Synthesis and spectral properties of the metallophthalocyanines with the fragments of substituted pyrazoles

Article abstract of DOI:10.1134/S1070363213040233

By the reaction of 4-bromphthalonitrile with corresponding 1-phenyl-3-methyl-5-hydroxy- and 1-p-sulfophenyl-3-methyl-5-oxypyrazolaes the substituted phthalonitriles were synthesized and converted into metallophthalocyanines with the fragments of substitut

Full text of DOI:10.1134/S1070363213040233

ISSN 1070-3632, Russian Journal of General Chemistry, 2013, Vol. 83, No. 4, pp. 744–751. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © V.P. Kulinich, R.A. Badaukaite, T.V. Tikhomirov, G.P. Shaposhnikov, 2013, published in Zhurnal Obshchei Khimii, 2013, Vol. 83,
No. 4, pp. 662–669.
Synthesis and Spectral Properties
of the Metallophthalocyanines with the Fragments
of Substituted Pyrazoles
V. P. Kulinich, R. A. Badaukaite, T. V. Tikhomirov, and G. P. Shaposhnikov
Scientific-Research Institute of Macroheterocyclic Compounds,
Ivanovo State University of Chemical Technology, pr. Engelsa 7, Ivanovo, 153000 Russia
e-mail: ttoc@isuct.ru
Received March 1, 2012
Abstract—By the reaction of 4-bromphthalonitrile with corresponding 1-phenyl-3-methyl-5-hydroxy- and 1-p-
sulfophenyl-3-methyl-5-oxypyrazolaes the substituted phthalonitriles were synthesized and converted into
metallophthalocyanines with the fragments of substituted pyrazoles. The compounds obtained were identified
1
using the data of elemental analysis, gas chromatography–mass spectrometry, IR, H NMR, and electronic
spectroscopy. The influence of the peripheral environment of the phthalocyanine ligand in the resulting metal
complexes on the spectral and other properties of the latter was revealed.
DOI: 10.1134/S1070363213040233
Among the multitude of substituted phthalo-
cyanines, of special interest are the compounds con-
taining biophoric fragments on the periphery of the
macrocycle, in particular, the fragmrnts of substituted
pyrazoles. It is known that a pyrazole heterocycle is a
part of many drug molecules exhibiting anti-
inflammatory, sedative, and bacteriostatic effect [1], as
well as of high-performance dyes with pronounced
fungicidal activity against specific fungi growing on
textiles and causing destruction of the latter [2].
According to [1], compounds II and III exist in two
tautomeric forms: hydroxy- (a) and oxo- (b) (Scheme 1).
Scheme 1.
H
N
H
N
O
CH3
HO
CH3
N
N
This paper presents the data on the synthesis and
study of metallophthalocyanines containing methyl-
phenylhydroxypyrazole residues as substituents.
Х
Х
a
b
An effective method for preparing substituted
phthalocyanines is based on nitriles [3], and therefore
our first task was to obtain the corresponding
phthalonitriles with pyrazole substituents. As starting
compound for this synthesis we used 4-bromphthalo-
nitrile (I). The electron-withdrawing groups (CN) at
the benzene ring of compound I provide sufficiently
effective positive charge on the carbon atom bound to
the bromine, which facilitates replacement of the latter
at the action of nucleophilic reagents [4]. As the
reagents we used mainly 1-phenyl-3-methyl-5-hydroxy
(oxo)-pyrazole (II) and 1-p-sulfophenyl-3-methyl-5-
hydroxy(oxo)-pyrazole (III).
Х = Н (IIa, IIb); SO3H (IIIа, IIIb).
The tautomeric equilibrium can be shifted in one or
another direction, depending on the process conditions.
In particular, bases, including potassium carbonate
used by us, catalyze enolization [5, 6]. In addition, it
was noted [7] that the keto ↔ enol equilibrium in polar
solvents is shifted to the right. Based on the above, we
assume that in the process conditions used by us
(DMF, K2CO3) the most likely nucleophilic agents are
compounds IIa and IIIa. As will be shown below, this
assumption was experimentally confirmed in the study
744

SYNTHESIS AND SPECTRAL PROPERTIES OF THE METALLOPHTHALOCYANINES
745
Т
of the synthesized nitriles IV, V and respective metallo-
phthalocyanines VI–IX.
Quantum-chemical calculations performed by us
showed that the highest values of the effective negative
charges in the molecule of 1-phenyl-3-methyl-5-
oxypyrazole are on the oxygen atom of the hydroxy
group (–0.219) and the carbon atom in the position 4
of the pyrazole ring (–0.260).
0.179
H
H
–
0
–
-0.26
-0.219
C
C
O
CH
СH
O
33
4
4
0.228
3
H
3
H
C
C–
-0.072
CC55
0.097
1.42
ν, cm–1
1.37
-0.089
1
2
1
2
Fig. 1. IR spectrum of nitrile IVa.
N
N
N
–
N
–
-0.120
1.36
To confirm the structure of the synthesized
phthalonitriles IVa and Va we used the data of the
elemental analysis, gas chromatography–mass spectro-
metry, IR and 1H NMR spectroscopy.
PPhh
Accordingly, the substituted pyrazoles IIa and IIIa
can act as both O- and C-nucleophiles, in particular,
their reaction with the nitrile I can occur in two ways
(Scheme 2, routes a and b). However, the above
reaction conditions, in which the hydroxy group is
activated, suggests that the substitution of bromine in
nitrile I takes mainly the route A. In particular, the
reaction is carried out in DMF medium in the presence
of potassium carbonate, which serves as deprotonating
agent [8] with respect to the hydroxy groups of
compounds IIa, IIIa.
Thus, in the chromatogram of nitrile IVa a strong
single peak was recorded. The mass spectrum of this
compound has a peak at m/z 300 corresponding to the
main molecular ion, as well as several weak signals of
fragmentation products.
_O
NC
NC
O
_
_
CH3
N
N
N
N
N
N
The required duration for the reaction with 1-p-
sulfophenyl-3-methyl-5-oxypyrazol III as a nucleo-
phile was monitored by the total consumption of
phthalonitrile I in the reaction mixture: the sample of
the reaction mixture becomes almost completely
soluble in water. The same reaction duration (2 h) was
applied in the synthesis of the phthalonitrile IVa. The
dimethylformamide solution of the obtained phthalo-
nitrile was separated from the inorganic impurities
(KBr, K2CO3) by filtration, DMF was removed in a
vacuum at a temperature of 90–100°C. Final purifica-
tion of the phthalonitriles was performed using
chromatography on alumina, while eluting with DMF
(nitrile IV) or a mixture of DMF and water in a ratio
1: 1, v/v (nitrile V). Difference in mobility of nitriles
IVa, Va, and IVb, Vb allowed us to isolate them in
individual form at the chromatographic purification.
The proportion of nitriles IVb and Vb did not exceed
3%.
m/z 173
m/z 157
m/z 285
Analysing the IR spectrum of nitrile IVa (Fig. 1),
we should note retention of the stretching vibration
band (2230 cm–1) of the cyano group which is slightly
displaced (Δν = 6 cm–1 ) in the low-frequency region
compared to the spectrum of parent 4-bromophthalo-
nitrile I. The substitution of bromine resulted in the
disappearance in the IR spectrum of the band of stret-
ching vibrations CAr–Br (645 cm–1), and appearance of
new bands, among which these at 2852 and 2923 cm–1,
related to the symmetric and asymmetric stretching
vibrations of CH in methyl groups, and the band at
1668 cm–1, corresponding to the N–N stretching
vibrations in the pyrazole [9] are the most clear. In the
IR spectrum of nitrile Va containing sulfo group,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 4 2013

746
KULINICH et al.
Scheme 2.
H
CH3
N
O
NC
NC
N
H
CH3
Х
R
a
N
NC
NC
Br
HO
IVa, Va
M(OAc)2
N
+
_HBr
H3C
HO
b
NC
NC
N
N
Х
I
II, III
Х
IVb, Vb
R
N
N
N
M
N
R
N
N
R
N
N
R
MPcR4
X = H (II), SO3H (III); X = H, M = Co (VI), Cu (VII), Ni (VIII); X = SO3H, M = Co (IX).
besides the above bands are the bands at 1035 cm–1
related to the S=O symmetric stretching vibrations and
at 1130 cm–1 of the asymmetric stretching vibrations.
The IR spectra of the synthesized nitriles IVa and Va
practically do not contain absorption bands cor-
responding to the carbonyl and hydroxyl groups, which
confirm the above assumption of participation in
nucleophilic substitution predominantly of enol forms
of the substituted pyrazoles IIa and IIIa and the
reaction proceeding by the route a (Scheme 2).
1H NMR spectrum of the nitrile IVa (Fig. 2) was
compared with the theoretically calculated spectra of
nitriles with peripheral fragments A, B, and C.
The comparison of the positions of the signals of
aromatic and aliphatic protons leads to the following
conclusions. The signals in the weak field 7.75, 7.92,
and 7.31–7.54 ppm refer to the benzene ring protons of
the phthalonitrile and phenyl substituent. In the high
field there is a strong signal at 2.38 ppm of the protons
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 4 2013

SYNTHESIS AND SPECTRAL PROPERTIES OF THE METALLOPHTHALOCYANINES
747
H3C
H3C
H
NC
NC
O
CH3
N
N
N
NC
NC
NC
NC
N N
N
HO
O
B
C
A
of methyl group. The positions of these signals are in
good agreement with the theoretically calculated spec-
trum corresponding to the structure of A.
1 h. The urea is required to create a melt, and the
ammonia evolved at the urea decomposition is known
[10] to be involved in the formation of phthalocyanine.
Complexes of copper and nickel in these conditions
formed in trace amounts. This feature (that is, only the
formation of the cobalt complexes) was observed
earlier for other sulfophthalocyanine precursors [8],
but it is not explained so far. The cobalt complex IX
containing sulfo group after synthesis was washed with
hydrochloric acid at gradually decreased concentration
from 18 to 5% to colorless filtrates. The residue was
dried and the target product was extracted with water,
the aqueous solution was then evaporated to dryness.
Structures B and C are excluded according to the
following reasons:
(a) There are no signals in the spectrum of the
protons of the hydroxyl group (4.24 ppm) (structure
B), and the proton at the carbon atom C4 of the
pyrazole ring matching structure C.
(b) The signals of the protons of the methyl group
in structure C theoretically should appear at 1.90 ppm,
while they are fixed at 2.38 ppm (Fig. 2), which is
closer to the structure of A (2.22 ppm).
(c) The signal of the proton at the carbon atom C4
of the pyrazole ring (5.88 ppm) is close to the
theoretical value for the structure A (6.04 ppm).
Final purification of the synthesized complexes VI–
IX was performed by chromatography on alumina,
eluting with chloroform (VI–VIII) or 1-propanol with
1% solution of aqueous ammonia in a volume ratio of
1: 2 (IX).
Thus, the set of the experimental data confirms our
assumption that in the synthesis of the phthalonitriles
with pyrazole substituent the major products are phenyl-
methyl pyrazolyloxy-substituted compounds IVa and
Va.
The isolated metallophthalocyanines VI–IX are
dark blue crystalline substances. Complexes VI–VIII
not containing sulfo group are readily soluble in
organic solvents of low polarity. Complex IX
containing sulfo group is soluble in DMF, water, and
aqueous alkali. To identify them we used elemental
Using the obtained nitriles IVa and Va we synt-
hesized the corresponding substituted metallophthalo-
cyanines VI–IX in accordance with the Scheme 2
(route a). The synthesis of metallophthalocyanines VI–
VIII not containing sulfo group was performed by
heating the corresponding substituted nitrile IVa with
anhydrous copper, cobalt or nickel acetate at a tem-
perature of 190–195°C for 45–60 min.
A solid reaction mixture isolated after the synthesis
was thoroughly crushed, washed first with 18%
aqueous solution of HCl, then with water to neutral
filtrates. The residue was dried and the target com-
plexes were extracted from it with chloroform in a
Soxhlet apparatus.
When using sulfophthalonitrile Va, we succeeded
to get only cobalt complex IX by fusing Va with
anhydrous cobalt acetate and urea at 190–195°C for
δ, ppm
Fig. 2. 1H NMR spectrum of nitrile IVa.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 4 2013

748
KULINICH et al.
Т
D
ν, cm–1
Fig. 3. IR spectrum of copper phthalocyanine VII.
λ, nm
Fig. 4. EAS of copper complex VII in chloroform.
1
analysis, vibration, electronic, and H NMR spec-
troscopy.
The good solubility of the synthesized complexes
VI–IX allowed us to analyze the electron absorption
spectra (EAS) of their solutions in a wide range of
solvents (see the table). As can be seen from the table
and Figs. 4 and 5, the EAS in organic solvents (chloro-
form, DMF) are characterized by an intense band (Q-
band) in the wavelength region of 660–677 nm due to
π–π* electron transition in the phthalocyanine macro-
ring. In addition to the main peak, there is a shoulder
or a low-intensity band at 600–645 nm on the short-
wavelength slope of the spectral curve.
In the IR spectrum of complex VII (Fig. 3) we must
first identify the bands of stretching vibrations of the
CH methyl groups mentioned above in the analyzis of
phthalonitriles IVa and Va; N–N bonds of pyrazole
heterocycle, and N–CPh bond; in the spectrum of the
complex IX containing sulfo group r additional bands
appea of symmetric and asymmetric stretching vibra-
tions of the S=O in aromatic sulfonic acids.
1
In the H NMR spectrum of the nickel complex
VIII the signals in the weak field at 7.87 and 7.73 ppm
refer to the protons of benzene ring of the
phthalocyanine ligand, and at 7.55 and 7.46 ppm, to
the protons of the phenyl substituent at the pyrazole
heterocycle. The signals in the strong field at 2.20 and
2.39 ppm belong to the protons of the methyl groups.
We succeeded to record the Soret band in the
ultraviolet region (340 and 352 nm) for the copper
complex VII in chloroform (Fig. 4) and cobalt
complex IX in DMF (Fig. 5). This band is known [11]
to be genetically linked with the absorption of
isoindole fragments. The position of the Q-band
Position of the bands in the electron absorption spectra of complexes VI–IX
λmax, nm (Irel)
Comp. no.
chloroform
DMF
H2O
–
0.5% NaOH
–
H2SO4
670:607 w
(1.00:0.31)
663:600 w
(1.00:0.33)
777:690 sh:415 w
(1.00:0.52:0.57)
VI
677:645 sh:611 w:340
(1.00:0.29:0.29:0.64)
660:640 sh:605 w
(1.00:0.37:0.33)
–
673:640 inf:610 sh
(1.00:0.41:0.36)
669:640
–
–
–
–
788:745 sh:700 w:420 w
(1.00:0.46:0.32:0.36)
776:690 sh:420
VII
VIII
IX
(1.00:0.80)
(1.00:0.28:0.31)
668:608 sh:352
(1.00:0.35:0.50)
628:679 inf
(1.00:0.80)
640:690 w
(1.00:0.93)
772:690 sh:412
(1.00:0.43:0.31)
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SYNTHESIS AND SPECTRAL PROPERTIES OF THE METALLOPHTHALOCYANINES
749
D
D
λ, nm
λ, nm
Fig. 6. EAS of complex IX: (1) in water, (2) in 0.5%
NaOH, (3) in 0.25% NaOH.
Fig. 5. EAS of cobalt complex IX in DMF.
depends on the nature of the metal. In the spectrum of
the copper complex VII the Q-band is shifted red by
4–17 nm in comparison with the cobalt (VI) and nickel
(VIII) complexes (see the table). Compared to the
corresponding unsubstituted complexes [12], this band
in DMF has a small red shift (up to 5 nm).
characteristic property of the synthesized metal
complexes is that the value of this displacement is
smaller (by 13–16 nm) than in the spectra of the non-
substituted complexes. This is due to the presence of
nitrogen atoms in the pyrazole ring, which may add
protons,and the degree of protonation of the nitrogen
meso-atoms in the phthalocyanine macrocycle is reduced.
The sulfo groups in the molecules of the complex
IX are responsible for the good solubility of the
complex in water and aqueous alkali medium, so it was
possible to record the EAS in these solvents. As with
most well-known sulfo-substituted phthalocyanines
[13], at the replacement of dimethylformamide by
water and water-alkaline solutions the nature of the
spectrum of complex IX changes significantly (see the
table and Fig. 6).
EXPERIMENTAL
Electron absorption spectra were recorded in the
region 330–900 nm on a Hitachi UV–2001 spectro-
photometer at room temperature. The solvents used are
chloroform, DMF, aqueous NaOH, sulfuric acid. The
concentration of the complexes in these solvents was
≈10–5 mol l–1. IR spectra were obtained on an Avatar
360 FT-IR ESP spectrophotometer in the range of
400–4000 cm–1. Samples were prepared by the usual
method in KBr tablet. Elemental analysis was
performed on a Flash EA CHNS-O Analyzer.
Chromato-mass spectra were taken on a Saturn 200
GC/MS instrument. 1H NMR spectra were recorded on
a Bruker DRX-500 instrument, solvent CDCl3.
The EAS have broad absorption bands with peaks
at 628–640 and 679–690 nm. As noted, the ratio of the
intensities of the long-wave and short-wave
components of the Q-band depends on the concentra-
tion of the studied complex and the medium pH. In
particular, the higher the concentration of the complex,
the more pronounced short-wavelength component of
the Q-band. The observed features of the spectrum are
due to the presence in the solution of a mixture of
associated and non-associated molecules [14].
4-[(3-Methyl-1-p-sulfophenyl-1H-pyrazol-5-yl)-
oxy]phthalonitrile (Va). A mixture of 1.04 g (5 mmol)
of 4-bromophthalonitrile, 2.54 g (10 mmol) of 1-p-
sulfophenyl-3-methyl-5-oxypyrazole, and 2.76
g
The replacemen of organic or aqueous solvent by
concentrated sulfuric acid results in a red shift of the
Q-band in the EAS by 104–116 nm (see the table and
Fig. 7). A similar change in the spectra is typical of the
majority of known phthalocyanine compounds and is
explainable by the process of protonation of the
nitrogen mesoatoms of the macro ring [15]. The
(20 mmol) of potassium carbonate in 50 ml of DMF
was heated with stirring to 125–130°C and kept for 2 h
at this temperature. After cooling, the dimethylform-
amide solution was separated from the inorganic
precipitate by filtration. The solvent was removed in a
vacuum and the dry residue was dissolved in water.
The saturated aqueous solution of the nitrile obtained
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750
KULINICH et al.
D
solidification of the reaction mixture. After cooling to
room temperature, the reaction mixture was thoroughly
crushed, washed on a glass frit filter with 18% hydro-
chloric acid to colorless filtrate, and then with water to
neutral medium. The filtered off solid was dried at 80°C.
The resulting complex VI was extracted with chloro-
form in a Soxhlet apparatus. Final purification was
carried out by chromatography on alumina of Ist
activity grade, using chloroform as an eluent. After
distillation of the eluent, the residue was dried at 70°C
to constant weight. Yield 0.28 g (44%), a dark blue
powder, soluble in chloroform, DMF, and concentrated
sulfuric acid. IR spectrum, ν, cm–1: 1668 [ν(N–N)],
1265 [ν(Ar–O–Cpyrazole)], 2852, 2923 [ν(CH)]. Found,
%: C 68.4, H 3.7, N 18.0. C72H48CoN16O4. Calculated,
%: C 68.8, H 3.8; N 17.8.
λ, nm
Fig. 7. EAS of copper complex VII in sulfuric acid.
was acidified with concentrated hydrochloric acid to
pH 2–3. The resulting precipitate was filtered off,
washed with 5% hydrochloric acid, and dried. Final
purification was carried out by chromatography on
alumina of I-st activity grade, eluent DMF–H2O (1: 1).
After removal of the eluent by vacuum distillation, the
solid residue was kept in a vacuum drying cabinet at
70°C to constant weight. Yield 0.61 g (32%), light
brown powder, decomp. point > 260°C, soluble in
water and DMF. IR spectrum, ν, cm–1: 2227 [ν(C≡N)],
1060 [νas(S=O)], 1270 [ν(Ar–O–Cpyrazole)], 2853, 2923
[ν(CH)]. Found, %: C 56.6, H 3.1, N 14.8, S 8.5.
C18H12N4O4S. Calculated, %: C 56.8, H 3.2, N 14.7, S
8.4.
Copper tetra-{4-[(3-Methyl-1-phenyl-1H-pyrazol-
5-yl)oxy]}phthalocyanine (VII) was prepared by the
same method using 0.18 g (1 mmol) of copper acetate.
Yield 0.20 g (32%), dark blue powder, soluble in
chloroform, DMF, and concentrated sulfuric acid. IR
spectrum, ν, cm–1: 1662 [ν(N–N)], 1230 [ν(Ar–O–Cpyrazole)],
2850, 2920 [ν(CH)]. Found, %: C 68.1, H 3.7, N 17.8.
C72H48CuN16O4. Calculated, %: C 68.4, H 3.8, N 17.7.
Nickel tetra-{4-[(3-Methyl-1-phenyl-1H-pyrazol-
5-yl)oxy]}phthalocyanine (VIII) was prepared similar
to compound VI using 0.18 g (1 mmol) of nickel
acetate. Yield 0.23 g (37%), dark blue powder, soluble
in chloroform, DMF, and concentrated sulfuric acid. IR
spectrum, ν, cm–1: 1660 [ν(N–N)], 1258 [ν(Ar–O–Cpyrazole)],
1
4-[(3-Methyl-1-phenyl-1H-pyrazol-5-yl)oxy]-
phthalonitrile (IVa). Obtained by the above method
using 1.74 g (10 mmol) of 1-phenyl-3-methyl-5-oxy-
pyrazole. The dimethylformamide solution after
separation from the inorganic precipitate was purified
by chromatography on alumina of I-st grade activity
eluting with DMF. Yield 0.63 g (42%), a beige powder,
mp > 125°C, soluble in DMF and acetone. IR spectrum,
ν, cm–1: 2230 [ν(C≡N)], 1272 [ν(Ar–O–Cpyrazole)],
2852, 2921 [ν(CH)]. H NMR spectrum (CDCl3), δ,
ppm: 7.87, 7.73 (12H, H1–3), 7.55, 7.46 (20H, Ph),
2.20, 2.39 (12H, CH3). Found, %: C 68.7, H 3.6, N
17.9. C72H48N16NiO4. Calculated, %: C 68.6, H 3.8; N
17.8.
Cobalt tetra-{4-[(3-Methyl-1-p-sulfophenyl-1H-
pyrazol-5-yl)oxy]}phthalocyanine (IX). A mixture of
0.76 g (2 mmol) of nitrile Va and 0.18 g (1 mmol) of
anhydrous cobalt acetate was heated to 160°C and 0.30 g
(5 mmol) of urea was added. The temperature was
raised to 190–195°C and maintained for 40–45 min to
solidification of the reaction mixture. After cooling to
room temperature, the reaction mixture was thoroughly
crushed, washed on a glass frit filter in succession with
18% and 5% hydrochloric acid to colorless filtrate.
The solid residue was dried at 70°C to constant weight.
The resulting complex was extracted with water and
the aqueous solution was evaporated to dryness on a
water bath. Final purification was carried out by
1
2852, 2923 [ν(CH)]. H NMR spectrum (CDCl3), δ,
ppm: 7.75 (1H, H1), 7.92 (2H, H2,3), 7.31–7.54 (5H,
Ph), 2.38 (3H, CH3). Mass-spectrum (m/z): 300.
Found, %: C 71.8, H 4.1, N 18.6. C18H12N4O. Cal-
culated, %: C 72.0, H 4.0, N 18.6.
Cobalt tetra-{4-[(3-Methyl-1-phenyl-1H-pyrazol-
5-yl)oxy]}phthalocyanine (VI). A mixture of 0.6 g
(2 mmol), of nitrile IVa and 0.18 g (1 mmol) of
anhydrous cobalt acetate was heated to 190–195°C and
maintained at that temperature for 45–60 min to reach
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SYNTHESIS AND SPECTRAL PROPERTIES OF THE METALLOPHTHALOCYANINES
751
6. Stepanov, B.I., Vvedenie v khimiiu i tekhnologiiyu
organicheskikh krasitelei (Introduction to Chemistry
and Technology of Organic Dyes), Moscow: Kimiya,
1984, p. 319.
7. Berezin, B.D. and Berezin, D.B., Kurs sovremennoi
organicheskoi khimii (Course of Modern Organic
Chemistry), Moscow: Vysshaya Shkola, 1999.
chromatography on alumina of I-st activity grade,
using as eluent 1-propanol–1% aqueous ammonia in
1:2 ratio. After distilling off the eluent, the residue was
dried in a vacuum drying cabinet at 70 ° C to constant
weight. Yield 0.43 g (54%), dark blue powder, soluble
in water, DMF, aqueous alkali solutions, and con-
centrated sulfuric acid. The substance crystallizes from
an aqueous solution as needles. IR spectrum, ν, cm–1:
1668 [ν(N–N)], 1260 [ν(Ar–O–Cpyrazole)], 2850, 2923
[ν(CH)], 1030, 1040 [ν(S=O)]. Found, %: C 54.6, H
3.0, N 14.3, S 8.1. C72H48CoN16O16S4. Calculated, %:
C 54.7, H 3.0; N 14.2; S 8.1.
8. Kulinich, V.P., Shaposhnikov, G.P., and Badaukaite, R.A.,
Makrogeterocikly, 2010, vol. 3, no. 1, p. 23.
9. Daier, D.R., Prilozheniya absorbtsionnoi spektroskopii
organicheskikh soedinenii (Applications of Absorption
Spectroscopy of Organoc Compounds), Moscow:
Khimiya, 1970.
10. Khimiia sinteticheskikh krasitelei (Chemistry of
Synthetic Dyes), Venkataraman, K., Ed., Leningrad:
Khimiia, 1977, vol. 5.
11. Porfiriny: struktura, svoistva, sintez (Porphyrines:
Structure, Properties, Synthesis), Enikolopyan, N.S.,
Ed., Moscow: Nauka, 1985.
Position of the bands in the electron absorption
spectra of the synthesized complexes VI–IX and their
relative intensities are listed in the table.
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12. Elektronnye spektry ftalotsianinov
i rodstvennykh
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