Dimeric and Trimeric Supramolecular Systems Formed by Donor?Acceptor Interactions of ZnII, MnIII, and SnIV Porphyrin Complexes

Article abstract of DOI:10.1134/S1070363217120556

The paper presents the methods of synthesis of dimeric and trimeric compounds formed by donor–acceptor interactions of Zn^II, Mn^III, and Sn^IV porphyrin complexes. The structure of the porphyrin ensembles was determined by <

Full text of DOI:10.1134/S1070363217120556

ISSN 1070-3632, Russian Journal of General Chemistry, 2017, Vol. 87, No. 12, pp. 3071–3078. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © E.M. Kuvshinova, O.V. Gornukhina, A.S. Semeikin, O.A. Golubchikov, 2015, published in Rossiiskii Khimicheskii Zhurnal, 2015,
Vol. 59, No. 5, pp. 17–25.
Dimeric and Trimeric Supramolecular Systems
Formed by Donor‒Acceptor Interactions
of ZnII, MnIII, and SnIV Porphyrin Complexes
E. M. Kuvshinova*, O. V. Gornukhina, A. S. Semeikin, and O. A. Golubchikov
Ivanovo State University of Chemistry and Technology, Sheremetevskii pr. 7, Ivanovo, 153000 Russia
*e-mail: kuvshinovae@isuct.ru
Received May 15, 2015
Abstract―The paper presents the methods of synthesis of dimeric and trimeric compounds formed by donor–
acceptor interactions of ZnII, MnIII, and SnIV porphyrin complexes. The structure of the porphyrin ensembles
1
was determined by H NMR spectroscopy. The extra coordination properties of the synthesized dimeric and
trimeric supramolecular systems in relation to nitrogen-containing compounds were studied and the stability
constants of the resulting porphyrin extra complexes were determined.
Keywords: porphyrins, metal porphyrins, supramolecular systems, donor–acceptor interactions
DOI: 10.1134/S1070363217120556
Synthesis and study of dimeric, trimeric, and oligo-
meric derivatives of macroheterocyclic compounds
have attached are receiving much attention all over the
world. The results of numerous experimental works in
this field have been summarized in a number of mono-
graphs [1–4]. Supramolecular porphyrin systems are
not only of theoretical interest: they are also
considered as a basis for the design of new materials
with practically useful properties, for example, light
sensors, catalysts, materials with nonlinear optical
properties, etc. [5–8]. Quite a promising platform for
the design of tetrapyrrole supramolecular systems is
provided by coordinately unsaturated metal porphyrins
which can react with a great variety of macrohetero-
cyclic compounds containing peripheral electron-donor
functional groups. Of key importance for the formation
of stable axial complexes of metal porphyrins are the
charge of the metal and the nature of the extra ligand [9].
In the present paper we describe the synthesis and
properties of dimeric and trimeric compounds formed
by donor‒acceptor interactions of ZnII, MnIII , and SnIV
porphyrin complex.
Dimeric porphyrin 1 was synthesized by the
coordination of zinc 2,3,7,8,12,13,17,18-octaethyl-
prophyrin complex 2 to 15-(3,5-di-tert-butylphenyl)-
2,8,12,18-tetraethyl-3,7,13,17-tetramethyl-5-(pyridin-4-
yl)porphyrin (3) (Schemes 1, 2).
Scheme 1.
Et
Et
Et
Et
Et
Et
Me
Me
Et
Et
Me
Me
Et
Et
Et
N
t-Bu
t-Bu
Et
Et
N
NH
N
N
N
N
N
N
N
N
N
Zn
Zn
HN
Et
Et
Et
Et
Et
Et
Et
1
2
3071

3072
KUVSHINOVA et al.
Scheme 2.
Me
Et
Et
Et
CHO
N
CHO
Me
Me
Me
t-Bu
t-Bu
NH
NH
N
NH
N
(1) H+
(2) [O]
+
+
N
t-Bu
t-Bu
HN
Et
Me+
Me
Me
Et
Et
4
5
6
3
Et
Et
Et
Et
Me
Me
Me
Me
t-Bu
t-Bu
N
NH
N
NH
N
+
N
N
HN
N
HN
Me+
t-Bu
t-Bu
Me
Me
Et
Et
Et
Et
7
8
The key starting material porphyrin 3 was syn-
thesized by the mixed-aldehyde condensation of
pyridine-4-carbaldehyde (4) and 3,5-di-tert-butyl-
benzaldehyde (5) with 2,2'-methylenebis(3-ethyl-4-
methyl-1H-pyrrole) (6).
butylphenyl)-2,8,12,18-tetraethyl-3,7,13,17-tetramethyl-
porphyrin (7) and 3,7,13,17-tetramethyl-2,8,12,18-tetra-
ethyl-5,15-di(pyridin-4-yl)porphyrin (8).
The resulting mixture of porphyrins was separated
by column chromatography.
Along with porphyrin 3, the condensation reaction
gave as by-products symmetrical 5,15-bis(3,5-di-tert-
The starting 2,2'-methylenebis(3-ethyl-4-methyl-1H-
pyrrole) (6) was synthesized from 2,2'-methylene bis-
[3-ethyl-5-(ethoxycarbonyl)-4-methyl-1H-pyrrole] by
its combined hydrolysis and decarboxylation in ethylene
glycol. The resulting compound 6 was used without
further purification.
0.4
Systematic research into the extra coordination of
metal porphyrins to nitrogen-containing molecules
showed that zinc porphyrinates form fairly stable penta-
coordinated complexes with pyridine, piperidine, and
other nitrogenous bases. The complex formation was
accompanied by large red shifts of bands in the
electronic absorption (EA) spectra (Fig. 1).
1
0.3
2
0.2
0.1
0.0
The stability constants (Ks) of planar Zn porphyrin
extra complexes vary in the range (4‒6)×103 L/mol
depending on the electronic effects of the substituents
[2, 9–11]. This allowed spectral detection of molecular
complex 1 formed by the donor‒acceptor interaction of
zinc complex 2 with porphyrin 3. The bands of the
complex appeared in the EA spectrum after con-
500
520
540
560
580
λ, nm
Fig. 1. EA spectra of zinc octaethylporphyrin in (1) benzene
and (2) benzene containing 0.2 M pyridine.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 12 2017

DIMERIC AND TRIMERIC SUPRAMOLECULAR SYSTEMS
437 nm
3073
0.5
0.4
0.3
0.2
3
1.8
1.4
1.0
0.6
0.2
2
1
2
1
0.1
0.0
500
550
600
λ, nm
350 400 450 500 550 600 650
Fig. 2. EA spectra in benzene: (1) 15-(3,5-di-tert-butyl-
phenyl)-2,8,12,18-tetraethyl-3,7,13,17-tetramethyl-5-
(pyridin-4-yl)porphyrin; (2) zinc octaethylporphyrin; and
(3) coordination dimer 1.
λ, nm
Fig. 3. EA spectra of (1) porphyrin 9 and (2) mixture of
porphyrins 9 and 10 in chloroform
centrated (1×10–5‒2.5×10–5 M) solutions of 2 and 3
had been mixed in a 1 : 2 ratio and the mixture allowed
to stand under argon. Analytical TLC of the mixture
gave three bands, two of which were assigned to zinc
complex 2 and ligand 3. The second, medium band
was isolated and characterized spectrally (Fig. 2).
The EA spectra of manganese porphyrin complexes
having the central atom in different oxidation states
strongly differ from each other, which is used for
identification purposes [12]. The manganese cation is
most frequently present in the stable oxidation state
+3. MnIII porphyrins have a characteristic so-called
hyper-type EA spectrum with a strong π→d charge-
transfer band in the shortwave region and a great
number of well-resolved bands in the near-IR region.
An example of a typical EA spectrum is provided by
the spectrum of ClMn 2,8,12,18-tetrabutyl-3,7,13,17-
tetramethyl-5,15-diphenylporphyrin (9) (Fig. 3, curve 1).
Mixing solutions of 9 and 2,8,12,18-tetrabutyl-15-(4-
hydroxyphenyl)-3,7,13,17-tetramethyl-5-phenylpor-
phyrin (10) (Scheme 3) (solvent chloroform, solution
concentrations ~10–4 M) in a 1 : 1 ratio leads to
appearance of a new EA band near 437 nm (Fig. 3,
curve 2).
Table 1 lists the characteristics of the EA spectrum
and Rf values.
Excess nitrogen-containing reagents, for example,
pyridine, destroyed the molecular ensemble. The EA
spectrum in this case looked like the superposition of
the spectra of 2 and 3 (as pyridinate). The thin-layer
chromatogram no longer contained the second band.
The stability constant of the coordination dimer was
estimated using the current concentrations of the
reagents in the course of spectral changes:
Kst = 9×106 L/mol.
As pyridine is added, the band at 437 nm attenuates
until it disappears completely, and the EA spectrum
takes the form of a superposition of the spectera of the
reagents. This fact suggests that the two porphyrin
In should be noted that the stability complex of the
dimeric complex is 3‒4 orders of magnitude higher
compared to those of usual zinc porphyrin extra
complexes.
Table 1. EA spectra of porphyrins 1–3 in benzene at 298 K
Porphyrin
λ, nm (log ε)
Rfa
1
2
3
575
539
506
507(4.36)
–
412
0.46
0.21
0.85
625(3.61)
–
573(3.79)
540(3.96)
407(5.39)
403(5.19)
568(4.12)
530(3.93)
a Developer benzene–chloroform (1 : 1) + 2% EtOH.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 12 2017

3074
KUVSHINOVA et al.
Scheme 3.
Bu
Bu
Bu
Bu
Me
Me
Me
Me
Me
Me
Me
N
NH
N
N
N
N Cl
Mn
OH
HN
N
Me
Bu
Bu
Bu
Bu
10
9
macrocycles react by way of extra coordination to
form supramolecular structure 11 via manganese–
oxygen bonding.
As known, SnIV in its coordination compounds with
porphyrins shows a high affinity to oxygen-containing
extra ligands [15] (Scheme 4).
Thin-layer chromatography of the mixture of 9 and
10 on Alufol plates (eluent 1 : 1 chloroform–benzene +
0.5% ethanol) gave two bands. The spectrum of the
first band corresponded to porphyrin 10, and the
spectrum of the second band, to molecular complex 11.
We made use of this property to prepare trimeric
molecular ensemble 13 by reacting Sn(II) 2,8,12,18-
tetrabutyl-3,7,13,17-tetramethyl-5,15-diphenylpor-
phyrin 12 and 2,8,12,18-tetrabutyl-15-(4-hydroxy-
phenyl)-3,7,13,17-tetramethyl-5-phenylporphyrin (10).
The synthesis was performed by mixing benzene
solutions of porphyrin 10 (с = 6.6×10–5 M) and
complex 12 (с = 6.2×10–5 M) in a 2 : 1 ratio. The
mixture was stirred for 8 h under argon. Thin-layer
chromatography of the resulting mixture gave thre
bands which were isolated and characterized by spectral
methods (see Experimental).
The addition of a solution of phenol in chloroform
(с = 1.35×10–2 M) to a solution of 11 leads to minor
changes in the EA spectrum (bathochromic shifts of
the charge-transfer and I bands: 475 → 478 and 555 →
566, respectively); no new bands appear. However, the
addition of sodium phenolate in alkaline medium
results in disappearance of the band at 477 nm and
appearance of new bands at 426 and 437 nm, which
suggests redox processes. Similar spectra with a
maximum at 437 nm are characteristic of Mn(II)
porphyrin complexes [12‒14]. We can suggest that the
molecular dimer formation in the present case involves
the change of the oxidation state of manganese from
MnIII in 11 to MnII and stabilization of the latter state
by the porphyrin macrocycle with a peripheral
phenoxy group.
The structure of molecular ensemble 13 was
1
determined using the H NMR spectra and published
chemical shifts the оrtho- and meta-protons of the
phenoxy group coordinated to metal porphyrins: Δδ =
δ(complex) – δ(phenol) (Fig. 4). The chemical shifts of
the proton signals of coordination trimer 13, porphyrin
9, and complex 12 are compared in Table 2. The
presence of the electron-donor OH group in one of the
phenyl groups in porphyrin 10 increases the electron
density, thereby enhancing proton shielding. The
proton signals of the substituted ring are shifted
upfield compared to those of an unsubstituted phenyl
ring and appear at 6.67‒6.71 ppm (о-Н with respect to
oxygen) and 7.34 ppm (m-Н with respect to oxygen).
H
−1.20
H
−1.61
O
In molecular ensemble 13, the porphyrin phenoxy
group protons are shielded by the metal porphyrin
macroring current. The signals of these protons are
strongly shifted upfield with respect to those in
uncoordinated porphyrin 10 and appear at 2.64 ppm
(2H, ortho with respect to oxygen) and 7.07 ppm (2Н;
meta with respect to oxygen). These findings provide
H
Sn
O
−4.65
R
Fig. 4. Relative chemical shifts (Δδ) of the proton signals
of the phenoxy group in the complex [SnTTP(OС6Н5)2]
(300 MHz).
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DIMERIC AND TRIMERIC SUPRAMOLECULAR SYSTEMS
3075
Scheme 4.
Bu
Bu
Me
Me
Me
Bu
Bu
Me
Me
Bu
Bu
N
NH
N
N
N
N
N
O
Mn
HN
Me
Bu
Bu
Me
Me
11
Bu
Bu
Me
Me
N
N
N OH
Sn
OH
N
Me
Me
Bu
Bu
12
Bu
Bu
Bu
Me
Bu
Me
Me
Me
Me
Bu
Me
Me
Me
Bu
Bu
N
N
NH
N
NH
N
N
N
N
O
Sn
O
HN
HN
N
Me
Bu
Me
Bu
Bu
Bu
Bu
Me
Me
13
evidence for the interaction of the oxygen atom with
the coordination center of the Sn complex and,
consequently, formation of а trimeric structure.
using quartz ground glass stoppered cells. The wavel-
ength settings were accurate to within ±0.1 nm and
reproducible to within ±0.002 nm (by wavelength); the
photometric accuracy was ±0.002 nm.
EXPERIMENTAL
1
The electronic absorption spectra were measured on
Hitachi U-2000 and Shimadzu UV-1800 scanning
spectrophotometer in the range 300‒900 nm at 298 K,
The H NMR spectra were recorded on a Bruker-
200 spectrometer at 200 MHz in CDCl3 (internal standard
TMS).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 12 2017

3076
KUVSHINOVA et al.
Table 2. 1H NMR data for porphyrins 10, 12, and 13 in CDCl3
Porphyrin
NH
β-CH3
ms-H
β-Alk
3.97 t (8H)
2.14 quintet (8H)
1.73 sextet (8H)
1.10 t (12H)
Phenyl H
8.06 m (2H, o-H)
7.93 m (3H, m, p-H)
6.71–6.67 d
(2H, o-H to OH)
7.34 d (2H, m-ОН)
10
–2.40 s (2H)
2.53 s (6H)
2.45 s (6H)
10.21 s (2H)
12
13
–
2.46 s (6H)
2.53 s (6H)
2.55 s (12H)
3.93–4.02 m (16Н)
2.23 m (16Н)
1.78 sextet (16Н)
1.11 m (24H)
2.64 s (2H, o-H to OH)
7.07 m (2Н, m-Н to OH)
7.82 m (3H, m, p-H)
8.07 m (2H, o-H)
10.22 s (2H)
10.6 s (2H)
–2.40 s (2H)
2.52 s (12H)
10.55 s (2H)
4.02 t (8H)
–4.95 d (4H, o-H)
–1.61 t (4H, m-H)
–1.20 t (4H, p-H)
2.25 quintet (8H)
1.80 sextet (8H)
1.15 t (12H)
Solvents (benzene, chloroform, pyridine, DMF) were
purified by published procedures [15, 16].
15-(3,5-Di-tert-butylphenyl)-2,8,12,18-tetraethyl-
3,7,13,17-tetramethyl-5-(pyridin-4-l)porphyrin (3).
A solution of 0.45 g (4.79 mmol) of chloroacetic acid
in 20 mL of methylene chloride was added with
stirring under CO2 at room temperature to a solution of
0.56 g (2.43 mmol) of compound 6, 0.13 g (1.22 mmol)
of pyridine-4-carbaldehyde (4), and 0.26 g (1.22 mmol)
of 3.5-di-tert-butylbenzaldehyde (5) in 150 mL of
methylene chloride. The mixture was stirred for 4 h
under light-proof conditions, after which a solution of
0.9 g (3.66 mmol) of p-chloranil in 20 mL of THF was
added. The resulting mixture was stirred for 16 h at
room temperature, and the solvent was removed
completely on a rotary evaporator. The residue was
stirred with 5% KOH, the precipitate was filtered off,
washed with water, and dried in air at 70°C. The
porphyrin mixture was dissolved in chloroform and
chromatographed on alumina, eluent chloroform. The
first band contained 5,15-bis(3,5-di-tert-butylphenyl)-
2,8,12,18-tetraethyl-3,7,13,17-tetramethylporphyrin
(7), the second band contained the target compound 3,
and the last eluted was 2,8,12,18-tetraethyl-3,7,13,17-
tetramethyl-5,15-di(pyridin-4-yl)porphyrin (8). For
further purification the eluate of the second band was
reduced to a small volume and subjected to repeated
chromatography under the same conditions. The eluate
was evaporated, the product was precipitated with
methanol, filtered off, washed with ethanol, and dried
Porphyrins 11 and 12 were synthesized by pub-
lished procedures [17, 18].
Thin-layer chromatography was performed on
alumina (Brockmann activity grade III).
Zinc(II) 2,3,7,8,12,13,17,18-octaethylporphyrin
(2). А boiling solution of 2.0 g (3.68 mmol) of
2,3,7,8,12,13,17,18-octaethylporphyrin was poured into
a solution of 1,3 g (4.9 mmol) of zinc acetylacetonate
in 150 mL of methylene chloride, the mixture was
refluxed for 1 h, reduced to 100 mL, cooled down, the
complex that precipitated was filtered off, washed with
methylene chloride, and dried in air at 70°C. Yield
1.7 g. The filtrate was reduced by half and chromato-
graphed on alumina, eluent methylene chloride. The
eluate was evaporated, and the product was
precipitated with methanol. Yield 0.3 g. Total yield
2.0 g (90.9 %). Rf (Silufol): 0.85 (1 : 1 benzene‒
chloroform + 2% ethanol). EA spectrum, λmax, nm (log ε):
1
568 (4.12); 530 (3.93); 403 (5.19) (chloroform). Н
NMR spectrum, δ, ppm: 10.07 s (4H, ms-H); 3.98 q
(16H, CH2CH3); 1.70 t (24H, CH2CH3).
2,2'-Methylenebis(3-ethyl-4-methyl-1H-pyrrole)
(6). A mixture of 1 g 2,2'-methylenebis[3-ethyl-5-
(ethoxycarbonyl)-4-methyl-1H-pyrrole], 0.1 g of hyd-
razine sulfate, 1 g of potassium hydroxide, and 30 mL
of ethylene glycol was refluxed for 1 h and then
poured into 200 mL of water, left to stand at room
temperature for 3 h, the precipitate was filtered off,
washed with water, and dried at room temperature.
Yield 0.56 g (2.43 mmol). The product was further
used without purification.
in air at 70°C. Yield 0.20 g (22%). EA spectrum, λmax
,
nm (log ε): 625 (3.68); 573 (4.06); 540 (3.98); 507
1
(4.36); 408 (5.39) (chloroform). Н NMR spectrum, δ,
ppm: 10.20 s (2H, ms-H); 8.95 d (2H, α-H); 8.06 d
(2H, β-H); 7.84 d (2H, o-H); 7.74 t (1H, p-H); 3.95 q
(8H, CH2CH3); 2.46 s (6H, 13,17-CH3); 2.39 s (6H,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 12 2017

DIMERIC AND TRIMERIC SUPRAMOLECULAR SYSTEMS
3077
3,7-CH3); 1.71 t (12H, CH2CH3); 1.49 s (18H, t-Bu);
–2.52 s (2H, NH) (CDCl3).
methanol, filtered off, washed with ethanol, and dried
in air at 70°C.
15-(3,5-Di-tert-butylphenyl)-2,8,12,18-tetraethyl-
3,7,13,17-tetramethylporphyrin (7). Мr 855.312. Rf
(Silufol): 0.80 (benzene‒hexane, 1 : 1). EA spectrum,
Compound 10. Мr 759.095. Rf (Silufol): 0.19
(chloroform); 0.20 (0.25) (1 : 1 benzene‒chloroform +
2% ethanol). EA spectrum (chloroform), λmax, nm
(log ε): 626 (3.36); 575 (3.89); 542 (3.78); 509 (4.24);
411 (5.33). 1Н NMR spectrum (CDCl3), δ, ppm: 10.21
s (2H, ms-H); 8.06 d (2H, J = 7.2 Hz, 2,6-H-Ph); 7.93
d (2H, 1J = 8.0 Hz, 2,6-H-Ar); 7.71–7.67 m (3H, 3,4,5-
H-Ph) 7.34 d (2H, 1J = 8.0 Hz, 3,5-H-Ar); 2,53 s, 2.45
s (2×6H, CH ); 3.97 t (8H, 2J = 7.5 Hz, CH2–Bu); 2.14
λ
max, nm (log ε): 626 (3.26); 574 (3.90); 542 (3.73);
509 (4.27); 410 (5.40) (chloroform). 1Н NMR
spectrum (CDCl3), δ, ppm: 10.21 s (2H, ms-H); 7.91 d
(4H, J = 1.6 Hz, 2,6-H-Ar); 7.86 t (2H, J = 1.6 Hz,
1
4-H-Ar); 4.03 q (8H, J = 7.5 Hz, CH2–Et); 2.45 s
(12H, CH3); 1.76 t (12H, J = 7.5 Hz, CH3–Et); 1.49 s
(36H, t-Bu); –2.45 br.s (2H, NH).
2
2
q (8H, J = 7.5 Hz, CH2–Bu); 1.73 sextet (8H, J =
2
7.5 Hz, CH2–Bu); 1.10 t (12H, J = 7.5 Hz, CH3–Bu);
2,8,12,18-Tetraethyl-3,7,13,17-tetramethyl-5,15-
di(pyridin-4-yl)porphyrin (8). Мr 632.856. Rf (Silufol):
0.39 (benzene‒methanol, 10 : 1). EA spectrum
(chloroform), λmax, nm (log ε): 625 (3.48); 574 (3.88);
–2.40 br.s (2H, NH).
2,8,12,18-Tetrabutyl-3,7,13,17-tetramethyl-5,15-
diphenylporphyrin. Мr 743.096. Rf (Silufol): 0.50
(benzene‒heptane, 1 : 1); 0.87 (chloroform). EA
spectrum (chloroform), λmax, nm (log ε): 625 (3.42);
1
540 (3.85); 507 (4.23); 408 (5.32). Н NMR spectrum
(CDCl3), δ, ppm: 10.28 s (2H, ms-H); 9.04 d.d (2H, J =
1
1
5.8 Hz, J = 1.5 Hz, 3',5'-H-Py); 8.11 d.d (2H, J =
574 (3.84); 541 (3.73); 507 (4.20); 409 (5.31). H
1
2
5.8 Hz, J = 1.5 Hz, 2',6'-H-Py); 4.03 q (8H, J =
NMR spectrum (CDCl3), δ, ppm: 10.27 s (2H, ms-H);
8.09 d (4H, J = 7.2 Hz, 2,6-H-Ph); 7.80 t (2H, J =
7.2 Hz, 4-H-Ph); 7.76 t (4H, J = 7.2 Hz, 3,5-H-Ph);
2
7.7 Hz, CH2–Et); 2.53 s (12H, CH3); 1.80 t (12H, J =
7.7 Hz, CH3–Et); –2.45 br.s (2H, NH).
1
4.01 t (8H, J = 7.4 Hz, CH2–Bu); 2.51 s (12H, CH3);
2,8,12,18-Tetrabutyl-15-(4-hydroxyphenyl)-
3,7,13,17-tetramethyl-5-phenylporphyrin (10). A
solution of 0.45 g (4.79 mmol) of chloroacetic acid in
20 mL of methylene chloride was added at room
temperature under argon to a stirred solution of 0.52 g
(1.82 mmol) of compound 6 (prepared from 1.0 g of
2,2'-methylenebis[3-ethyl-5-(ethoxycarbonyl)-4-
methyl-1H-pyrrole], yield 78,2 %), 0.12 g (0.98 mmol)
of 4-hydroxybenaldehyde, and 0.1 mL (0.99 mmol) of
benzaldehyde in 150 mL of methylene chloride. The
mixture was stirred for 4 h under light-proof condi-
tions, after which a solution of 0.7 g (2.84 mmol) of
p-chloranil in 20 mL of THF was added. The resulting
mixture was stirred for 16 h at room temperature, and
the solvent was removed completely on a rotary
evaporator. The porphyrin mixture was dissolved in
chloroform and chromatographed on alumina. The first
band contained 2,8,12,18-tetrabutyl-3,7,13,17-tetra-
methyl-5,15-diphenylporphyrin, yield 0.23 g (33.3%),
the second band contained the target compound 10,
yield 0.25 g (36.2%), and the last eluted was 2,8,12,18-
tetrabutyl-5,15-bis(4-hydroxyphenyl)-3,7,13,17-tetra-
methylporphyrin, yield 0.08 g (11.3%). For further
purification the eluate of the second band was reduced
to a small volume and subjected to repeated
chromatography under the same conditions. The eluate
was evaporated, the product was precipitated with
1
2.19 q (8H, J = 7.4 Hz, CH2–Bu); 1.77 sextet (8H,
1
1J = 7.4 Hz, CH2–Bu); 1.12 t (12H, J = 7.4 Hz, CH3–
Bu); –2.37 br.s (2H, NH).
2,8,12,18-Tetrabutyl-5,15-bis(4-hydroxyphenyl)-
3,7,13,17-tetramethylporphyrin. Мr 775.094. Rf
(Silufol): 0.07 (chloroform). EA spectrum (chloro-
form), λmax, nm (log ε): 626 (3.04); 574 (3.56); 543
1
(3.46); 509 (3.90); 410 (5.00). H NMR spectrum
(CDCl3‒CF3COOH), δ, ppm: 10.19 s (2H ms-H); 8.06
d (4H, J = 8.1 Hz, 2,6-H-Ar); 7.47 d (4H, J = 8.1 Hz,
3,5-H-Ar); 2.27 s (12H, CH3); 3.67 t (8H, 1J = 7.4 Hz,
1
CH2–Bu); 1.71 q (8H, J = 7.4 Hz, CH2–Bu); 1.43
1
1
sextet (8H, J = 7.4 Hz, CH2–Bu); 0.91 t (12H, J =
7.4 Hz, CH3–Bu); ‒2.70 br.s (4H, NH).
Manganese 2,8,12,18-tetrabutyl-3,7,13,17-tetra-
methyl-5,15-diphenylporphyrin chloride (9) was
synthesized by the reaction of 2,8,12,18-tetrabutyl-
3,7,13,17-tetramethyl-5,15-diphenylporphyrin with a
10-fold excess of manganese chloride in DMF under
reflux for 8 h. The reaction mixture was then diluted
by half with chloroform, and excess manganese
chloride removed by washing with water. The target
complex was purified by chromatography on alumina,
eluent chloroform. EA spectrum (chloroform), λmax
nm (log ε): 567 (4.00); 477 (4.78); 365 (4.84).
,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 12 2017

3078
KUVSHINOVA et al.
in Porphyrin Chemistry), Golubchikov, O.A., Ed., St.
Tin(II) 2,8,12,18-tetrabutyl-3,7,13,17-tetrame-
Petersburg: Sankt-Peterb. Gos. Univ., 2007, vol. 5, p. 198.
thyl-5,15-diphenylporphyrin chloride (12) was
synthesized by the reaction of 2,8,12,18-tetrabutyl-
3,7,13,17-tetramethyl-5,15-diphenylporphyrin with a
10-fold excess of tin chloride in DMF under reflux for
10 h. The solvent was removed in a vacuum. The tin
complex was extracted from the residue and purified
by chromatography on alumina, eluent chloroform.
The solution of tin(IV) 2,8,12,18-tetrabutyl-3,7,13,17-
tetramethyl-5,15-diphenylporphyrin dichloride in
chloroformе was successively washed with aqueous
ammonia and water. The resulting dihydroxytin(IV)
2,8,12,18-tetrabutyl-3,7,13,17-tetramethyl-5,15-diphenyl-
porphyrin was chromatographed on silica, eluent
chloroform Rf (Silufol): 0.15 (1 : 1 benzene‒chloro-
form +2% ethanol). EA spectrum, λmax, nm (log ε): 580
(3.69); 547 (4.36); 507 sh; 420 (5.57).
5. Wasielewski, M.R., Chem. Rev., 1992, vol. 92, no. 3,
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ACKNOWLEDGMENTS
The work was performed under the state order from
the Ministry of Education and Science of the Russian
Federation (no. 4.7305.2017/8.9).
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