 1345, 1300, 1273, 1184, 1120,
1064, 905, 848, 708, 684, 588. 1H NMR (
d, ppm) 7.64 (s, 8H, Ar–H),
This work was supported by the Scientific Research Fund of
Fatih University under the project number P50020901_1.

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