Supramolecular self-assembly of 5,10,15,20-tetrakis-(3-hydroxyphenyl) porphyrinatozinc with some transition metals and bidentate ligands

Article abstract of DOI:10.1134/S1070428008090224

Coordination interactions between 5,10,15,20-tetrakis(3-hydroxyphenyl) porphyrinatozinc(II) and transition metal chlorides [La(III), Mn(II), Cr(III), Sn(II)], 1,4-diazabicyclo[2.2.2]octane, and 4,4′-bipyridine were studied. Self-assembly of supramolecular

Full text of DOI:10.1134/S1070428008090224

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 9, pp. 1378–1383. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © V.S. Tyurin, Yu.P. Yashchuk, I.P. Beletskaya, 2008, published in Zhurnal Organicheskoi Khimii, 2008, Vol. 44, No. 9,
pp. 1393–1399.
Supramolecular Self-Assembly of 5,10,15,20-Tetrakis-
(3-hydroxyphenyl)porphyrinatozinc with Some Transition Metals
and Bidentate Ligands
V. S. Tyurin, Yu. P. Yashchuk, and I. P. Beletskaya
Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences,
Leninskii pr. 31, Moscow 119991 Russia
e-mail: tv@org.chem.msu.ru
Received August 30, 2007
Abstract—Coordination interactions between 5,10,15,20-tetrakis(3-hydroxyphenyl)porphyrinatozinc(II) and
transition metal chlorides [La(III), Mn(II), Cr(III), Sn(II)], 1,4-diazabicyclo[2.2.2]octane, and 4,4′-bipyridine
were studied. Self-assembly of supramolecular bis-porphyrin structures was developed.
DOI: 10.1134/S1070428008090224
Studies on porphyrin-based supramolecular struc-
which are held together through axial coordination of
a bidentate ligand and possessing additional peripheral
centers for binding metal cations. As base structural
component we selected 5,10,15,20-tetrakis(3-hydroxy-
phenyl)porphyrinatozinc(II) (II, ZnTHPP) having
several potential reaction centers and therefore capable
of forming numerous bonds. The central Zn(II) ion in
II is coordinately unsaturated, so that extra coordina-
tion is possible. Peripheral hydroxy group can also be
involved in donor–acceptor interactions with metal
cations.
tures are important due to unique optical and electro-
chemical properties and high thermal and chemical
stability of such systems, which make them promising
from the viewpoint of design of new materials for
photoconductors, nonlinear optics, catalysis, mem-
brane technology, and medicine [1–3]. Self-assembly
involves selective binding of a substrate (guest mole-
cule) by receptor (host) via molecular recognition [4].
The rigid porphyrin skeleton makes cyclic tetrapyr-
roles ideal structural units of a supramolecular asso-
ciate (host molecule) where substituents capable of
interacting in different ways with guest molecules are
arranged in a definite order.
Self-assembly processes imply that the components
be complementary, i.e., the ratio between information
provided by receptor and information that can be per-
ceived by substrate should be optimal. Such informa-
tion may be encoded in the receptor architecture and
its binding sites [4]. Thus, “instruction” for assembly
of a supramolecular system is put into the structure of
its low-molecular components.
Metal porphyrin receptors are capable of recogniz-
ing various species via axial (extra) coordination of
ligands at the central metal ion [5]. Coordination
structures containing metalloporphyrins belong to
a specific group of structurally organized systems
whose molecular components possess unique selec-
tivity; the conditions of their formation and stability
depend on the metal nature and properties of the metal-
loporphyrin which constitutes the base of supra-
molecule [6].
Structural specificity of metalloporphyrin receptor
II imply assembly of just dimeric supramolecular as-
sociates so that axial ligand be oriented orthogonally to
the plane of the porphyrin macroring. If a bidentate
ligand is coordinated through both coordination cen-
ters, two porphyrin fragments are arranged in parallel
planes. Zinc porphyrins are capable of accepting only
one axial ligand to give five-coordinate central metal
ion [7]), which prevents formation of polymeric
structures.
The goal of the present study was to build up bis-
porphyrin structures formed as a result of self-asso-
ciation of molecular components via coordination
interactions. The target structure was supramolecular
dimer I consisting of two metalloporphyrin fragments
1
378

SUPRAMOLECULAR SELF-ASSEMBLY OF 5,10,15,20-TETRAKIS(3-HYDROXYPHENYL)...
1379
O
O
HO
M
O
N
M
HO
O
N
N
N
Zn
N
Ligand
N
N
Zn
N
Zn
N
N
N
N
β
2
'
M
O
OH
O
6
'
4
'
5
'
M
O
O
OH
I
II
Peripheral hydroxy groups in the meta positions of
the α -atropoisomer are oriented in accordance with
plexes should be determined by the reaction medium.
4
The largest association constants (K ) are usually ob-
a
the axial ligand position (Scheme 1), whereas para
position of the self-complementary hydroxy groups
favors formation of netlike polymeric structures [8, 9].
Two zinc porphyrin fragments may be linked via coor-
dination with a bidentate ligand which plays the role of
intermolecular spacer. Taking into account the nature
of the central metal ion, we examined nitrogen-con-
taining bidentate ligands, 1,4-diazabicyclo[2.2.2]oc-
tane (III, DABCO) and 4,4′-bipyridine (IV, 4,4′-bpy).
served in inert aromatic solvents (benzene, toluene),
while polar solvents favor displacement of the com-
plex formation equilibrium toward initial metallopor-
phyrin [5, 6]. 5,10,15,20-Tetrakis(3-hydroxyphenyl)-
porphyrinatozinc is soluble only in polar medium,
which considerably hinders the extra coordination
process.
The reaction of ZnTHPP with 0.5 equiv of DABCO
was accompanied by upfield shift of signals from the
β-protons and (Δδ = –0.33 ppm) and protons in the
Porphyrinatozinc II can react with a bidentate
ligand to give 1:1 and 2:1 complexes (Scheme 2)
whose composition will depend on the reactant ratio
and ligand nature [10, 11]. Extra coordination is read-
ily reversible, and the stability of the resulting com-
1
benzene rings (Δδ ≈ –0.2 ppm) in the H NMR spec-
trum; the signal from protons in DABCO was also
displaced upfield (δ –4 to –5 ppm; Δδ ≈ –7 ppm). In
keeping with published data [10–13], we presumed
Scheme 1.
OH
MX
N
HO
N
N
N
Zn
N
HO
N
HO
n
OH
N
N
MX
n
N
Zn
N
MX
n
OH
N
N
HO
N
MX
n
MX
n
HO
OH
OH
N
Zn
N
OH
N
II
HO
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 9 2008

1
380
TYURIN et al.
Scheme 2.
N
Zn
N
N
N
N
2
''
2:1
N
3''
or
N
N
III
IV
1:1
formation of a 2:1 complex in which two ZnTHPP
molecules are linked through DABCO molecule. Mu-
tual influence of the two porphyrin fragments leads to
additional shielding of protons therein. The coordinat-
ed ligand is weakly held in the cavity formed by the
porphyrin macrorings; free and coordinated ligands are
readily exchanged in solution at room temperature,
thus leading to considerable broadening of the ligand
Obviously, additional binding centers are necessary to
ensure stability of structure I.
Bidentate coordination of a ligand by two metallo-
porphyrin macrorings makes the latter spatially closer,
so that the peripheral hydroxy groups adopt appro-
priate orientation for donor–acceptor interaction with
external metal ions (Scheme 1). Just the presence of
a bidentate ligand should favor assembly of the
desired structure from monomeric species present
in solution [17].
1
signals in the H NMR spectrum [14, 15]. In the
presence of more than 1 equiv of DABCO, the upfield
shift of the ZnTHPP proton signals is insignificant;
presumably, in this case ZnTHPP–DABCO complex
with a composition of 1:1 is formed. Upfield shift of
signals from protons in the guest molecule results from
strong shielding by the ring current in the porphyrin
macroring [10, 11]. The upfield shift attains its maxi-
mal value when 2:1 complex is formed, for the shield-
ing produced by two porphyrin macrorings is twice as
strong.
We used anhydrous oxophilic metal salts MX (M =
n
2+
3+
2+
3+
Mn , Cr , Sn , La ) to ensure binding at the hy-
droxy groups and avoid competition between the latter
and electron-donating nitrogen atoms in the ligand.
The reactions were carried out at low reactant concen-
–3
trations (~10 M) to prevent formation of various
oligomers. In the reaction of ZnTHPP with MnCl in
2
the presence of DABCO or 4,4′-bpy, signals in the
1
H NMR spectrum of the reaction mixture were
In the reaction of ZnTHPP with 0.5 equiv of
strongly broadened and were difficult to interpret;
a probable reason is paramagnetic effect of manganese
cation. The reactions of ZnTHPP with SnCl and CrCl
4
,4′-bpy and more, the chemical shifts of protons in the
former change insignificantly (Δδ ≈ –0.05 ppm). By
contrast, the signals from 4,4'-bpy are displaced con-
siderably upfield, the 3″-H signal being displaced to
a lesser extent (Δδ ≈ –1.3 ppm) than that of 2′′-H (Δδ ≈
2
3
in the presence of 0.5 equiv of DABCO or 4,4′-bpy
were accompanied by protonation of the porphyrin
macroring, presumably due to liberation of hydrogen
chloride.
–
3.3 ppm). This is readily understood, for the 3″-H
protons are more distant from the porphyrin macro-
rings. As with DABCO, the signals from protons (es-
pecially from 2″-H) in the 4,4′-bpy ligand are broad-
ened. Probably, in this case 1:1 complex is formed.
According to published data [16], the upfield shift of
The best results were obtained in the reaction of
ZnTHPP with 2 equiv of anhydrous lanthanum(III)
chloride. The resulting complexes were soluble only in
strongly coordinating solvents like DMSO-d that are
6
capable of destroying coordination dimers; in this case
4
,4′-bpy signals upon formation of 2:1 complex should
1
H NMR spectroscopy becomes noninformative.
be greater (Δδ ≈ –3 and –7 ppm for 3″-H and 2″-H,
respectively).
Therefore, the self-assembly processes were studied by
MALDI TOF mass spectrometry. The energy of inter-
molecular interactions is much smaller than the energy
of covalent bonds, so that weak coordination bonds are
partially disrupted as a result of ionization, and the
Thus ZnTHPP with the above ligands in polar
medium forms preferentially 1:1 complexes, though
the formation of labile 2:1 complexes is also possible.
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SUPRAMOLECULAR SELF-ASSEMBLY OF 5,10,15,20-TETRAKIS(3-HYDROXYPHENYL)...
1381
intensity of ion peaks corresponding to supramolecular
associates is much lesser than the intensity of those
corresponding to molecular fragments.
sorption maximum (Δλ = 23 nm). Analogous shift is
observed in the absence of ligand (DABCO or
4,4′-bpy), indicating selective coordination of LaCl at
3
the hydroxy groups of ZnTHPP. The position of the
Soret band in the spectrum of complex VII remains
unchanged; it also does not change in the presence of
various amounts of lanthanum(III) chloride and
In the reaction with 4,4′-bpy as ligand, the mass
spectrum of the reaction mixture contained three
groups of signals (isotope multiplets) corresponding to
three dimeric structures V–VII. Presumably, lantha-
num cations coordinate water molecules on exposure
to air during application of a sample onto the target.
Thus two modes of association of ZnTHPP are pos-
sible: self-complementary via hydrogen bonding with
4
,4′-bipyridine. In keeping with published data, coordi-
nation of 4,4′-bipyridine inside the porphyrin dimer
cavity should be accompanied by a 1–2-nm red shift of
the Soret band, but such shift is often not observed in
the spectra [10]. The formation of “face-to-face” dimer
should lead to a blue shift of the Soret band as a result
of interactions between electrons in the two porphyrin
systems [18]; presumably, these opposite effects com-
pensate each other.
formation of simple (ZnTHPP) dimer VII and hetero-
2
complementary through coordination to Ln(III) with
formation of structure VI which can accommodate
4
,4′-bpy molecule.
According to the mass spectra, only dimers VI and
To conclude, we have studied self-assembly of co-
ordination dimers from 5,10,15,20-tetrakis(3-hydroxy-
phenyl)porphyrinatozinc(II) and a number of metal
cations and exobidentate ligands. The formation of
supramolecular dimers with different structures was
detected by MALDI TOF mass spectrometry. In par-
ticular, coordination dimer with lanthanum(III) chlo-
ride possesses a cavity where reversible coordination
of 4,4′-bipyridine is possible. Stable supramolecular
bis-porphyrin structures can be formed via coordina-
tion of four peripheral centers to external metal ions.
These structures give rise to labile complexes with
exobidentate ligands. The stability of such complexes
could be enhanced by introducing stronger peripheral
ligand centers with a view to isolate them as individual
substances.
VII are formed in the presence of DABCO. A probable
reason is that the size of the DABCO molecule
(
3.75 Å; cf. 7 Å for 4,4′-bpy) does not fit the dimer
cavity, so that coordination bonds with the ligand are
weak, and complex like V is not formed.
Dimer VII was detected in the mass spectra of all
reaction mixtures containing ZnTHPP. It is readily
formed in solution via hydrogen bonding between the
peripheral hydroxy groups. Similar orientations of the
phenyl rings in II with respect to the porphyrin macro-
4
ring (α -atropoisomer) give rise to four binding centers
which ensure stability of that dimeric structure in
solution.
The electronic absorption spectra of the complexes
are characterized by blue shift of the lanthanum ab-
OH
OH
N
N
N
N
Zn
N
Zn
N
HO
LaCl3
HO
N
HO
LaCl3
HO
N
N
H O
2
LaCl3
H O
2
LaCl3
OH
OH
H O
2
H O
2
OH
OH
HO
HO
H O
2
LaCl3
H O
2
LaCl3
H O
2
H O
2
LaCl3
LaCl3
N
OH
OH
N
N
N
N
Zn
Zn
N
N
N
N
HO
HO
V
VI
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 9 2008

1
382
TYURIN et al.
the progress of the reaction being monitored by TLC.
The mixture was filtered through a layer of silica gel
~30 g) to collect the main purple fraction. Removal of
H
O
(
N
N
the solvent on a rotary evaporator gave 257 mg (98%)
Zn
N
of complex II as a dark red amorphous substance.
O
N
1
H
H NMR spectrum (acetone-d ), δ, ppm: 7.31 d.d (4H,
6
H
3
3
O
O
4′-H, J = 8.3, 1.5 Hz), 7.61 t (4H, 5′-H, J = 7.8 Hz),
7
O
H
3
.71 d (4H, 6′-H, J = 7.8 Hz), 7.73 s (4H, 2′-H), 8.73 s
H
(
4H, OH), 8.96 s (8H, β-H). Electronic absorption
O
O
H
N
–3
–1
–1
spectrum (THF), λmax, nm (ε×10 , l mol cm ): 555
10), 595 (2.7), 422 (164) (Soret band). Mass spec-
H
(
+
N
trum: m/z 740 (I 100%) [M] .
rel
Zn
N
N
H
Reaction of ZnTHPP with 1,4-diazabicyclo[2.2.2]-
octane (III). a. A 0.061 M solution of DABCO (III) in
carbon tetrachloride, 80 μl (0.005 mmol), was added to
O
a solution of 7.7 mg (0.01 mmol) of ZnTHPP (II) in
VII
1
0
.5 ml of acetone-d . H NMR spectrum (acetone-d ),
6
6
δ, ppm: –5 to –4 br.s (6H, C H N ), 7.19 d (4H, 4′-H,
J = 7.5 Hz), 7.38 br.s (4H, 5′-H), 7.43–7.47 m (8H,
6
12
2
EXPERIMENTAL
The progress of reactions and the purity of products
3
6
′-H, 2′-H), 8.21–8.25 br.s (4H, OH), 8.63 s (8H, β-H).
were monitored by thin-layer chromatography on
Merck 60 F254 silica gel plates. Column chromatog-
raphy was performed on silica gel 60 (Alfa Aesar,
b. A 0.061 M solution of DABCO (III) in carbon
tetrachloride, 165 μl (0.01 mmol), was added to a solu-
tion of 7.7 mg (0.01 mmol) of ZnTHPP (II) in 0.5 ml
1
7
0–230 mesh).
of acetone-d . H NMR spectrum (acetone-d ), δ, ppm:
6
6
0
.07 br.s (12H, C H N ), 7.28 m (4H, 4′-H), 7.55 m
6 12 2
The electronic absorption spectra in the visible and
(
8H, 5′-H, 6′-H), 7.62 s (4H, 2′-H), 8.53 s (4H, OH),
UV regions were measured on a Varian Cary-100 spec-
trophotometer using rectangular quartz cells (cell path
8
.81 s (8H, β-H).
1
length 10 mm). The H NMR spectra were recorded at
c. A 0.061 M solution of DABCO (III) in carbon
room temperature on a Bruker AM-400 spectrometer
tetrachloride, 1 ml (0.06 mmol), was added to a solu-
(
400 MHz); the chemical shifts were determined rela-
tion of 7.7 mg (0.01 mmol) of ZnTHPP (II) in 0.5 ml
1
tive to the residual proton signals of deuterated sol-
vents (acetone-d , δ 2.06 ppm; DMSO-d , δ 2.50 ppm).
The mass spectra (MALDI TOF) were obtained on
a Bruker Daltonics Ultraflex mass spectrometer (posi-
tive ion registration, target voltage 20 mV, no matrix).
of acetone-d . H NMR spectrum (acetone-d ), δ, ppm:
6
6
3
6
6
2.23 s (72H, C H N ), 7.17 d.d (4H, 4′-H, J = 8.3,
1.5 Hz), 7.50 t (4H, 5′-H, J = 7.8 Hz), 7.60 m (8H,
6′-H, 2′-H), 8.87 s (8H, β-H). H NMR spectrum of
6 12 2
3
1
pure DABCO (acetone-d ): δ 2.67 ppm, s.
6
Anhydrous lanthanum(III) chloride was prepared
by reaction of 0.63 g (3.07 mmol) of La O with 2 ml
of 37% hydrochloric acid. Excess HCl and water were
removed on a rotary evaporator, and the residue was
Reaction of ZnTHPP with 4,4′-bipyridine (IV).
a. A 0.013 M solution of 4,4′-bipyridine (IV) in aceto-
nitrile, 420 μl (0.006 mmol), was added to a solution
of 8 mg (0.011 mmol) of ZnTHPP (II) in 6 ml of
2
3
dried with SOCl . 5,10,15,20-Tetrakis(3-hydroxy-
acetonitrile, and the mixture was stirred for 1 h.
2
1
phenyl)porphyrin (THPP) was synthesized in 20%
yield according to the procedure described in [19]; its
NMR, UV, and mass spectra were consistent with
published data.
H NMR spectrum (acetone-d ), δ, ppm: 5.43 br.s (2H,
6
2″-H), 6.45 br.s (2H, 3″-H), 7.26 m (4H, 4′-H), 7.54 t
3
(4H, 5′-H, J = 7.8 Hz), 7.62 m (4H, 6′-H), 7.65 m
(4H, 2′-H), 8.68 s (4H, OH), 8.89 s (8H, β-H).
5
,10,15,20-Tetrakis(3-hydroxyphenyl)porphyri-
natozinc(II) (II). Zinc(II) acetate dihydrate, 1676 mg
7.6 mmol), was dissolved in ~100 ml of acetonitrile
b. A 0.013 M solution of 4,4′-bipyridine (IV) in
acetonitrile, 1.7 ml (0.022 mmol), was added to a solu-
tion of 8 mg (0.011 mmol) of ZnTHPP (II) in 6 ml
(
on heating under stirring, 260 mg (0.383 mmol) of
THPP was added, and the mixture was stirred for 4 h,
of acetonitrile, and the mixture was stirred for 1 h.
1
H NMR spectrum (acetone-d ), δ, ppm: 6.84 br.s (8H,
6
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 9 2008

SUPRAMOLECULAR SELF-ASSEMBLY OF 5,10,15,20-TETRAKIS(3-HYDROXYPHENYL)...
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5
6
7
8
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1
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3
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0.0135 mmol) of ZnTHPP (II) in 15 ml of anhydrous
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1
1
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1
stirred for 2 h. H NMR spectrum (DMSO-d –ace-
6
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6
6
12
2
3
3
vol. 4, p. 2129.
(
7
4H, 4′-H, J = 8.1 Hz), 7.54 t (4H, 5′-H, J = 7.8 Hz),
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rel
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7
(
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by the Russian Academy of Sciences (Program of
Basic Research of the Chemistry and Material Science
Department, no. 7, “Chemistry and Physical Chemistry
of Supramolecular Systems and Atom Clusters”),
and by the Russian Foundation for Basic Research
8. Koifman, O.I., Mamardashvili, N.Zh., and Antipin, I.S.,
Sinteticheskie retseptory na osnove porfirinov i ikh
kon”yugatov s kaliks[4]arenami (Synthetic Receptors
Based on Porphyrins and Their Conjugates with Calix-
[4]arenes), Konovalov, A.I., Ed., Moscow: Nauka, 2006.
(
project nos. 05-03-32833, 08-03-00994).
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