Synthesis and properties of dimeric octaalkylporphyrins with a polyether linker

Article abstract of DOI:10.1134/S1070428010030255

Octaalkylporphyrin dimers with a polyether linker were synthesized, and their physicochemical properties were studied. Specific response of the tetrapyrrole chromophore to complexation with potassium cation at the polyether moiety was examined.

Full text of DOI:10.1134/S1070428010030255

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 3, pp. 444–449. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © O.V. Mal’tseva, Yu.I. Churakhina, N.Zh. Mamardashvili, 2010, published in Zhurnal Organicheskoi Khimii, 2010, Vol. 46, No. 3,
pp. 448–453.
Synthesis and Properties of Dimeric Octaalkylporphyrins
with a Polyether Linker
O. V. Mal’tseva, Yu. I. Churakhina, and N. Zh. Mamardashvili
Institute of Solution Chemistry, Russian Academy of Sciences, ul. Akademicheskaya 1, Ivanovo, 153045 Russia
e-mail: ngm@isc-ras.ru
Received June 3, 2008
Abstract—Octaalkylporphyrin dimers with a polyether linker were synthesized, and their physicochemical
properties were studied. Specific response of the tetrapyrrole chromophore to complexation with potassium
cation at the polyether moiety was examined.
DOI: 10.1134/S1070428010030255
Development of effective methods for detection of
chemical compounds, including biologically important
ones, with the use of sensors is an essential problem of
modern science [1–6]. Progress in the development of
methods of organic synthesis stimulated considerable
interest in nanosized molecular sensors in which
a specific receptor giving a response to the presence of
a definite substrate and molecular signaling fragment
that transforms primary response into analytical signal
are chemically linked to each other in a single mole-
cule [7–9]. Substrate recognition generally involves
a chemical reaction, i.e., a system produces primary
response as a result of chemical interaction between
receptor and substrate.
The present work was aimed at developing new
molecular sensors for ion recognition on the basis of
porphyrin dimers in which mutual arrangement of the
tetrapyrrole chromophores can be controlled via com-
plex formation of the polyether linker with alkali metal
cations. The results of studying the response of tetra-
pyrrole chromophore to complex formation with alkali
metal cations indicated that polyether-bridged bis-por-
phyrins are promising as base structures for the design
of molecular devices with useful functionalities.
By reaction of ethyl 3-butyl-4-methylpyrrole-2-car-
boxylate (I) with 3-methoxybenzaldehyde (II) in
ethanol in the presence of a catalytic amount of hydro-
chloric acid we obtained (3-methoxyphenyl)dipyrrolyl-
methane III. Compound III was subjected to demeth-
ylation by treatment with BBr3, and (3-hydroxyphenyl)-
dipyrrolylmethane IV thus obtained was brought into
condensation with polyethylene glycol bis(4-toluene-
sulfonates) V and VI in the presence of cesium car-
bonate in a mixture of dimethylformamide with aceto-
nitrile. The condensation products were bis-dipyrrolyl-
methanes VII–X in which the dipyrrolylmethane frag-
ments were linked through conformationally labile
polyether bridges (Scheme 1).
Tetrapyrrole compounds possess unique electronic
properties (i.e., absorption and fluorescence and/or
phosphorescence spectra), and they may be optimal
transducers of primary analytical signal into optical
response of a sensor. On the other hand, these com-
pounds may be also used as source of primary analyti-
cal signal, for they are capable of forming complexes
with various ionic species [10–13]. Thus a single
molecule may act as both receptor and transducer,
which makes it possible to simplify the synthetic
procedure and reduce the size of molecular sensor.
Alkaline hydrolysis and subsequent thermal decar-
boxylation of compounds VII and VIII gave the corre-
sponding derivatives IX and X having no substituents
on C5 in the pyrrole rings. The condensation of IX and
X with 5,5′-methylenedi(3-butyl-4-methyl-1H-pyrrole-
2-carbaldehyde) (XI) in acid medium, followed by
oxidation with tetrachloro-1,4-benzoquinone, afforded
bis-porphyrins XII and XIII. The latter reacted with
From the above viewpoint, undoubted interest is
attracted by tetrapyrrole chromophores chemically
modified with polyether fragments which possess their
own complexing ability toward cations [6, 14, 15].
Polyether fragments can also be used as building blocks
in the design of preorganized three-dimensional struc-
tures via covalent bonding with porphyrin macrorings.
444

SYNTHESIS AND PROPERTIES OF DIMERIC OCTAALKYLPORPHYRINS
445
Scheme 1.
OMe
OH
Me
CHO
Me
Bu
Me
Me
Me
H+
BBr3
O
+
Bu
Bu
Bu
Bu
N
MeO
H
NH HN
NH HN
OEt
O
O
O
O
OEt
EtO
OEt
EtO
I
II
III
IV
O
O
O
n–1
Me
Me
Me
Me
4-MeC6H4SO2O(CH2CH2O)nSO2C6H4Me-4 (V, VI)
Bu
Bu Bu
Bu
NH HN
NH HN
R
R
O
R
R
VII–X
O
O
Me
Me
n–1
Me
Me
Me
Me
Bu
Bu
NH HN
Bu
Bu
Bu
Bu
Bu
Bu
Bu
OCH
CHO
N
N
N
N
N
N
N
N
XI
M
M
Bu
Me
Me
Me
Me
XII–XV
XII, XIII, M = H2; XIV, XV, M = Zn; VII, VIII: R = COOEt; IX, X, R = H; V, VII, XII, XIV, n = 4; VI, VIII, X, XIII, XV, n = 5.
zinc acetate in boiling dimethylformamide to produce
bis-porphyrin zinc complexes XIV and XV. The as-
sumed structures of compounds XII–XV were consist-
ent with their elemental compositions and electronic
absorption, 1H NMR, and mass spectra.
XVI were displaced and broadened, and their intensity
was lower, as compared to porphyrin XIV (see figure).
Thus there are all characteristic features indicating
exciton interaction between π-electron systems of
closely located (oriented face-to-face) tetrapyrrole
chromophores [6]. Mutual shielding of ring currents in
the neighboring tetrapyrrole macrorings gives rise to
upfield shift of proton signals in the 1H NMR spectrum
of complex XVI relative to the corresponding signals
of porphyrin XIV.
We examined how complex formation of porphy-
rins XIV and XV with potassium cation (K+) in tolu-
ene–methanol (5:1) affects the properties of the tetra-
pyrrole chromophores. Compound XIV was found to
bind K+ ion yielding complex XVI (Scheme 2) due to
correspondence of geometric parameters of the poly-
ether cavity to those of the substrate. The complexa-
tion is accompanied by change of conformation of the
molecule so that the porphyrin fragments in the dimer
become closer to each other, which is reflected in the
According to the spectrophotometric titration data,
the composition of complex XVI is 1 :1: only one
jump is observed on the titration curve (see figure),
and the electronic absorption spectra revealed a family
of isosbestic points. The stability constant of the com-
plex (Ks = 0.081×106 l mol–1) was calculated accord-
ing to standard procedure [16] from the spectrophoto-
1
electronic absorption and H NMR spectra. In partic-
ular, absorption bands in the electronic spectrum of
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 3 2010

MAL’TSEVA et al.
446
Scheme 2.
O
O
O
O
O
K+
K+
Me
Me
Me
Me
XIV (n = 4)
Bu
Bu
Bu
Bu
Bu
Bu
Bu
Bu
N
N
N
N
N
N
N
N
Zn
Zn
Me
Me
Me
Me
XVI
metric data obtained at two wavelengths (correspond-
ing to ascending and descending parts of the graph)
using the following formula:
on an MKh-1310 mass spectrometer (ion source tem-
perature 150–200°C). The electronic absorption spec-
tra were measured from solutions in toluene on a Varian
Cary 100 spectrophotometer. Tetraethylene glycol bis-
(4-toluenesulfonate) (V) and pentaethylene glycol bis-
(4-toluenesulfonate) (VI) were commercial products
(from Sigma). Ethyl 3-butyl-4-methyl-1H-pyrrole-2-
carboxylate (I) and 5,5′-methylenedi(3-butyl-4-methyl-
1H-pyrrole-2-carbaldehyde) (XI) were synthesized as
described in [13]. The products were isolated by
column chromatography on aluminum oxide using
toluene–hexane (1:2) as eluent. Organic solvents were
purified by standard procedures [17]. The progress
of reactions was monitored by TLC on Silufol UV-
254 plates.
[ZnP·K+]
[ZnP]·[K+]
1
ΔAi, λ ΔA0, λ
1
2
2
Ks =
=
mol–1.
[K+] ΔA0, λ ΔAi, λ
1
Here, λ1 is the descending wavelength, λ2 is the
ascending wavelength, [K+] is the concentration of
potassium ions, ΔA0 is the maximal variation of the
optical density at the given wavelength, and ΔAi is
variation of the optical density at a given wavelength
and at a given concentration [6, 16]. The error in the
determination of Ks was 7–10%.
Our results showed that complex formation involv-
ing the polyether fragment in polyether-bridged por-
phyrin dimer gives a distinct response in the electronic
absorption spectrum. Receptors like XIV are more
advantageous than crown ethers that are traditionally
used to bind alkali metal cations. The presence of
a tetrapyrrole chromophore in the receptor supramol-
ecule makes it possible to use spectrophotometric
method (which is traditionally used in the chemistry of
porphyrins) to study selective binding of cations. Such
tetrapyrrole compounds may be promising as cation-
controlled molecular switchers in extraction and mem-
brane transport processes.
Diethyl 5,5′-(3-methoxyphenylmethylene)di(3-
butyl-4-methyl-1H-pyrrole-2-carboxylate) (III).
Ester I, 5 g (0.01 mol), and aldehyde II, 0.67 ml
(0.01 mol), were dissolved in 100 ml of ethanol con-
taining 3 ml of hydrochloric acid, and the solution was
stirred for 3 h at 65°C. It was then cooled and diluted
with 100 ml of water, and the precipitate was filtered
off, washed with water, dried at room temperature, and
recrystallized from methanol–water (2:1). Yield 6.1 g
1
(79%). H NMR spectrum, δ, ppm: 0.79 t (6H,
CH2CH2CH3), 0.98 m (4H, CH2CH2CH3), 1.15 m (4H,
CH2CH2CH3), 1.36 t (6H, OCH2CH3), 2.20 s (6H,
4-CH3), 2.28 t (4H, 3-CH2), 3.66 s (3H, CH3O), 4.24 m
(4H, OCH2), 5.28 s (1H, CH), 6.47 d (1H, 4′-H), 6.52 t
(1H, 3′-H), 6.71 d (1H, 2′-H), 6.92 s (1H, 6′-H),
9.50 s (2H, NH).
EXPERIMENTAL
1
The H NMR spectra were recorded on a Bruker
VC-200 spectrometer at 200 MHz using benzene-d6 as
solvent and tetramethylsilane as internal reference. The
mass spectra (electron impact, 70 eV) were obtained
Diethyl 5,5′-(3-hydroxyphenylmethylene)di(3-
butyl-4-methyl-1H-pyrrole-2-carboxylate) (IV).
A solution of 0.19 ml (0.2 mol) of BBr3 in 5 ml of
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 3 2010

SYNTHESIS AND PROPERTIES OF DIMERIC OCTAALKYLPORPHYRINS
447
ΔA
(a)
(b)
A
0.25
0.20
0.15
0.10
0.5
0.4
0.3
0.2
0.1
0.0
0.05
0.00
0.0
0.5
1.0
1.5
2.0
2.5
3.0
cK+/cXIV
500
550
600
λ, nm
(a) Variation of the electronic absorption spectra in the system XIV–K+ (cXIV = 1×10–5, cK = 1×10–6–1×10–4 M) and (b) spectro-
+
photometric titration curve of complex XIV with potassium ion K+ in the system toluene–methanol, 5:1 (сXIV = 1×10–5 M;
λ = 568 nm; temperature 298 K).
chloroform was added to a solution of 6.0 g (0.02 mol)
of dipyrrolylmethane III in 70 ml of chloroform, and
the mixture was heated for 1 h at room temperature.
Methanol, 5 ml, was then added, and the mixture was
stirred for 30 min at room temperature and neutralized
with aqueous ammonia. The organic phase was washed
twice with water, the solvent was distilled off under
reduced pressure at 35°C, and the residue was recrys-
tallized from ethanol–water (2:1). Yield 5.5 g (96%).
1H NMR spectrum, δ, ppm: 0.78 t (6H, CH2CH2CH3),
0.97 m (4H, CH2CH2CH3), 1.12 m (4H, CH2CH2CH3),
1.33 t (6H, OCH2CH3), 2.18 s (6H, 4-CH3), 2.27 t (4H,
3-CH2), 4.21 m (4H, OCH2), 5.23 s (1H, CH), 6.44 d
(1H, 4′-H), 6.49 t (1H, 5′-H), 6.67 s (1H, 2′-H), 6.78 s
(1H, 6′-H), 9.48 s (2H, NH).
chloride, and the organic phase was separated, washed
twice with water, dried over sodium sulfate, and evap-
orated to a volume of 15 ml. The residue was diluted
with 8 ml of methanol, and the precipitate was filtered
off and dried at 55°C. Yield 175.9 mg (65%). 1H NMR
spectrum, δ, ppm: 0.77 t (12H, CH2CH2CH3), 0.95 m
(8H, CH2CH2CH3), 1.11 m (8H, 4-CH2CH2), 1.31 t
(12H, OCH2CH3), 2.16 s (12H, 3-CH3), 2.25 t (8H,
4-CH2), 3.68 m and 4.13 m (8H each, OCH2CH2O),
4.19 m (8H, OCH2CH3), 5.21 s (2H, CH), 7.36 m
(4H, 2′-H, 6′-H), 7.56 t (2H, 5′-H), 7.77 d (2H, 4′-H),
9.42 s (4H, NH).
1,14-Bis[3-bis(4-butyl-5-ethoxycarbonyl-3-meth-
yl-1H-pyrrol-2-yl)methylphenoxy]-3,6,9,12-tetra-
oxatetradecane (VIII) was synthesized in a similar
1
way. Yield 202.5 mg (72%). H NMR spectrum, δ,
1,11-Bis[3-bis(4-butyl-5-ethoxycarbonyl-3-meth-
yl-1H-pyrrol-2-yl)methylphenoxy]-3,6,9-trioxaun-
decane (VII). Dipyrrolylmethane IV, 60 mg
(0.24 mmol), was dissolved at room temperature in
50 ml of a 1:2 dimethylformamide–acetonitrile mix-
ture, 32.5 mg (0.10 mmol) of cesium carbonate and
42.9 mg (0.12 mmol) of tetraethylene glycol bis-
(4-toluenesulfonate) were added in succession to the
solution under argon, and the mixture was stirred for
24 h. The solvent was distilled off under reduced pres-
sure, the residue was treated with a mixture of 5 ml of
10% hydrochloric acid and 50 ml of methylene
ppm: 0.79 t (12H, CH2CH2CH3), 0.97 m (8H,
CH2CH2CH3), 1.09 m (8H, 4-CH2CH2), 1.29 t (12H,
OCH2CH3), 2.13 s (12H, 3-CH3), 2.23 t (8H, 4-CH2),
3.68 m (16H, OCH2CH2O), 4.14 m (4H, OCH2CH2O),
4.21 m (8H, OCH2CH3), 5.17 s (2H, CH), 7.34 m (4H,
2′-H, 6′-H), 7.52 t (2H, 5′-H), 7.76 d (2H, 4′-H), 9.40 s
(4H, NH).
1,11-Bis[3-bis(4-butyl-3-methyl-1H-pyrrol-2-yl)-
methylphenoxy]-3,6,9-trioxaundecane (IX). A solu-
tion of 10 mg of potassium hydroxide in 15 ml of
water was added to a solution of 50 mg of dipyr-
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MAL’TSEVA et al.
448
rolylmethane VII in 75 ml of ethanol. The mixture was
heated for 30 min at 90°C, the solvent was distilled
under reduced pressure, and the residue, a yellow oily
substance, was washed with water, dried at room tem-
perature, and used in further syntheses without addi-
tional purification. Yield 37.9 mg (81%).
10.13 s (2H, meso-H). Mass spectrum: m/z 1569.27
(Irel 69%) [M + 1]+. Found, %: C 77.22; H 8.66;
N 7.06. C102H134N8O6·H2O. Calculated, %: C 77.25;
H 8.63; N 7.01.
5,5′-[3,6,9-Trioxaundecane-1,11-diyldioxydi-1,3-
phenylene]bis[(2,8,12,18-tetrabutyl-3,7,13,17-tetra-
methylporphyrinato)zinc(II)] (XIV). Porphyrin XII,
30 mg, was dissolved in 70 ml of dimethylformamide,
excess zinc(II) acetate (1:10) was added, and the mix-
ture was heated for 30 min at the boiling point, cooled,
and diluted with 50 ml of water. The precipitate was
filtered off, dried, and subjected to chromatography on
aluminum oxide using toluene–hexane (1:2) as eluent.
The product was additionally purified by recrystalliza-
tion from methylene chloride–methanol (1:1). Yield
27.2 mg (87%). Rf 0.55 (Al2O3, toluene–hexane, 1:2).
Electronic absorption spectrum (toluene), λmax, nm
(log ε): 403.0 (5.75), 532.5 (4.51), 568.1 (4.70).
1H NMR spectrum, δ, ppm: 1.00 t (24H, CH2CH3),
1.13 s (12H, CH3), 1.21 s (12H, CH3), 1.49 m (16H,
CH2CH3), 2.40 m (16H, CH2CH2CH3), 3.61 m (8H,
OCH2CH2O), 3.79 t (16H, CH2CH2CH2CH3), 4.06 m
(8H, OCH2CH2O), 7.28 m (4H, 2′-H, 6′-H), 7.39 t (2H,
5′-H), 7.76 d (2H, 4′-H), 9.96 s (4H, meso-H), 10.10 s
1,14-Bis[3-bis(4-butyl-3-methyl-1H-pyrrol-2-yl)-
methylphenoxy]-3,6,9,12-tetraoxatetradecane (X)
was synthesized in a similar way. Yield 36.1 mg (77%).
1,11-Bis[3-(2,8,12,18-tetrabutyl-3,7,13,17-tetra-
methylporphyrin-5-yl)phenoxy]-3,6,9-trioxaun-
decane (XII). Compound IX, 168.9 mg (0.16 mmol),
and dialdehyde XI, 65.8 mg (0.32 mmol), were added
simultaneously to a solution of 1 ml of hydrobromic
acid in 80 ml of ethanol. The mixture was stirred for
2 h at room temperature and treated with a solution of
24 mg (0.32 mmol) of tetrachloro-1,4-benzoquinone in
10 ml of chloroform. Water, 50 ml, and 15% aqueous
ammonia, 5 ml, were added in succession, the organic
phase was separated and evaporated under reduced
pressure, and the residue was dried and subjected to
chromatography on aluminum oxide using toluene–
hexane (1:2) as eluent. The product was additionally
recrystallized from methylene chloride–methanol
(1:1). Yield 85.4 mg (35%). Rf 0.47 (Al2O3, toluene–
hexane, 1:2). Electronic absorption spectrum (tolu-
ene), λmax, nm (logε): 404.7 (5.38), 504.1 (4.39), 537.5
1
(2H, meso-H). H NMR spectrum of XIV–K+ com-
plex, δ, ppm: 0.67 s (12H, CH3), 0.91 s (12H, CH3),
1.09 t (24H, CH2CH3), 1.48 m (16H, CH2CH3), 2.49 m
(16H, CH2CH2CH3), 3.59 m (8H, OCH2CH2O), 3.77 t
(16H, CH2CH2CH2CH3), 4.04 m (8H, OCH2CH2O),
7.26 m (4H, 2′-H, 6′-H), 7.39 t (2H, 5′-H), 7.76 d (2H,
4′-H), 9.66 s (4H, meso-H), 9.95 s (2H, meso-H).
5,5′-[3,6,9,12-Tetraoxatetradecane-1,14-diyl-
dioxydi-1,3-phenylene]bis[(2,8,12,18-tetrabutyl-
3,7,13,17-tetramethylporphyrinato)zinc(II)] (XV)
was synthesized in a similar way. Yield 28.7 mg
(92%). Rf 0.59 (Al2O3, toluene–hexane, 1:2). Electron-
ic absorption spectrum (toluene), λmax, nm (logε):
403.5 (5.75), 532.1 (4.56), 568.5 (4.76). 1H NMR spec-
trum, δ, ppm: 1.05 t (24H, CH2CH3), 1.15 s (12H,
CH3), 1.19 s (12H, CH3), 1.52 m (16H, CH2CH3),
2. 39 m (16H, CH2CH2CH3), 3. 60 m (16H,
OCH2CH2O), 3.81 t (16H, CH2CH2CH2CH3), 4.09 m
(4H, OCH2CH2O), 7.29 m (4H, 2′-H, 6′-H), 7.41 t (2H,
3′-H), 7.76 d (2H, 4′-H) 10.11 s (2H, meso-H), 9.98 s
(4H, meso-H).
1
(4.26), 570.1 (4.17), 629.1 (4.09). H NMR spectrum,
δ, ppm: –2.95 s (4H, NH), 1.02 t (24H, CH2CH3),
1.14 s (12H, CH3), 1.22 s (12H, CH3), 1.51 m (16H,
CH2CH3), 2.42 m (16H, CH2CH2CH3), 3.62 m and
4.09 m (8H each, OCH2CH2O), 3.80 t (16H, CH2CH2-
CH2CH3), 7.29 m (4H, 2′-H, 6′-H), 7.41 t (2H, 5′-H),
7.77 d (2H, 4′-H), 9.99 s (4H, meso-H), 10.12 s (2H,
meso-H). Mass spectrum: m/z 1525.21 (Irel 76%)
[M + 1]+. Found, %: C 77.94; H 8.70; N 7.20.
C100H130N8O5 · CH3OH. Calculated, %: C 77.99;
H 8.45; N 7.21.
1,14-Bis[3-(2,8,12,18-tetrabutyl-3,7,13,17-tetra-
methylporphyrin-5-yl)phenoxy]-3,6,9,12-tetraoxa-
tetradecane (XIII) was synthesized in a similar way.
Yield 98.2 mg (41%). Rf 0.42 (Al2O3, toluene–hexane,
1:2). Electronic absorption spectrum (toluene), λmax
,
nm (logε): 404.5 (4.98), 504.6 (3.59), 537.1 (3.46),
570.0 (3.32), 623.1 (3.30). 1H NMR spectrum, δ, ppm:
–2.97 s (4H, NH), 1.07 t (24H, CH2CH3), 1.16 s (12H,
CH3), 1.21 s (12H, CH3), 1.53 m (16H, CH2CH3),
2. 41 m (16H, CH2CH2CH3), 3. 61 m (16H,
OCH2CH2O), 4.11 m (4H, OCH2CH2O), 3.82 t (16H,
CH2CH2CH2CH3), 7.31 m (4H, 2′-H, 6′-H), 7.42 t
(2H, 5′-H), 7.79 d (2H, 4′-H), 10.00 s (4H, meso-H),
This study was performed under financial support
by the Russian Foundation for Basic Research (project
nos. 08-03-90000-Bel-a, 08-03-00009-a) and by the
Chemistry and Materials Science Department of the
Russian Academy of Sciences (program no. 7, “Chem-
istry and Physical Chemistry of Supramolecular
Systems and Atom Clusters”).
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SYNTHESIS AND PROPERTIES OF DIMERIC OCTAALKYLPORPHYRINS
449
9. Sato, W., Miyaji, H., and Sessler, J.L., Tetrahedron Lett.,
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