Synthesis, Spectral, and Coordination Properties of Halogen-Substituted Tetraarylporphyrins

Article abstract of DOI:10.1134/S1070363219030150

2,3,7,8,12,13,17,18-Ocatbromo-5,10,15,20-tetra-(4-chloroprienyl)porphyrin and 2,3,7,8,12,13,17,18-octachloro-5,10,15,20-tetra-(4-bromophenyl)porphyrin have been synthesized. The obtained compounds have been identified by electronic absorption and ¹

Full text of DOI:10.1134/S1070363219030150

ISSN 1070-3632, Russian Journal of General Chemistry, 2019, Vol. 89, No. 3, pp. 459–465. © Pleiades Publishing, Ltd., 2019.
Russian Text © Yu.B. Ivanova, N.V. Chizhova, Yu.V. Khrushkova, A.I. Rusanov, N.Zh. Mamardashvili, 2019, published in Zhurnal Obshchei Khimii, 2019,
Vol. 89, No. 3, pp. 434–440.
Synthesis, Spectral, and Coordination Properties
of Halogen-Substituted Tetraarylporphyrins
Yu. B. Ivanovaa*, N. V. Chizhovaa, Yu. V. Khrushkovab,
A. I. Rusanovb, and N. Zh. Mamardashvilia
a G.A. Krestov Institute of Solutions Chemistry of the Russian Academy of Sciences,
ul. Akademicheskaya 1, Ivanovo, 153045 Russia
*e-mail: jjiv@yandex.ru
b Ivanovo State University of Chemical Technology, Ivanovo, Russia
Received September 20, 2018; revised September 20, 2018; accepted September 27, 2018
Abstract—2,3,7,8,12,13,17,18-Ocatbromo-5,10,15,20-tetra-(4-chlorophenyl)porphyrin and 2,3,7,8,12,13,17,18-
octachloro-5,10,15,20-tetra-(4-bromophenyl)porphyrin have been synthesized. The obtained compounds have
1
been identified by electronic absorption and Н NMR spectroscopy as well as mass spectrometry. The complex-
forming properties of the synthesized porphyrins in the zinc acetate (II)–acetonitrile system at 278–298 K have
been studied. Kinetic parameters of the formation of the corresponding zinc complexes in acetonitrile have
been determined.
Keywords: 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetra-(4-chlorophenyl)porphyrin, 2,3,7,8,12,13,17,18-
octachloro-5,10,15,20-tetra-(4-bromophenyl)porphyrin, halogen-substituted tetraarylporphyrins, Co(II) complexes,
Zn(II) complexes
DOI: 10.1134/S1070363219030150
Porphyrins play significant role in natural bio-
chemical and biophysical processes [1–6]. The use of
porphyrins in specific practical applications demands
certain molecular structure modification aiming to
selectively tune the property required for the applica-
tion. Synthetic porphyrins containing chlorine and
bromine atoms in the β-positions are of particular
interest, since the induced geometry distortion of the
macrocycle allows otherwise impossible chemical
modifications. Porphyrins exhibit biological and
catalytical functions being a part on metallic com-
plexes [7]. Porphyrin complexes with transition metals
are of great interest. In particular, cobalt porphyrinates
are efficient catalysts of SO2 and different hydro-
carbons oxidation [8]. The ability of polyhalogenated
metalloporphyrins to exhibit catalytic activity in
oxygenation reactions is of great interest [9, 10]. In
view of the above, this study aimed at the synthesis of
porphyrins with halogen substituents in the pyrrole and
phenol cycles and investigation of the influence of
chlorine and bromine atoms in tetraphenylporphyrin on
the complex-forming properties of molecules.
We studied the bromination reaction of Со(II)
5,10,15,20-tetra-(4-chlorophenyl)porphyrinate 1 with
N-bromosuccinimide (NBS) in a chloroform–DMF
mixture and chlorination of Co(II) 5,10,15,20-tetra-(4-
bromophenyl)porphyrinate 2 with excess of N-chloro-
succinimide (NCS) in a chloroform–DMF mixture, as
well as the coordination properties of the halogenated
porphyrins with zinc(II) acetate in acetonitrile at 278–
298 K (Scheme 1).
Bromination of Со(II)-porphyrin 1 with NBS
(molar ratio 1 : 25) in a chloroform–DMF (4 : 1)
mixture at room temperature during 6 h led to the
formation of a mixture of Со(II) and Со(III)
porphyrins complexes. The signals with λmax = 634,
584, and 455 nm corresponding to Со(II) and Со(III)
porphyrinates were present in the electronic absorption
spectrum of the product. The signals of the starting
complex with λmax = 529 and 410 nm are absent.
1Н NMR spectrum (in CDCl3) of the cobalt-porphyrins
isolated from reaction mixture showed the signals of
ortho- and meta-protons at 8.90–7.80 ppm (3d6
459

460
IVANOVA et al.
Scheme 1.
R
Co
R
R
Co
R
R1
R1
R1
R1
N
N
N
N
N
N
N
N
NBS, NCS
R
R
R
R
CHCl3, DMF
R1
R1
R1
R1
R
R1
R1
R1
R1
N
NH
N
R
HClO4, H2SO4
R
HN
R1
R1
R1
R1
R
R1 = Cl, R2 = Br (3, 5); R1 = Br, R2 = Cl (4, 6).
configuration) and the signals at 15.10–10.08 ppm (3d7
configuration). Purification of the obtained substance
by chromatography on alumina gave Co(II)
2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetra-(4-chloro-
phenyl)porphyrinate 3. The electronic absorption spec-
trum of the obtained substance in chloroform
also led to the formation of a mixture of Со(II) and
Со(III) β-octachloro-substituted porphyrins. Purifica-
tion of the mixture by chromatography on alumina
gave Co(II) 2,3,7,8,12,13,17,18-octachloro-5,10,15,20-
tetra-(4-bromphenyl)porphyrinate 4, and only the latest
fractions contained the mixture of cobalt-porphyrins.
The electronic absorption spectrum of compound 4 in
chloroform contained the bands with λmax = 554 and
438 nm (for the latest fraction: λmax = 624, 558, and
1
contained the bands with λmax = 564 and 449 nm. Н
NMR spectrum of Co(II) porphyrinate 3 in CDCl3
contained the signals of ortho- and meta-protons at
15.10 and 10.08 ppm. The spectra of paramagnetic
Co(II) octaethylporphyrinates have been discussed in
detail elsewhere [11].
1
445 nm). Н NMR spectrum of compound 4 in CDCl3
showed broadened signals of ortho- and meta-protons
at 14.30 and 10.14 ppm.
Chlorination of bromine-substituted cobalt-por-
phyrin 2 with 130-fold excess of N-chlorosuccinimide
in the boiling chloroform-DMF mixture during 10 min
Treatment of a solution of complex 3 in a mixture
of perchloric and sulfuric acids (4 : 3) during 2 h
afforded the double-protonated form (Н4ОВР2+) of the
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SYNTHESIS, SPECTRAL, AND COORDINATION PROPERTIES
461
Table 1. Electronic absorption spectra data for Co(II) tetra-
phenylporphyrinates 1–4
free base. The bands with maximums at 746, 499, and
434 nm were observed in the electronic absorption
spectrum of Н4ОВР2+ in chloroform. After removal of
the inorganic acids and the treatment of a solution of
the protonated form H4ОВР2+ with a solution of
ammonia, 2,3,7,8,12,13,17,18-octabomo-5,10,15,20-tetra-
λ, nm, (log ε)
Complex
Solvent
band I
529 (4.23)
528 (4.50)
Soret band
410 (5.32)
411 (5.57)
1
2
3
СHCl3
1
(4-chlorophenyl)porphyrin 5 was obtained. Н NMR
CHCl3
spectrum of the brominated porphyrin 5 in CDCl3
showed the signals of ortho- and meta-protons at 8.14
and 7.78 ppm.
CHCl3
DMF
564 (4.17)
567 (4.29)
449 (5.04)
457 (5.12)
4
CHCl3
DMF
554 (4.16)
557 (4.31)
438 (5.01)
446 (5.07)
Treatment of complex 4 with a mixture of
perchloric and sulfuric acids (4 : 3) during 5 h did not
lead to, complete demetalation of the cobalt por-
phyrinate. Repeated treatment the obtained solution of
free base and cobalt complex in chloroform with the
same acids mixture during 3 h gave the double-
protonated form (Н4ОСР2+) of the chlorinated
porphyrin. The electronic absorption spectrum of
Н4ОСР2+ in chloroform contained the bands with
maximums at 734, 489, and 422 nm. After removal of
the acids and the treatment of the protonated form
H4ОСР2+ with ammonia solution, 2,3,7,8,12,13,17,18-
octachloro-5,10,15,20-tetra-(4-bromophenyl)porphyrin
basic properties were weakened and, correspondingly,
the acidic properties were enhanced in comparison
with the unsubstituted tetraphenylporphyrin. The com-
pounds acidity was strengthened in the H2Br8TPP <
H2Br8T(4-ClPh)P < H2Cl8T(4-BrPh)P series (Table 2).
The porphyrins possessing pronounced acidic
properties in acetonitrile are capable of coordination of
zinc cation via two mechanisms [molecular (1) and
ionic (2)], depending on the molecular state in the
solution [16, 17].
1
6 was obtained. Н NMR spectrum of the chlorinated
porphyrin 6 in CDCl3 showed the signals of ortho- and
meta-protons at 8.04 and 7.92 ppm.
Н2P + [Zn(OAc)2(Solv)n–2
]
→ ZnР + 2НOAc + (n–2)Solv,
(1)
[DBU·2H]2+P2– + [Zn(OAc)2(Solv)n–2
]
Parameters of electronic absorption spectra of
Co(II) tetraphenylporphyrinates are given in Table 1.
Halogenation of the β-positions of cobalt-porphyrins
led to bathochromic shift of the absorption bands in
comparison with unsubstituted complexes 1 and 2. The
signals corresponding to molecular ions of compounds
1-6 were observed in the mass spectra of halogen-
substituted Cо(II)-porphyrins and their free bases.
→ ZnР + 2HOAc + (n–2)Solv + DBU,
(2)
where (Н2P) porphyrin, (OAc) acido ligand (salt
anion), (Solv) solvent molecule, (n) coordination
number of the metal cation.
The complex formation reaction of porphyrins 5
and 6 conducted at low temperatures occurred
exclusively via the mechanism (1). In the presence of
the organic base, the zinc complexes were formed
instantly via the mechanism (2), which complicated the
determination of reaction kinetic parameters.
2,3,7,8,12,13,17,18-Octabromo-5,10,15,20-tetra-(4-
chlorophenyl)porphyrin and 2,3,7,8,12,13,17,18-
octachloro-5,10,15,20-tetra-(4-bromophenyl)porphyrin
could be protonated and deprotonated at the trans-
annular nitrogen atoms in the presence of acids and
bases dissolved in acetonitrile [12]. The acid-base
properties of porphyrins 5 and 6 have been earlier
studied [12] in the acetonitrile–HClO4 and acetonitrile–
1,8-diasobicyclo[5.4.0]-undec-7-ene systems by means
of spectrophotometric titration [13] at 298 K. Results
of this study (in particular, analysis of the values of
porphyrins protonation and deprotonation constants)
showed that the introduction of bromine atom at the
β-positions of tetraphenylporphyrin led to the change
in π-electron density in the macrocycle so that the
The isosbestic points were clearly observed in the
electronic absorption spectra of the reacting systems,
and reaction (1) followed the first reaction rate order
with respect to porphyrin, which was confirmed by the
linearity of the log [с0(H2P)/с(H2P)] vs τ(с) depen-
dence. The reaction order with respect to the salt was
estimated from the slope of the log Keff dependence on
log с[Zn(ОAc)2].
Electronic absorption spectra parameters for por-
phyrins, their double-deprotonated forms, and the
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462
IVANOVA et al.
Table 2. Parameters of electronic absorption spectra of molecular and ionic forms of porphyrins and theirs zinc complexes in
acetonitrile and the corresponding basicity and acidity constants
λ, nm (log ε)
Form, compound
pKb1,2
pKa1,2
Soret band
413 (5.02)
413 (5.01)
441 (5.04)
471 (5.14)
490 (5.19)
497 (5.30)
475 (5.09)
495 (5.21)
Q-band
512 (3.56), 546 (3.12), 589 (2.92), 646 (2.96)
512 (3.69), 547 (3.42), 660 (3.47)
661 (4.17)
H2TPP
H3TPP+
H4TPP2+
19.8 [14]
18.61 [15]
H2Br8TPP
646 (4.16), 765 (3.92)
741 (4.52)
16.60
16.06
10.77 [15]
10.15 [12]
H4Br8TPP2+
Br8TPP2–29
734 (4.80)
H2Br8T(4-ClPh)P (5)
H4Br8T(4-ClPh)P2+
646 (4.17), 763 (3.94)
743 (4.54)
Br8T(4-ClPh)P2–
ZnBr8T(4-ClPh)P
500 (4.96)
472 (5.20)
733 (4,18)
611 (4.04), 675 (4.10)
H2Cl8T(4-BrPh)P (6)
H4Cl8T(4-BrPh)P2+
458 (5.04)
486 (5.23)
554 (4.07), 623 (4.16), 732 (3.99)
736 (4,56)
14.76
9.66 [12]
Cl8T(4-BrPh)P2–
ZnCl8T(4-BrPh)P
491 (5.03)
455 (5.18)
755 (4.32)
593 (4.18), 647 (4.18)
corresponding metal complexes are given in Table 2,
and the kinetic parameters of the zinc complexes
formation in the acetonitrile–HClO4 system are given
in Table 3.
creating an excessive positive charge on transannular
nitrogen atoms of the reactive site. The listed factors
affect the zinc complexes formation rate: the
deceleration of the complex formation was observed
along with the change in the electronegativity and the
number of the introduced substituents. The reaction
rate constant for compound 6 was lower than that for
compound 5, and the increase in enthalpy of the
reaction process was observed. The comparative
analysis of the rate constants for compounds 5 and 6,
unsubstituted tetraphenylporphyrin (H2TPP) [14], and
2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraphenyl-
porphyrin (H2Br8TPP) [15] (Table 3) showed that the
introduction of bromine and chlorine atoms at the β-
positions of the macrocycle and the para-positions of
the phenyl rings reduced the reaction complex forma-
Introduction of electronegative substituents at the
β-positions of the porphyrin molecule promotes the
distortion of the macrocyclic plane, and the degree of
the macrocycle distortion increases along with the
increase in electronegativity of the introduced atom
[15]. Deformation of the porphyrin structure leads to
the partial isolation of the π-electron systems of
pyrrole fragments and the increase in electron density
on tertiary nitrogen atoms [18, 19]. In turn, electron-
accepting atoms such as bromine or chlorine draw off
the electron density from transannular nitrogen atoms,
Table 3. Kinetic parameters of the formation of zinc–porphyrins complexes in the zinc(II) acetate–acetonitrile system
[Zn(OAc)2]×103,
mol/L
kv298×103,
Ea,
kJ/mol
ΔS≠,
Porphyrin
H2TPP[14]
L mol–1 s–1
J mol–1 K–1
1.84
4.50
4.50
4.50
302±1
69±1
60±1
48±1
70±2
56±1
65±1
75±2
–28± 2
–88±2
–58±3
–26±2
H2Br8TPP [15]
H2Br8T(4-ClPh)P
H2Cl8T(4-BrPh)P
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SYNTHESIS, SPECTRAL, AND COORDINATION PROPERTIES
463
tion rate constant kv in ~4–6 times. For β-substituted
porphyrins, the rate constant was increased in the
following series: H2Br8TPP ˃ H2Br8T(4-ClPh)P >
H2Cl8T(4-BrPh)P. It is known that the reactivity of
porphyrins as ligands in the complex formation
reactions depends on the interaction of macrocyclic
tertiary nitrogen atoms in the transition state with the
metal cations entering the coordination site of
porphyrine, and the activation energy of reaction (1)
increases along with the strength of this interaction [1].
In our case, the increase in the activation energy of the
complex formation reaction (Table 3) was probably
related to the weakening of that interaction due to the
appearance of excessive positive charge on
macrocyclic transannular nitrogen atoms caused by the
influence of the introduced halogen atoms.
Shimadzu Biotech Axima Confidence mass spectro-
meter (matrix: dihydroxybenzoic acid). 1Н NMR
spectra (in CDCl3) were registered with the use of a
Bruker AV III-500 (internal reference: TMS).
Electronic absorption spectra were registered at room
temperatureusing a Cary-100 spectrophotometer.
Co(II) 5,10,15,20-tetra-(4-chlorophenyl)por-
phyrinate (1). A mixture of 0.04 g (0.065 mmol) tetra-
(4-chlorophenyl)porphyrin and 0.096 g (0.65 mmol) of
Со(ОAc)2 in 30 mL of DMF was boiled for 30 s and
then cooled to ambient. The mixture was poured into
water, and NaCl was added. The precipitate was
filtered off, washed with water, dried, and purified by
chromatography on alumina eluting with dichloro-
methane. Yield 0.033 g (0.0407 mmol, 77%). 1Н NMR
spectrum, δ, ppm: 15.82 br. s (8Н, pyrrole),13.00 br. s
(8Н, Нo), 8.15 d (8Н, Нm, J = 7.6 Hz). Mass spectrum,
m/z (Ir, %): 809.02 (97) [M]+ (calculated for
C44H24N4Cl4Cо: 810).
In summary, 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-
tetra-(4-chlorophenyl)porphyrin and 2,3,7,8,12,13,17,18-
octachloro-5,10,15,20-tetra-(4-bromophenyl)porphyrin
were synthesized and identified by electronic
Co(II) 5,10,15,20-tetra-(4-bromophenyl)por-
phyrinate (2) was obtained similarly from 0.04 g
(0.043 mmol) of tetra-(4-bromophenyl)porphyrin,
0.075 g (0.43 mmol) of Cо(OAc)2 and 40 mL of DMF.
Yield 0.034 g (0.0344 mmol, 80%). 1Н NMR
spectrum, δ, ppm: 15.88 br. s (8Н, pyrrole), 12.94 br. s
(8Н, Нo), 10.10 br. s (8Н, Нm). Mass spectrum, m/z (Ir,
%): 986.63 (98) [M]+ (calculated for C44H24N4Br4Cо:
987.3).
1
absorption and H NMR spectroscopy as well as mass
spectrometry. Spectrophotometric determination of the
complex-forming properties of 2,3,7,8,12,13,17,18-
octabromo-5,10,15,20-tetra-(4-chlorophenyl)porphyrin
and 2,3,7,8,12,13,17,18-octachloro-5,10,15,20-tetra-(4-
bromophenyl)porphyrin in the zinc(II) acetate–aceto-
nitrile system at 278–298 K and the determination of
kinetic parameters of the formation of the zinc com-
plexes in acetonitrile pointed out that it was possible to
tune the properties of the porphyrin molecule as a
whole so that they matched a specific application by
changing the substituent type in β- and para-positions
of the phenyl ring of tetraphenylporphyrin.
Co(II) 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-
tetra-(4-chlorophenyl)porphyrinate (3). 0.11
g
(0.618 mmol) of NBS was added to a solution of 0.02 g
(0.0247 mmol) of complex 1 in 12 mL of chloroform
and 3 mL of DMF. The mixture was kept at room
temperature during 6 h and evaporated to minimal
volume; 4 mL of DMF, water, and NaCl were then
added. The precipitate was filtered off, washed with
water, dried, and purified by column chromatography
on alumina (eluent: dichloromethane, chloroform).
Yield 0.027 g (0.0187 mmol, 77%). 1Н NMR spectrum,
δ, ppm: 15.10 br. s (8Н, Нo), 10.07 br. s (8Н, Нm).
Mass spectrum, m/z (Ir, %): 1440.9 (48) [M]+ (cal-
culated for C44H16N4Cl4Br8Cо: 1440.5).
EXPERIMENTAL
Tetra-(4-chlorophenyl)-porphyrin and tetra-(4-
bromophenyl)porphyrin (Porphychem) were used.
Coordination properties of the halogenated porphyrins
were studied in solutions in acetonitrile purchases from
Lab-Scan. The measurements were performed at
278–298 K in a closed cell (at least three measurements
at each temperature; temperature was maintained constant
within ±0.1 K) using a Cary-100 spectrophotometer
(Varian). The details of the preparative chemistry and
experimental data processing are given elsewhere
[13, 16]. The solvents (dimethylformamide, chloroform,
and dichloromethane of “chemical pure” grade),
N-bromosuccinimide and N-chlorosuccinimide (Acros),
and alumina (Merck) were used as received. Mass
spectra were registered with the use of a MALDI TOF
Co(II) 2,3,7,8,12,13,17,18-Octachloro-5,10,15,20-
tetra-(4-bromophenyl)porphyrinate (4). 0.165 g
(1.015 mmol) of NСS was added to a solution of 0.02 g
(0.0203 mmol) of complex 2 in a mixture of 10 mL of
chloroform and 2.5 mL of DMF. The mixture was
boiled for 4 min, and then 1.5 mL of DMF and 0.165 g
of NСS were added to the mixture which was boiled
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464
IVANOVA et al.
for 2 min more. After cooling, the mixture was
evaporated to minimal volume, and 3 mL of DMF,
water, and NaCl were added. The precipitate was
filtered off, washed with water, dried, and purified by
column chromatography on alumina (eluent: hexane,
synthesis of halogen-substituted porphyrins and theirs
complexes with cobalt cation; project no. 18-03-
00048_a, investigation of coordination properties of
synthesized porphyrin ligands) with the use of
equipment of “The upper Volga region center of
physico-chemical research.”
dichloromethane, chloroform). Yield 0.015
g
1
(0.0119 mmol, 60%). Н NMR spectrum, δ, ppm:
14.30 br. s (8Н, Нo), 10.14 br. s (8Н, Нm). Mass
spectrum, m/z (Ir, %): 1263.05 (42) [M]+ (calculated
for C44H16N4Cl8Br4Cо: 1262.7).
CONFLICT OF INTEREST
No conflict of interest was declared by authors.
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2,3,7,8,12,13,17,18-Octabromo-5,10,15,20-tetra-
(4-chlorophenyl)porphyrin (5). 3 mL of 58%
perchloric acid and 2.5 mL of 96% sulfuric acid were
added to a solution of 0.02 g (0.0139 mmol) of
compound 3 in 10 mL of chloroform. The mixture was
stirred for 2 h at room temperature. After the reaction
was complete, the organic fraction was separated,
washed with water, ammonia solution, then again with
water, and dried over Na2SO4; after that, the residue
was evaporated. The residue was purified by column
chromatography on alumina eluting with dichloro-
methane, and then reprecipitated from hexane. Yield:
0.014 g (0.0101 mmol, 72%). EAS (MeCN), λmax, nm
(log ε): 763 (3.94), 646 (4.17), 474 (5.09), 372 (4.44).
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7.7 Hz), 7.78 d (8Н, Нm, J = 7.6 Hz). Mass spectrum,
m/z (Ir, %): 1385 (39) [M]+ (calculated for
C44H18N4Cl4Br8: 1383.7).
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2,3,7,8,12,13,17,18-Octachloro-5,10,15,20-tetra-
(4-bromophenyl)porphyrin (6). 3 mL of 58%
perchloric acid and 2.5 mL of 96% sulfuric acid were
added to a solution of 0.02 g (0.0158 mmol) of
compound 4 in 10 mL of chloroform. The mixture was
stirred for 5 h at room temperature. 3 mL of prchloric
acid and 2.5 mL of sulfuric acid were added to the
separated organic fraction. The obtained mixture was
stirred for 3 h and then treated as described above. The
product were isolated via chromatography on alumina,
eluent: dichloromethane–hexane (1 : 1). Yield 0.01 g
(0.0083 mmol, 54%). EAS (MeCN), λmax, nm (log ε):
732 (3.99), 623 (4.16), 554 (4.07), 458 (5.04).
1Н NMR spectrum, δ, ppm: 8.04 d (8Н, Нo, J = 7.7
Hz), 7.92 d (8Н, Нm, J = 7.6 Hz). Mass spectrum, m/z
(Ir, %): 1207.3 (53) [M]+ (calculated for
C44H18N4Cl8Br4: 1205.9).
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