Synthesis and Spectral and Coordination Properties of Perhalogenated Tetraphenylporphyrins

Article abstract of DOI:10.1134/S1070363220110122

Abstract: The reaction of [5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrinato]zinc(II) with N-halosuccinimides in chloroform–methanol, chloroform–butan-1-ol, or DMF gave [2,3,7,8,12,13,17,18- octachloro(bromo)-5,10,15,20-tetrakis(2,6-dichlorophenyl)porph

Full text of DOI:10.1134/S1070363220110122

ISSN 1070-3632, Russian Journal of General Chemistry, 2020, Vol. 90, No. 11, pp. 2098–2104. © Pleiades Publishing, Ltd., 2020.
Russian Text © The Author(s), 2020, published in Zhurnal Obshchei Khimii, 2020, Vol. 90, No. 11, pp. 1724–1731.
Synthesis and Spectral and Coordination Properties
of Perhalogenated Tetraphenylporphyrins
Yu. B. Ivanovaa,*, N. V. Chizhovaa, and N. Zh. Mamardashvilia
a G.A. Krestov Institute of Solution Chemistry of the Russian Academy of Sciences, Ivanovo, 153040 Russia
*e-mail: jjiv@yandex.ru
Received June 17, 2020; revised June 17, 2020; accepted June 29, 2020
Abstract—The reaction of [5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrinato]zinc(II) with N-halosuccinimides
in chloroform–methanol, chloroform–butan-1-ol, or DMF gave [2,3,7,8,12,13,17,18- octachloro(bromo)-5,10,15,20-
tetrakis(2,6-dichlorophenyl)porphyrinato]zinc(II) which were treated with trifluoroacetic acid to obtain the cor-
responding free porphyrin ligands. The synthesized compounds and their dianions were studied by electronic
1
absorption and H NMR spectroscopy and mass spectrometry. The kinetic parameters of the complexation of
these ligands with zinc in the systems acetonitrile–Zn(OAc)2 and acetonitrile–Zn(OAc)2–1,8-diazabicyclo[5.4.0]-
undec-7-ene in the temperature range 298–318 K were determined.
Keywords: halogen-substituted tetraphenylporphyrins, zinc complexes, bromination, chlorination, spectral and
coordination properties
DOI: 10.1134/S1070363220110122
Porphyrins and their metal complexes have found
application as components of solar cells, semiconductors,
sensor systems, and photosensitizers for photodynamic
therapy [1]. Metal porphyrins containing nitro groups
and bromine atoms on the macroheterocycle have been
found to be efficient in the treatment of malignant tumors
[2]. Halogen-substituted porphyrins are also used in the
manufacture of new materials with catalytic and nonlinear
optical properties [3].
butan-1-ol. Treatment of the resulting halogenated
zinc porphyrins with trifluoroacetic acid afforded
2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetrakis(2,6-
dichlorophenyl)porphyrin (4) and 2,3,7,8,12,13,17,18-
octachloro-5,10,15,20-tetrakis(2,6-dichlorophenyl)-
porphyrin (5) (Scheme 1).
Initialzinccomplex1waspreparedbythecomplexation
of 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin (6)
with zinc(II) acetate, as well as by metal exchange of
[5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrinato]-
cadmium(II) (7) with zinc(II) chloride in boiling DMF
[7]. It was shown that the synthesis of complex 1 via
transmetalation [8] using zinc(II) chloride instead of
zinc(II) acetate takes an order of magnitude shorter time
than that in the direct complexation method.
Itisknownthatbrominationof[5,10,15,20-tetrakis(2,6-
dichlorophenyl)porphyrinato]zinc(II) (1) with
N-bromosuccinimide (NBS) in boiling methanol gives
[2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetrakis(2,6-
dichlorophenyl)porphyrinato]zinc(II) (2) in yield 45% [4].
Thereactinof1withN-chlorosuccinimide(NCS)inboiling
methanol afforded [2,3,7,8,12,13,17,18-octachloro-
5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrinato]-
zinc(II) (3). We previously synthesized unsymmetrical
β-octabromo nitrophenylporphyrins [5] and isomeric
tetrachlorooctabromo- and tetrabromoctachloro-
tetraphenylporphyrins [6] and studied their acid–base
properties.
The mass spectrum of 1 showed the molecular ion
peak at m/z 952.9 (calculated for C44H20Cl8N4Zn: 953.7).
1
In the H NMR spectrum of 1, protons in the pyrrole
rings resonated as a singlet at δ 8.75 ppm, and signals
of protons of the benzene rings were observed at δ 7.80
(d, m-H) and 7.70 ppm (t, p-H).
By heating complex 1 and 20 equiv of NBS in
chloroform–methanol (1 : 1) under reflux for 30 min
we obtained octabromo derivative 2 (Scheme 1). The
electronic absorption spectrum of a sample of the reaction
Inthiswork,dichlorophenylderivative1wasbrominated
withNBSinDMFandchloroform–methanolandchlorinated
with NCS in chloroform–methanol and chloroform–
2098

SYNTHESIS AND SPECTRAL AND COORDINATION PROPERTIES
2099
Scheme 1.
mixture dissolved in chloroform showed bands with
their maxima at λ 470, 606, and 658 nm. The spectral
pattern did not change when the reaction time was
prolonged to 50 min. The yield of 2 isolated by column
chromatography (basic alumina) was 73%.
Complex 1 reacted with 20 equiv of NCS in
chloroform–methanol under reflux for 5 h to produce
[2,3,7,8,12,13,17,18-octachloro-5,10,15,20-tetrakis(2,6-
dichlorophenyl)porphyrinato]zinc(II) (3) (Scheme 1). The
reaction time was almost twice as short as that reported
in [4]. When chloroform–butan-1-ol was used as solvent,
the reaction was complete in 1 h. Absorption maxima at
λ 451, 584, and 635 nm were observed in the electronic
The reaction of 1 with excess NBS in DMF at room
temperature for 30 h also gave compound 2 with ~80%
yield (Scheme 1). After completion of the reaction, the
electronic absorption spectrum of a sample of the reaction
mixture in DMF showed bands at λmax 474, 612, and
663 nm. The 1H NMR spectrum displayed a multiplet at δ
7.71–7.62 ppm for aromatic protons. The mass spectrum
of 2 contained the molecular ion peak at m/z 1584.7
(calculated for C44H12Br8Cl8N4Zn: 1584.9).
1
spectrum of a sample of the reaction mixture. The H
NMR spectrum of zinc porphyrin 3 showed an aromatic
multiplet at δ 7.73–7.65 ppm. The mass spectrum of
3 contained the molecular ion peak at m/z 1231.04
(calculated for C44H12Cl16N4Zn: 1229.3). Characteristics
of the electronic absorption spectra of halogenated zinc
porphyrin complexes 1–3 and cadmium porphyrin 7 are
given in Table 1.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 11 2020

2100
IVANOVA et al.
Table 1. Electronic absorption spectra of halogen-substituted tetraphenylporpyrin complexes 1–3 and 7
λ, nm (log ε)
Compound
Solvent
Soret band
Q band
1
1
2
2
3
DMF
CHCl3
DMF
CHCl3
DMF
CHCl3
DMF
405 (4.66), 426 (5.50)
405 (4.64), 425 (5.53)
368 (4.52), 474 (5.31)
368 (4.64), 469 (5.45)
364 (4.66), 455 (5.40)
362 (4.63), 451 (5.45)
418 (4.77), 438 (5.53)
559 (4.35), 594 sh
557 (4.32), 592 sh
612 (4.16), 660 (4.06)
604 (4.35), 656 (4.16)
592 (4.34), 643 sh
584 (4.38), 635 sh
578 (4.34), 620 (3.98)
3
7а
а Data of [7].
Treatment of a solution of 2 in chloroform with
trifluoroacetic acid (TFA) for 30 min led to the formation
of doubly protonated metal-free octabromoporphyrin
(H4OBP2+) (Scheme 1). Its electronic absorption spectrum
in chloroform showed bands at λmax 494, 636, and
696 nm. The free ligand, 2,3,7,8,12,13,17,18-octabromo-
5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin (4),
was obtained by treatment of the doubly protonated form
with a solution of NaHCO3. The electronic absorption
spectrum of 4 in chloroform displayed bands with their
The spectral and complexing properties of porphyrins
4 and 5 in comparison to tetrakis(2,6-dichlorophenyl)-
porphyrin (6) were studied by spectrophotometric
titration [9, 10] in the systems acetonitrile–Zn(OAc)2 and
acetonitrile–Zn(OAc)2–1,8-diazabicyclo[5.4.0]undec-7-
ene (DBU) in the temperature range 298–318 K.
The nature and position of substituents on the
macrocycle largely affect acid–base properties of
porphyrins. Comparison of the deprotonation constants
of porphyrins 4 and 5 [equilibria (1) and (2)] in the
system acetonitrile–DBU showed that the overall
acidity of chlorinated porphyrin 5 is higher by an order
of magnitude than the acidity of bromine-containing
analog 4; furthermore, the deprotonation steps are
visually distinguishable [11]. Compound 6 did not
undergo deprotonation in the same system. However, all
porphyrins 4–6 were protonated in acetonitrile–HClO4,
and their basicity decreased in the series 6 > 4 > 5 [11].
1
maxima at λ 463, 559, and 644 nm. In the H NMR
spectrum of 4, aromatic protons resonated at δ 7.71–
7.67 ppm, and the NH protons resonated at δ –1.26 ppm.
The mass spectrum of 4 showed the molecular ion peak
at m/z 1523.7 (calculated for C44H14Br8Cl8N4: 1521.6).
Likewise,treatmentofzinccomplex3withtrifluoroacetic
acid afforded 2,3,7,8,12,13,17,18-octachloro-5,10,15,20-
tetrakis(2,6-dichlorophenyl)porphyrin (5) (Scheme 1)
which showed the molecular ion at m/z 1168.3 in the
mass spectrum (calculated for C44H14Cl16N4: 1165.9).
(1)
(2)
Here, H2P, HP–, and P2– are, respectively, neutral and
singly and doubly deprotonated forms.
The complexation of porphyrins 4 and 5 in the systems
MeCN–Zn(OAc)2 and MeCN–Zn(OAc)2–DBU follows
Eqs. (3) and (4) [9]:
H2P
P2–
H2P
P2–
(3)
(4)
where H2P and P2– are, respectively, neutral and double
–
deprotonated forms of porphyrins 4 and 5; OAc is
anionic ligand (acetate ion); Solv is a solvent molecule;
and n is the metal coordination number. With account
taken of deprotonation equilibria (1) and (2), the acid
dissociation constants of compounds 4 and 5 in the
Fig. 1. Concentrations of the neutral (H2P) and doubly
deprotonated forms (P2–) of porphyrins 4 and 5 in the system
MeCN–DBU versus logarithm of the DBU concentration.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 11 2020

SYNTHESIS AND SPECTRAL AND COORDINATION PROPERTIES
2101
Table 2. Electronic absorption spectra of halogen-substituted porphyrins, their dianions, and zinc complexes in the systems
MeCN–Zn(OAc)2 and MeCN–Zn(OAc)2–DBU
λ, nm (log ε)
Porphyrin species
H2Br8TPP [12]
Br8TPP2–
H2Br8(2,6-ClPh)P (4) [11] 463 (5.13)
pKb1,2
16.60
pKa1,2
10.77
Soret band
471 (5.14)
497 (5.30)
Q band
646 (4.16), 765 (3.92)
734 (4.80)
560 (4.21), 646 (3.92), 603 sh, 15.63
713 (3.73)
674 (3.90), 729 (3.99)
603 (4.13), 667 (3.79)
9.9
Br8(2,6-ClPh)P2–
502 (4.97)
ZnBr8(2,6-ClPh)P
367 (4.46), 467 (5.17)
Zn2+Br8(2,6-ClPh)P2–
421 sh (4.49), 480 (5.08) 620 (4.07), 674 (3.93)
H2Cl8(2,6-ClPh)P (5) [11] 449 (5.11)
548 (4.13), 590 sh, 636 (3.67), 13.25 pKb1 9.63, 8.82 pKb1 4.72,
706 (3.42)
pKb2 3.62
pKb2 4.1
Cl8(2,6-ClPh)P2–
ZnCl8(2,6-ClPh)P
461 (4.77)
599 (3.84), 643 (3.82)
362 sh (4.52), 452 (5.25) 428 sh (5.09), 547 (4.22), 592
(4.13)
361 (4.21), 457 (4.88)
409 (5.42)
Zn2+Cl8(2,6-ClPh)P
593 (3.83), 648 (3.51)
H2T(2,6-ClPh)P (6)
510 (4.20), 543 sh, 586 (3.78)
17.04
–
Table 3. Kinetic parameters for the complexation of halogen-substituted porphyrins with zinc in the systems MeCN–Zn(OAc)2
and MeCN–Zn(OAc)2–DBU
Porphyrin
H2Br8TPP [15]
H2Br8(2,6-ClPh)P (4)
Br8(2,6-ClPh)P2–
H2Cl8(2,6-ClPh)P (5)
Cl8(2,6-ClPh)P2–
a Determined with an accuracy of 3–5%.
[Zn(OAc)2]×103, M
kv298×103,a L mol–1 s–1
Ea, kJ/mol
56±1
ΔS≠, J mol–1 K–1
–88±2
4.50
1.84
1.84
1.84
1.84
69±1
50±1
98±1
40±1
83±1
68±1
38±1
80±2
45±1
–48±2
–141±2
–11±2
–122±2
system acetonitrile–DBU determined previously [11],
and material balance equation (5) (proportionality of the
optical density of a solute and its concentration according
to the Beer–Lambert–Bouguer law), we determined the
concentrations of the neutral and doubly deprotonated
forms of porphyrins 4 and 5, depending on the DBU
concentration (Fig. 1).
absorption spectra parameters of porphyrins 4 and 5
and their zinc complexes and kinetic parameters of
reactions (3) and (4) in the systems MeCN–Zn(OAc)2
and MeCN–Zn(OAc)2–DBU. The rate constants kv298 and
activation parameters Ea and ΔS≠ for reactions (3) and
(4) were calculated according to the known procedure
[9]. Our attempts to obtain zinc complex directly from
(5)
We thus were able to determine the DBU concentration
corresponding to complete deprotonation of ligands 4 and
5. Zinc complexes of porphyrins 4 and 5 were synthesized
in the system MeCN–Zn(OAc)2–DBU where the ligands
were present as dianions.
Analysis of the electronic absorption spectra and rates
of formation of complexes from the neutral porphyrins 4
and 5 and their dianions [reactions (3) and (4)] revealed
distinct isosbestic points (Fig. 2) and first reaction order
in the ligand. This followed from the linear dependences
of ln(c0H2P/cH P) versus time in the temperature range
298–318 K. 2Tables 2 and 3 contains the electronic
Fig. 2. Electronic absorption spectra of porphyrin 4 in the
system Zn(OAc)2–acetonitrile in the temperature range
298–318 K; [4] = 1.88×10–5 M, [Zn(OAc)2] = 1.84×10–3 M.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 11 2020

2102
IVANOVA et al.
neutral ligand 6 in acetonitrile were unsuccessful even
at elevated temperature. As we already noted, porphyrin
6 does not undergo deprotonation in acetonitrile–DBU.
Anionic forms of porphyrins are better solvated, which
favors stronger polarization of the ligand molecule [9].
As seen from Table 3, the complexation rate constants for
porphyrins 4 and 5 in MeCN–Zn(OAc)2–DBU are almost
twice as high as those in the system MeCN–Zn(OAc)2.
corresponding free ligands, and spectral properties of the
latter and their dianions in acetonitrile have been studied.
Kinetic parameters for complexation the ligands with zinc
in the systems acetonitrile–Zn(OAc)2 and acetonitrile–
Zn(OAc)2–DBU at 298–318 K have been determined.
The obtained results may be useful for the design of new
materials with enhanced n-type conductivity. Chemical
modification of porphyrin macrocycle is an important
tool for controlling spectral and coordination properties
of porphyrins, which provides the possibility of obtaining
systems with desired physicochemical characteristics.
The rate of formation of zinc complexes with
porphyrins 4 and 5 depends on the acidity of the latter.
Introduction of halogen atoms into the meso-phenyl
rings and β-pyrrole positions is likely to increase the
NH acidity and favor deprotonation due to stabilization
of the resulting anions. Correspondingly, more acidic
ligand 5 with a higher deprotonation constant reacts
at a lower rate and is characterized by a higher energy
of activation (in comparison to 4; Table 3). The same
conclusion followed from analysis of reported data
for 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetra-
phenylporphyrin (H2Br8TPP) [12] and comparison with
those for compounds 4 and 5 in the system MeCN–
Zn(OAc)2 (Table 3). Presumably, higher strength of the
N→M bond in the transition state for more basic ligand
4 is responsible for the higher rate of its complexation
with zinc. Deprotonation of ligands 4 and 5 reduces
the difference in the rates of their complexation with
zinc, which may be due to higher symmetry of their
dianions and lower energy consumption for dissociation
of the N–H bond. It should be noted that the electronic
absorption spectra of zinc complexes 2 and 3 in Me–
Zn(OAc)2 and MeCN–Zn(OAc)2–DBU showed a red
shift of the absorption maxima relative to those of free
ligands 4 and 5. In particular, the red shift of the Soret
band for porphyrin 4 was 27 nm, and the corresponding
shift for ligand 5 was as small as 5 nm in MeCN–
Zn(OAc)2–DBU relative to Me–Zn(OAc)2. This may be
rationalized by extra coordination of DBU to the zinc
complex, as was described in detail in [13–15]. Increase
of the complexation rate constant implies reduction of the
energy of activation due to higher polarity of the complex
than the polarity of the initial ligand. This assumption is
also confirmed by the negative value of the entropy of
activation.
EXPERIMENTAL
Commercial acetonitrile (water content 0.03%,
Aldrich), DBU (Aldrich, 98%), 5,10,15,20-tetrakis(2,6-
dichlorophenyl)porphyrin (Porphychem), N-bromo-
succinimide, N-chlorosuccinimid, trifluoroacetic
acid (Acros), alumina, solvents, cadmium(II) acetate,
zinc(II) acetate, and zinc(II) chloride (Merck) were used
without further purification. [5,10,15,20-Tetrakis(2,6-
dichlorophenyl)porphyrinato]cadmium(II) was
synthesized according to the procedure described in [7].
The electronic absorption spectra were measured on a
Varian Cary-100 spectrophotometer. The 1H NMR spectra
were recorded on a Bruker AV III-500 spectrometer at
500 MHz using tetramethylsilane as internal standard.
The mass spectra (MALDI TOF) were run on a Shimadzu
Biotech Axima Confidence mass spectrometer using
2,5-dihydroxybenzoic acid as matrix. The complexations
reactions were studied according to the reported
procedures [9, 10].
[5,10,15,20-Tetrakis(2,6-dichlorophenyl)por-
phyrinato]zinc(II) (1). a. A mixture of 0.04 g
(0.0225 mmol) of porphyrin 6 and 0.082 g (0.450 mmol)
of Zn(OAc)2 in 30 mL of DMF was refluxed for 30 min.
The mixture was cooled and poured into water, and the
precipitate was filtered off, washed with water, dried, and
purified by alumina chromatography using chloroform
as eluent. Yield 0.035 g (0.0367 mmol, 82%). 1H NMR
spectrum (CDCl3), δ, ppm: 8.75 s (8H, CH=), 7.79 d
(8H, m-H, J = 7.6 Hz), 7.70 t (4H, p-H, J = 7.65 Hz).
Mass spectrum: m/z 952.9 (Irel 98%) [M]+. Calculated for
C44H20Cl8N4Zn: 953.7.
b. Complex 1 was synthesized in a similar way
from 0.04 g (0.040 mmol) of complex 7 and 0.054 g
(0.40 mmol) of ZnCl2 in 25 mL of DMF; reaction time
2 min. Yield 0.034 g (0.0357 mmol, 89%).
In summary, we have synthesized and identified
[2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetrakis-
(2,6-dichlorophenyl)porphyrinato]zinc(II) and
2,3,7,8,12-13,17,18-octachloro-5,10,15,20-tetrakis(2,6-
dichlorophenyl)porphyrinato]zinc(II). Treatment of
these complexes with trifluoroacetic acid gave the
[2,3,7,8,12,13,17,18-Octabromo-5,10,15,20-
tetrakis(2,6-dichlorophenyl)porphyrinato]zinc(II)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 11 2020

SYNTHESIS AND SPECTRAL AND COORDINATION PROPERTIES
2103
(2). a. N-Bromosuccinimide, 0.038 g (0.210 mmol), was
added to a solution of 0.02 g (0.0210 mmol) of complex 1
in a mixture of 5 mLof chloroform and 5 mLof methanol.
The mixture was refluxed for 15 min, an additional
0.038 g (0.210 mmol) of NBS was added, and the mixture
was refluxed for 15 min more, cooled, and evaporated.
The residue was dissolved in methylene chloride, and
the product was isolated by alumina chromatography
using first methylene chloride and then chloroform as
of 0.02 g (0.0126 mmol) of complex 2 in 7 mL of
chloroform. The mixture was stirred at room temperature
for 20 min and treated with water, and the organic layer
was separated, washed with water, a solution of sodium
hydrogen carbonate, and water again and dried. The
solvent was removed, and the residue was purified by
alumina chromatography using chloroform as eluent.
Yield 0.014 g (0.0092 mmol, 75%). Electronic absorption
spectrum (CH2Cl2), λ, nm (logε): 369 (4.43), 462 (5.13),
1
1
eluent. Yield 0.024 g (0.0151 mmol, 73%). H NMR
558 (4.21), 604 sh, 645 (3.92), 713 (3.73). H NMR
spectrum (CDCl3): δ 7.71–7.62 ppm, m (Harom). Mass
spectrum: m/z 1584.7 (Irel 98%) [M – H]+. Calculated for
C44H12Br8Cl8N4Zn: 1584.9.
spectrum (CDCl3), δ, ppm: 7.71–7.67 m (12H, Harom),
–1.26 s (2H, NH). Mass spectrum: m/z 1523.7 (Irel 96%)
[M + 2H]+. Calculated for C44H14Br8Cl8N4: 1521.6.
b. N-Bromosuccinimide, 0.075 g (0.420 mmol), was
added to a solution of 0.02 g (0.0210 mmol) of complex 1
in 5 mL DMF. The mixture was kept at room temperature
for 24 h, an additional 0.075 g (0.420 mmol) of NBS was
added, and the mixture was kept for 6 h. The mixture was
then diluted with water and treated with sodium chloride,
and the precipitate was filtered off, washed with water,
and dried. Yield 0.026 g (0.0164 mmol, 80%).
2,3,7,8,12,13,17,18-Octachloro-5,10,15,20-
tetrakis(2,6-dichlorophenyl)porphyrin (5) was
synthesized in a similar way from 0.02 g (0.0163 mmol)
of complex 3 using 3 mL of trifluoroacetic acid; reaction
time 1.5 h. Yield 0.013 g (0.0112 mmol, 70%). Electronic
absorption spectrum (CH2Cl2), λ, nm (logε): 446 (5.11),
1
543 (4.13), 585 sh, 631 (3.67), 700 (3.42). H NMR
spectrum (CDCl3–CF3COOH), δ, ppm: 7.85–7.79 m
(12H, Harom), –1.03 s (4H, NH). Mass spectrum: m/z
1168.3 (Irel 96%) [M + 2H]+. Calculated for C44H14Cl16N4:
1165.9.
[2,3,7,8,12,13,17,18-Octachloro-5,10,15,20-
tetrakis(2,6-dichlorophenyl)porphyrinato]zinc(II)
(3). a. N-Chlorosuccinimide, 0.028 g (0.21 mmol), was
added to a solution of 0.02 g (0.021 mmol) of complex 1
in a mixture of 5 mLof chloroform and 5 mLof methanol.
The mixture was refluxed for 2 h, an additional 0.028 g
(0.210 mmol) of NCS was added, and the mixture was
refluxed for 3 h more, cooled, and evaporated. The residue
was dissolved in methylene chloride, and the product was
isolated by alumina chromatography using first methylene
chloride and then chloroform as eluent. Yield 0.017 g
ACKNOWLEDGMENTS
This study was performed using the equipment of the Upper
Volga Regional Joint Center for Physicochemical Studies.
FUNDING
This study was performed under financial support by the
Russian Foundation for Basic Research (project nos. 18-43-
370001_r-a, “Synthesis of Halogen-Substituted Porphyrins
and Their Zinc Complexes,” and 19-03-00078 A, “Study of
Spectral and Coordination Properties of Molecular and Doubly
Deprotonated Forms of Porphyrins and Their Complexes with
Zinc Cation”).
1
(0.0138 mmol, 66%). H NMR spectrum (CDCl3): δ
7.73–7.65 ppm, m (Harom). Mass spectrum: m/z 1231.04
(Irel 97%) [M + 2H]+. Calculated for C44H12Cl16N4Zn:
1229.3.
b. N-Chlorosuccinimide, 0.028 g (0.21 mmol), was
added to a solution of 0.02 g (0.021 mmol) of complex 1
in a mixture of 5 mL of chloroform and 5 mL of butan-
1-ol. The mixture was refluxed for 30 min, an additional
0.028 g (0.210 mmol) of NCS was added, and the mixture
was refluxed for 30 min more, cooled, and evaporated.
The residue was dissolved in methylene chloride, and the
product was isolated by alumina chromatography using
first methylene chloride and then chloroform as eluent.
Yield 0.018 g (0.0146 mmol, 70%).
CONFLICT OF INTEREST
The authors declare the absence of conflict of interest.
REFERENCES
1. Li, L.-L. and Diau, E.W.-G., Chem. Soc. Rev., 2013,
vol. 42, no. 1, p. 291.
https://doi.org/10.1039/C2CS35257E
2. Stuzhin, P.A., Goryachev, M.Yu., Ivanova, S.S., Naz-
arova, A., Pimkov, I., and Koifman, O.I., J. Porphy-
rins Phthalocyanines, 2013, vol. 17, p. 905.
https://doi.org/10.1142/S1088424613500892
3. Chumakov, D.E., Khoroshutin, A.V., Anisimov, A.V., and
2,3,7,8,12,13,17,18-Octabromo-5,10,15,20-
tetrakis(2,6-dichlorophenyl)porphyrin (4).
Trifluoroacetic acid, 2 mL, was added to a solution
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 11 2020

2104
IVANOVA et al.
Kobrakov, K.I., Chem. Heterocycl. Compd., 2009, vol. 45,
no. 3, p. 259.
https://doi.org/10.1007/s10593-009-0277-8
4. Chorghade, M.S., Dolphin, D., Dupré, D., Hill, D.R.,
Lee, E.C., and Wijesekera, T.P., Synthesis, 1996, vol. 11,
p. 1320.
10. Ivanova, Yu.B., Pukhovskaya, S.G., Semeikin, A.S., and
Syrbu, S.A., Russ. J. Gen. Chem., 2013, vol. 83, no. 7,
p. 1406.
https://doi.org/10.1134/S1070363213070177
11. Ivanova, Yu.B., Chizhova, N.V., Shumilova, I.A.,
Rusanov, A.I., and Mamardashvili, N.Zh., Russ. J.
Org. Chem., 2020, vol. 56, no. 6, p. 1054.
https://doi.org/10.1134/S1070428020060147
12. Pukhovskaya, S.G., Ivanova, Yu.B., Semeikin, A.S., Syr-
bu, S.A., and Kruk, N.N., Ross. Khim. Zh., 2017, vol. 61,
no. 1, p. 56.
13. Ivanova, Yu.B., Chizhova, N.V., and Kruk, N.N., Russ. J.
Gen. Chem., 2013, vol. 83, no. 3, p. 558.
https://doi.org/10.1055/s-1996-4401
5. Ivanova, Yu.B., Chizhova, N.V., and Mamardash-
vili, N.Zh., Russ. J. Org. Chem., 2019, vol. 55, no. 10,
p. 1554.
https://doi.org/10.1134/S1070428019100142
6. Mamardashvili, N.Zh., Ivanova, Yu.B., and Chizho-
va, N.V., Makrogeterotsikly, 2019, vol. 12, no. 1, p. 22.
https://doi.org/10.6060/mhc180900m
7. Chizhova, N.V., Mamardashvili, G.M., Dmitrieva, O.G.,
Mamardashvili, N.Zh., and Koifman, O.I., Makro-
geterotsikly, 2019, vol. 12, no. 4, p. 364.
https://doi.org/10.6060/mhc190556m
8. Hambright, P., Coord. Chem. Rev., 1971, vol. 6, nos. 2–3,
p. 247.
https://doi.org/10.1016/S0010-8545(00)80041-7
9. Berezin, B.D., Coordination Compounds of Porphyrins
and Phthalocyanines, Chechester: Wiley, 1981.
https://doi.org/10.1134/S1070363213030250
14. Ivanova, Yu.B., Semeykin, A.S., Pukhovskaya, S.G.,
and Mamardashvili, N.Zh., Russ. J. Org. Chem, 2019,
vol. 55, no. 12, p. 1878.
https://doi.org/10.1134/S107042801912011X
15. Lebedeva, N.Sh., Pavlycheva, N.A., and V’yugin, A.I.,
Russ. J. Org. Chem., 2004, vol. 40, no. 12, p. 1727.
https://doi.org/10.1007/s11178-005-0090-5
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 11 2020