Bisporphyrin-calix[4]arene heterotopic receptors of multifunctional substrates

Article abstract of DOI:10.1134/S1070363211030273

In order to create heterotopic receptors of polyfunctional substrates we have synthesized the bisporphyrin-calix[4]arene crown ethers [6] with the amino and hydroxy groups in tetrapyrrole fragments and polyethyleneoxide complexing cavity in the calix[4]arene fragment of the macrocycle. Their spectral properties and complexing ability toward the alkali metal cations, organic diamines, and dicarboxylic acid esters were investigated.

Full text of DOI:10.1134/S1070363211030273

ISSN 1070-3632, Russian Journal of General Chemistry, 2011, Vol. 81, No. 3, pp. 594–601. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © G.M. Mamardashvili, S.V. Zvezdina, N.Zh. Mamardashvili, 2011, published in Zhurnal Obshchei Khimii, 2011, Vol. 81, No. 3,
pp. 499–506.
Bisporphyrin–Calix[4]arene Heterotopic Receptors
of Multifunctional Substrates
G. M. Mamardashvili, S. V. Zvezdina, and N. Zh. Mamardashvili
Institute of Solution Chemistry, Russian Academy of Sciences, ul. Akademicheskaya 1, Ivanovo, 153045 Russia
e-mail: gmm@isc-ras.ru
Received February 18, 2010
Abstract—In order to create heterotopic receptors of polyfunctional substrates we have synthesized the
bisporphyrin–calix[4]arene crown ethers [6] with the amino and hydroxy groups in tetrapyrrole fragments and
polyethyleneoxide complexing cavity in the calix[4]arene fragment of the macrocycle. Their spectral properties
and complexing ability toward the alkali metal cations, organic diamines, and dicarboxylic acid esters were
investigated.
DOI: 10.1134/S1070363211030273
The chemistry of macrocyclic functional devices is
extremely interesting area of coordination and organic
chemistry rapidly developing in the last decade. Its
subject of study comprises the compounds combining
different classes of organic substances: calix[n]arenes,
calix[4]pyrroles, crown[n] ethers, cyclodextrins, por-
phyrins, and other macrocycles. Calix[4]arenepor-
phyrins [1–3] and calix[4]pyrroleporphyrins [4, 5] are
the examples of compounds formed by covalent fusing
of different macrocycles, which retain all individual
properties and acquire qualitatively new properties
compared with the original fragments.
with respect to metal cations [6–8]. On the other hand,
porphyrinate macrocycles possess the ability to axial
coordination by the central metal cation of small
organic molecules containing electron-releasing atoms
or functional groups in their structure [9–11]. If the
tetrapyrrole macrocycle has besides the other reaction
sites at the periphery of the molecule (amino, hydroxy,
carboxy, sulfo, etc.), then such porphyrinate molecules
acquire selective complexing ability with respect to the
polyfunctional substrates. Covalently combining in one
molecule a crown-calixarene fragment and two
appropriately functionalized porphyrinate macrocycles
allows the creation of sterically preorganized heter-
otopic receptors possessing polyfunctional complexing
power toward both charged particles and neutral
molecules of various nature.
Calix[4]areneporphyrins have
a
number of
advantages. Firstly, they often possess unique pro-
perties as molecular receptors. Secondly, the processes
of binding neutral and/or charged particles by different
fragments of calix[4]areneporphyrins are interrelated
that allows using one process (e.g., complexation of
the macrocycle of the calix[4]arene fragment with an
alkali metal cation) as a means to control another
process (complexation of the macrocycle of the
porphyrin fragments with neutral molecules).
In connection with our interests in the field of
coordination chemistry of macroheterocyclic com-
pounds, in this work new bisporphyrin–calix[4]arene–
crown[6] ethers were synthesized with the amino and
hydroxy groups in tetrapyrrole fragments and poly-
ethylenoxide complexing cavity in the calix[4]arene
fragment of the macrocycle. We investigated their
spectral properties and complexing ability towards
alkali metal cations, aromatic diamines, and dicar-
boxylic acids esters.
This paper describes the creation of heterotopic
receptors on the basis of bisporphyrin–calixarene–
crown–ethers containing amino and hydroxy groups in
the tetrapyrrole fragments and a polyethylenoxide
complexing cavity in the calixarene fragment of the
macroheterocycle. It is known that crown ethers and
calixarene crown ethers possess receptor properties
The bisporphyrin–calix[4]arene–crown[6] ethers
with nitro (I) and methoxy (II) groups in the
tetrapyrrole fragments were synthesized by a mixed-
594

BISPORPHYRIN–CALIX[4]ARENE HETEROTOPIC RECEPTORS
595
aldehyde condensation of 5,5'-unsubstituted dipyr-
rolylmethane, diformylcalixarene, and an appropriate
aromatic aldehyde [12–14]. By reduction of nitro
groups in the bis[(3-nitrophenyl)porphyrin]calix[4]
arene-crown[6] (I) we prepared bis[(3-aminophenyl)
porphyrin]calix[4]arene-crown[6] (III). By hydrolysis
3,8,13,18-tetraethylporphyrin (VII) and its zinc
complex (VIII) [14]. The shortwave shift (~6 nm) of
the Soret band in the EAS of bisporphyrin-calix[4]
arene-crowns[6] III–VI as compared with VII and
VIII also supports the cyclophane structure, where a
significant interaction of π-electronic systems of the
tetrapyrrole chromophores in the dimers is observed.
1H NMR spectra of III–VI contain the signals of the
protons of calixarene, crown ether, and porphyrin
fragments. The presence of a clear singlet of protons of
methylene groups (at δ ~3.88 ppm) according to
published data [3] indicates that the calix[4]arene
fragment in III–VI is in 1,3-alternate conformation. It
should also be noted that the signals of all porphyrin
fragments in III–VI are shifted upfield compared with
the corresponding signals in the spectra of VII and
VIII that, according to published data and to the
results of our own studies [10–11], confirms the
cyclophane structure of compounds III–VI.
of
bis[(3-methoxyphenyl)porphyrin]-calix[4]arene-
crown[6] (II) was prepared bis[(3-hydroxyphenyl)
porphyrin]-calix[4]arene-crown[6] (IV) (scheme). By
boiling III and IV with zinc acetate in dimethyl-
formamide the corresponding Zn(II) porphyrinates Zn
(V–VI) were synthesized.
Compounds III–VI are stable: in solid form they
are not oxidized under the action of atmospheric
oxygen. Electron absorption spectra (EAS) of
compounds III–VI are characterized by a significant
broadening of the Soret band and a reduced
coefficients of molar extinction compared to mono-
meric analogs, 5,15-diphenyl-2,7,12,17-tetramethyl-
NH
N
N
N
M
O
O
O
O
O
O
N
N
HN
N
O
O
O
O
R
O
O
O
O
R
R
R
O
O
NH
N
N
N
M
N
N
HN
N
I−II
III−VI
R = NO2 (I), OCH3 (II), NH2 (III, V), OH (IV, VI); M = 2H (III, IV), Zn (V–VI).
A characteristic feature of the dimeric porphyrins is
the presence of internal complexing cavity, where the
bidentate ligands can penetrate and form stable
complexes with two points of binding via donor–
acceptor bonds. The possibility of varying the size of
the cavity due to the length and nature of the bridges
binding porphyrin fragments, makes it possible to
prepare selective receptors for a particular type of
substrates. In [1, 2] and in a series of our works [3, 12,
14, 17] was shown that bisporphyrin-calix[4]arenes
can, depending on the structural features of calix[4]
arene platform, form stable complexes through two
intracavity binding sites with di- and triethylene-
diamines.
The study of the complexation of amino- (V) and
hydroxy-substituted (VI) bisporphyrinate-calix[4]arene-
1
crowns[6] (L1) by spectrophotometric titration and H
NMR spectroscopy revealed that it proceeds with the
formation of stable complexes IX with two intracavity
donor–acceptor bond. At the formation of the complex
IX with the ligand taken in a wide concentration range,
the spectral curves in the course of complexation have
one family of isobestic points (Fig. 1). They are
characterized by relatively small shifts of absorption
bands because the red shift (axial coordination of the
ligand) is compensated partially by a corresponding
blue shift and by a slight broadening of the Soret band
(the exciton interaction in the porphyrin fragments).
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MAMARDASHVILI et al.
(b)
(a)
0.6
0.4
0.2
0.0
0
0.5
1.5
CL1, M/Cporph, M
2.5
0.0
, nm
Fig. 1. (a) Spectral changes in the region of the Soret band at the titration of VI with diamine in toluene in the concentration range
of L1 from 0 to 6.6×10–6 M at 25°C (Cporph = 5.6×10–6 M); (b) the titration curves at increasing and decreasing wavelengths.
The upfield shift of the signals of CH2CH2 protons
of the ligand (Δδ = –3.72 ppm), their equivalence (they
N
N
N
N
appear as a singlet) and intensity ratio of the signals of
protons of the ligand and the porphyrin fragment in 1H
NMR spectra of the complex also indicate the
formation of intracavity complexes IX.
Zn
O
O
O
O
O
R
R
N
N
O
O
Stability constants of the intracavity complexes V–
L1 and VI–L1 in toluene calculated by the formula (1)
from the data of spectrophotometric titration of
porphyrin dimers with diamine L1 are 6.3×106 l mol–1
and 5.5×106 l mol–1, respectively.
O
N
N
N
N
Zn
The study of complexation of VI with 1,4-
phenylenediamine (L2) in toluene showed that in the
concentration range (Cligand from 0 to 8×10–4 M) also a
IX
complex of one type is produced (Fig. 2). The splitting
of proton signals of L2 and the ratio of the intensities
of the signals of porphyrinate protons and the protons
1
of the ligand in the H NMR spectrum of the VI–L2
complex support the formation of “external” complex
X of 1:2 composition when the ligand molecules
cannot penetrate the interporphyrin complexing cavity
and are located outside the tetrapyrrole macrocycles.
Protons of the aryl moiety L2 are no longer equivalent,
and some of them are located close to the tetrapyrrole
macrocycle, experiencing the ring current shielding
effect of π-electrons of the porphyrin fragment to a
greater extent shifting upfield their signals (4H, at
2.69 ppm). Another part of the protons being more
distant from the macrocycle give rise to the signals in a
weak field (4H, at 5.71 ppm). Similarly the proton
signals of the amino groups of the substrate are split in
0.0
, nm
Fig. 2. Spectral changes in the region of the Soret band at
the titration of VI with diamine in toluene in the
concentration range of L2 from 0 to 5.4×10–4 M at 25°C
(CVI = 5.6×10–6 M).
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BISPORPHYRIN–CALIX[4]ARENE HETEROTOPIC RECEPTORS
NH2
597
NH2
N
N
N
N
Zn
O
O
O
O
O
R
R
O
O
O
N
N
N
N
Zn
NH2
NH2
X
1
the H NMR spectrum of complex VI–L2 (singlets at
0.29 (4H) and 3.96 (4H) ppm, respectively). Stability
constant (Kst) characterizing the process of binding one
ligand L2 with one porphyrin fragment of VI,
calculated by Eq. (1) from the data of spectro-
photometric titration (1480 l mol–1) corresponds to the
stability constants of the monomeric zinc porphyrinate
complex VIII–L2, Kst = 1320 l mol–1) [8]. The stability
constants of VI–2L2 complex of 1:2 composition
calculated by Eq. (2) is 1.96×106 l2 mol–2.
Compounds III–VI can form complexes with the
esters of dicarboxylic acids through the hydrogen
bonding. The complexation is accompanied by a
change in the distance between the porphyn fragments
of the macrocycle which is reflected in the electron
absorption spectrum of the reaction system
bisporphyrin–carboxylic acid ester as a blue or red
shift and broadening or narrowing of the absorption
bands, which allows to examine the process by
spectrophotometric titration.
N
HN
O
O
O
NH
N
OMe
O
O
O
O
O
O
C
C
O
O
CH2
O
N
MeO
HN
N
NH
XI
The study of the complexation of III and IV with
methyl esters of several dicarboxylic acids [malonic
(L3), maleic (L4), fumaric (L5), succinic (L6), and
isophthalic (L7)] showed that the spectral changes
typical of the formation of 1:1 complex XI with a
family of isobestic points occur in the case of malonic
ester. Figure 3 shows the changes in EAS of III at
adding methyl malonate (L3). Probably, the formation
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MAMARDASHVILI et al.
The analysis of experimental data allows us a
conclusio that the size of intramolecular binding
cavities in compounds III and IV are best consistent
with the size of malonic acid among all the
investigated dicarboxylic acids, and these bispor-
phyrinates form intracavity complexes through two
hydrogen bonds only with the malonate ester.
The study of the complexation process of
porphyrinate V with dimethyl maleate (L4) showed
that in a wide concentration range of ligand (Cligand
from 0 to 5.3×10–5 M) the spectral changes during the
reactions occur with the preservation of the family of
isobestic points (Fig. 4). The titration curve has one
jump indicating the formation of the bisporphyrinate–
ligand complex of one type, and the slope of the plot
log [(A0 – Aeq)/(Aeq – Ac)] vs. log C of the ligand equals
two, indicating that the formed complex has a com-
position of 1:2. The process of complexation of V with
L4 is accompanied, in contrast to the complexes III–L3
and IV–L3, by a red shift of the bands in the EAS,
which probably indicates that the distance between the
porphyrin fragments increases upon the formation of
V–2L4 (XII). The stability constant of the complex
calculated by Eq. (3) is Kst = 2.45×105 l2 mol–2. The
complexation of V with dimethyl fumarate (L5)
proceeds similarly. The stability constants of the
complex V–2L5 is 1.81×105 l2 mol–2.
0.0
, nm
Fig. 3. Spectral changes in the region of the Soret band at
the titration of III with dimethyl dicarboxylate in toluene in
the concentration range of L3 from 0 to 5.2×10–3 M at 25°C
(Cporph = 6.6×10–6 M).
of complex XI in the case of methyl malonate is
accompanied by a approachment of the porphyrin
fragments, which is characterized by the corresponding
blue shift of the bands in the EAS. Spectral changes in
the IV–L3 system are similar. The stability constants
of the complexes III–L3 and IV–L3 calculated by
Eq. (1) from the data of spectrofotometric titration are
respectively 680 and 1320 l mol–1.
N
N
NH2
O
C
C O
Zn
N
O
O
O
O
N
O
O
O
O
O
O
O
O
N
N
C O
O
C
NH2
Zn
N
N
XII
Conformational changes of bisporphyrin-calix[4]-
arene-crown[6] molecules caused by the binding of
alkali metal cation by the polyether complexing cavity
of the supramolecule calix[4]arene fragment due to the
approachment or, conversely, removal of the porphyrin
fragments from each other, are also reflected in the
electron absorption spectra. The change in the position
and intensity of the absorption bands in the EAS
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BISPORPHYRIN–CALIX[4]ARENE HETEROTOPIC RECEPTORS
599
0.0
0.0
, nm
, nm
Fig. 4. Spectral changes in the region of the Soret band at
the titration of V with dimethyl dicarboxylate in toluene in
the concentration range of L4 from 0 to 5.3×10–5 M at 25°C
(Cporph = 6.6×10–6 M).
Fig. 5. Spectral changes in the region of the Soret band at
the titration of VI with K+ cation in dichloromethane in the
concentration range of KBF4 from 0 to 1.2×10–4 M at 25°C
(Cporph = 9.4×10–6 M).
accompanying the process of complexation allows the
application of the method of spectrophotometric
analysis to the study of the binding of metal cations by
the polyether cavity of the calixarene fragment.
amine, and methyl malonate. The most significant
conditions for the formation of such complexes is the
geometric correspondence by size of the substrate and
the intramolecular complexing cavity of the receptor
and the presence of several (two or more) com-
plementary binding sites.
Figure 5 shows the spectral changes in the reaction
system at the interaction of VI with KBF4. These
changes and spectrophotometric titration curves
derived from them indicate that the resulting complex
has a stoichiometry of 1:1 (XIII). Similar processes
take place between VI and NaBF4. Stability constants
of the complexes calculated by Eq. (1) from the data
on spectrophotometric titration of VI with tetrafluoro-
borates (KBF4 and NaBF4) are 8.2 ×107 and 9.6×
104 l mol–1, respectively. These data are in good
agreement with the published data obtained for calix
[4]arene-crown[6] of similar structure but without the
porphyrin fragments [18].
EXPERIMENTAL
Bisporphyrin-calix[4]arene-crowns[6] I and II were
synthesized by the methods [12–14]. Individual
compounds were isolated by column chromatography
on neutral alumina. As an eluent we used methylene
chloride–hexane 1:1 mixture. Organic solvents were
purified by known methods [19]. The reaction course
was monitored by TLC on the Silufol UV-254 plates.
1H NMR spectra of compounds III–VI were recorded
on a Bruker VC-500 spectrometer at the operating
frequency 500.17 MHz in deuterochlroform, internal
reference TMS. Electron absorption spectra (EAS) of
compounds III–VI in toluene were recorded on a
Varian Cary 100 spectrophotometer. EAS of III–VI
and their changes upon adding to the system of the
substrates of different nature are depicted in Figs. 1–5.
N
N
N
N
Zn
Zn
O
O
O
O
O
O
R
R
M+
Stability constants (Kst) of the porphyrin complexes
with different substrates the for the 1:1 complexes was
calculated by the Eq. (1).
O
O
N
N
N
N
Kst = [A·B]/([A]·[B])
= (1/[B])[(ΔAi,λ1/ΔA0,λ1)·(ΔA0,λ2/ΔAi,λ2)] (M)–1, (1)
XIII
Thus, the results obtained indicate that the
synthesized bisporphyrin-calix[4]arene-crown[6] are
multifunctional receptors forming stable complexes
with potassium and sodium cations, triethylenedi-
where λ1 is the wavelength of decreasing band, λ2 is
wavelength of the increasing band, [A] is the
porphyrinate concentration, [B] is the substrate
concentration, ΔA0 is maximum change in optical
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MAMARDASHVILI et al.
density of the solution at a given wavelength, ΔAi is the
change in optical density of the solution at a given
wavelength, at a given concentration [20].
solution of ammonia, evaporated to a minimum
volume, and subjected to chromatography on alumi-
num oxide (II degree of activity by Brockmann),
eluent chloroform. The eluate was evaporated and
porphyrin was precipitated with hexane. Yield 21.2 g,
40%. Rf 0.57 (Al2O3, eluent a mixture of CH2Cl2–
C6H14, 1:2). Electron absorption spectrum (toluene),
For 1: 2 complexes (A-2B) at stepwise (parallel or
sequential) complexation was used Eq. (2).
Kst = K1st·K2st (M)–2.
(2)
λ
max, nm (log ε): 407 (5.22), 532 (4.19), 567 (4.02),
At simultaneous complexation (third order reaction)
was used Eq. (3).
1
603 (4.11), 653.4 (4.37). H NMR spectrum of IV, δ,
ppm: 9.81 s (4 H, ms-H), 8.67 br.s (2H, OH), 7.69–
7.76 m (4H, Aro, porphyrin + 4H, Ar, calixarene)
7.55–7.59 m (2H, Arm, porphyrin + 4H, Ar,
calixarene), 7.06–7.09 m (4H, Arp, porphyrin, Arp,
calixarene), 4.11 s (6H, OCH3), 3.88 s (8H, ArCH2Ar),
3.80 q (8 H, CH2CH3), 3.72 m (8H, CH2CH3), 3.63 s
(4H, OCH2 CH2 O), 3.59 m ( 16 H, OCH2 CH2 O),
2.01 s (12H, CH3), 2.14 s (12H, CH3), 1.03 t (12H,
CH2CH3), 0.89 t (12H, CH2CH3), –2.23 br.s. (4H, NH).
Kst = [A·2B]/([A]·[B]2)
= (1/[B]2)[(ΔAi,λ1/ΔA0,λ1)·(ΔA0,λ2/ΔAi,λ2)]. (M)–2 (3)
The error in determining Kst is about 7–10%.
5,17-Bis-[meso-(3-aminophenyl)tetramethyltetra-
ethylporphyrin]-25,27-dimethoxy-26,28-crown[6]-
calix[4]arene, 1,3-alternate (III). A mixture of tin
dichloride dihydrate (0.67 g, 3.0 mmol), I (0.62 g,
0.3 mmol) and hydrochloric acid (50 ml) was stirred at
90–100°C for 30 min. The mixture was cooled,
filtered, and diluted with an equal volume of water.
Hydrochloride IV precipitate formed was filtered off
and washed in succession with dilute (1:2)
hydrochloric acid, ammonia and hot water. Compound
IV was dried, dissolved in benzene and subjected to
chromatography on aluminum oxide (II degree of
activity by Brockmann). The eluate was evaporated
and IV was precipitated with hexane. Yield 0.43 g,
71%. Rf 0.67 (Al2O3, eluent is a mixture CH2Cl2–
C6H14, 1:2). Electron absorption spectrum (toluene),
Zinc 5,17–bis[meso-(3-aminophenyl)tetramethyl-
tetraethylporphyrinate]-25,27-dimethoxy-26,28-
crown[6]-calix[4]arene, 1,3-alternate (V). To a
solution of III (30 mg) in dimethylformamide (70 ml)
was added an excess (1:10 mol) of zinc acetate. The
reaction mixture was refluxed for 30 min, cooled,
diluted with water (1:1), and the precipitate was
filtered off. The precipitate was dried and subjected to
chromatography on aluminum oxide, eluent a mixture
CH2Cl2–C6H14, 1:1. Solvent was distilled off in a
vacuum, the porphyrin was recrystallized from a
mixture CH2Cl2–CH3OH, 1:1. Yield 28.4 mg, 89%. Rf
0.69 (Al2O3), eluent a mixture CH2Cl2–C6H14, 1:1.
EAS (toluene), λmax, nm (log ε): 408 (4.89), 537 (4.19),
λ
max, nm (log ε): 406.0 (5.19), 530 (4.15), 566 (3.98),
1
602 (4.13), 650 (4.32). H NMR spectrum of III, δ,
ppm: 10.2 br.s (4H, NH2), 9.79 s. (4H, ms-H), 7.64–
7.69 m (4H, Aro, porphyrin + 4H, Ar, calixarene)
7.51–7.55 pm (2H, Arp, porphyrin + 4H, Ar,
calixarene), 7.02–7.07 m (4H, Arp, porphyrin. Arp,
calixarene), 4.13 s (6H, OCH3), 3.82 s (8 H,
ArCH2Ar), 3.76 q (8H, CH2CH3), 3.70 m (8H,
CH2CH3), 3.61 s (4H, OCH2CH2O), 3.57 m (16H,
OCH2CH2 O), 2.03 s (12H, CH3), 2.11 s (12H, CH3),
1.06 t (12H, CH2CH3), 0.85 t (12H, CH2CH3), –2.48
br.s. (4H, NH).
1
570 (3.82). H NMR spectrum of V, δ, ppm: 9.79 s (4
H, ms-H), 8.64 br.s (2H, OH), 7.65–7.71 m (4H, Aro,
porphyrin + 4H, Ar, calixarene), 7.52–7.56 m (2H,
Arm, porphyrin + 4H, Ar, calixarene), 7.01–7.05 m
(4H, Arp, porphyrin, Arp, calixarene), 4.07 s (6H,
OCH3), 3.86 s (8H, ArCH2Ar), 3.82 q (8 H, CH2CH3),
3.70 m (8H, CH2CH3), 3.60 s (4H, OCH2CH2O), 3.52
m (16H, OCH2CH2O), 2.06 s (12H, CH3), 2.15 s (12H,
CH3), 1.06 t (12H, CH2CH3), 0.93 t (12H, CH2CH3).
Similarly was synthesized zinc 5,17-Bis-[meso-(3-
hydroxyphenyl)tetramethyltetraethylporphyrinate]-
25,27-dimethoxy-26,28-crown[6]-calix[4]arene, 1,3-
alternate (VI). Yield 76%. Rf 0.46 (Al2O3), eluent a
mixture CH2Cl2–C6H14, 1:1. EAS (toluene), λmax, nm
5,17-Bis-[meso-(3-hydroxyphenyl)tetramethyltetra-
ethylporphyrin]-25,27-dimethoxy-26,28-crown[6]-
calix[4]arene, 1,3-alternate (IV). To a solution of II
(0.54 g, 0.3 mmol) in chloroform (10 ml) was added a
solution of boron tribromide (0.35 ml, 3.0 mol) in
chloroform (8 ml), and the mixture was stirred at room
temperature for 1 h. To the reaction mixture was added
methanol (5 ml) and the stirring was continued for
30 min. The resulting mixture was neutralized with a
1
(log ε): 409 (4.67), 535 (4.02), 568 (3.78). H NMR
spectrum of VI, δ, ppm: 9.75 s (4H, ms-H), 8.62 br.s
(2H, OH), 7.61–7.67 m (4H, Aro, porphyrin + 4H, Ar,
calixarene) 7.50–7.53 pm (2H, Arm, porphyrin + 4H,
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BISPORPHYRIN–CALIX[4]ARENE HETEROTOPIC RECEPTORS
601
5. Koifman, O.I., Kulikova, O.M., Mamardashvili, G.M.,
and Mamardashvili, N.Zh., Izv. VUZov, Ser. Khim. i
Khim. Tekhnol., 2009, vol. 52, no.3, p.76.
Ar, calixarene), 6.98–7.01 m (4H, Arp, porphyrin, Arp,
calixarene), 4.02 s (6H, OCH3), 3.84 s (8H, ArCH2Ar),
3.76 q (8H, CH2CH3), 3.73 m (8H, CH2CH3), 3.62 s
(4H, OCH2CH2O), 3.50 m (16H, OCH2CH2O), 2.01 s
(12H, CH3), 2.11 s (12H, CH3), 1.02 t (12H, CH2CH3),
6. Tsivadze, A.Yu., Varnek, A.A., and Khutorskii, V.E.,
Koordinatsionnye soedineniya metallov
s
kraun-
1
ligandami (Coordination Compounds of Metals with
Crown Ligands), Moscow: Nauka, 1991.
0.87 t (12H, CH2CH3). H NMR spectrum of complex
VI–L1 1:1, δ, ppm: 9.72 s (4H, ms-H), 8.60 br.s (2H,
OH), 7.63–7.70 pm (4H, Aro, porphyrin + 4H, Ar,
calixarene ) 7.52–7.55 m (2H, Arm, porphyrin + 4H,
Ar, calixarene), 7.01–7.04 m (4H, Arp, porphyrin, Arp,
calixarene), 4.05 s (6H, OCH3), 3.82 s (8H, ArCH2Ar),
3.77 q (8H, CH2CH3), 3.71 m (8H, CH2CH3), 3.65 s
(4H, OCH2CH2O), 3.52 m ( 16 H, OCH2CH2O), 2.03 s
(12H, CH3), 2.15 s (12H, CH3), 1.07 t (12H, CH2CH3),
0.89 t (12H, CH2CH3), –3.72 s (12H, N(CH2CH2)3N).
1H NMR spectrum of complex VI–2L2 1:2, δ, ppm:
9.74 s (4H, ms-H), 8.63 br.s (2H, OH), 7.67–7.72 m
(4H, Aro,, porphyrin + 4H, Ar, calixarene) 7.57–7.60 m
(2H, Arm, porphyrin + 4H, Ar, calixarene), 7.03–7.08
m (4H, Arp, porphyrin, Arp, calixarene), 4.09 s (6H,
OCH3), 3.96 s (4H, NH2), 3.83 s (8H, ArCH2Ar), 3.79
q (8 H, CH2CH3), 3.73 m (8H, CH2CH3), 3.67 s (4H,
OCH2CH2 O), 3.55 m ( 16H, OCH2CH2O), 5.71 d (4H
Ar, ligand), 2.07 s (12H, CH3), 2.17 s (12H, CH3), 1.09
t (12H, CH2CH3), 0.91 t (12H, CH2CH3), 2.69 d (4H,
Ar, ligand), 0.29 s (4H, NH2).
7. Hiraoka, M., Crown Compounds: Their Characteristics
and Applications, Moscow: Mir, 1986.
8. Gutsche, C.D., Calixarenes, in Host-Guest Complexes.
Synthesis, Structure and Use, Fegtle, F. and Weber, I.,
Eds., Moscow: Mir. 1988, p. 445.
9. Ogoshi, H., Mizutani, T., Hayashi, T., and Ruroda, Y.,
The Porphyrin Handbook, Kadish, K.M., Smith, K.M.,
and Guilard, R., Eds., New York: Academic, 2000,
vol. 6, p. 280.
10. Sanders, J.K.M., The Porphyrin Handbook, Kadish, K.M.,
Smith, K.M., and Guilard, R., Eds., New York:
Academic, 2000, vol. 3, p. 347.
11. Mamardashvili, G.M., Mamardashvili, N.Zh., and
Koifman, O.I., Usp. Khim., 2005, vol. 74, no. 8, p. 839.
12. Mamardashvili, G.M., Shinkar’, I.A., Mamardash-
vili, N.Zh., and Koifman, O.I., Koord. Khim., 2007,
vol. 33, no. 10, p. 787.
13. Churakhina, Yu.I., Zvezdina, S.V., and Mamardash-
vili, N.Zh., Zh. Org. Khim., 2007, vol. 43, no. 12,
p. 1858.
14. Mamardashvili, G.M., Doctorate (Chem.) Dissertation,
Ivanovo, 2009.
ACKNOWLEDGMENTS
15. Mamardashvili, N.Zh. and Golubchikov, O.A., Usp.
Khim., 2001, vol. 70, no. 7, p. 656.
This work was financially supported by Russian
Foundation for Basic Research (grants nos. 09-03-
00040-A and 09-03-97500-r_centerr_a) and the
Federal Target Program “Research and Scientific-
Pedagogical Cadres of the Innovation Russia for 2009–
2013,” GKno. 02.740.11.0106 and GKno. P 1105.
16. Koifman, O.I., Mamardashvili, N.Zh., and Antipin, I.S.,
Sinteticheskie retseptory na osnove porphyrinov i ikh
kon’yugatov s kaliks4. arenami (Synthetic Receptors
Based on Porphyrins and Their Conjugates with Calyx4.
Arenas), Moscow: Nauka, 2006, p. 246.
17. Mamardashvili, G.M., Kulikova, O.M., Mamardash-
vili, N.Zh., and Koifman, O.I., Koord. Khim., 2008,
vol. 34, no. 6, p. 435.
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