One and two point binding of organic bases molecules by meso-nitro substituted Zn-octaethylporphyrins

Article abstract of DOI:10.1142/S1088424614500916

A study of complex formation of Zn-octaethylporphyrin and its mono-, di-, tri- and tetra-nitro meso-substituted derivatives towards propylamine, 1,3-diaminopropane, 2-(4-imidazolyl)-ethylamine and 1,4-diazabicyclo[2.2.2]octane was carried out by UV-vis titration method and ¹H NMR. It has been determined that the nitro-substituted porphyrin receptors form with 1,3-diaminopropane and 2-(4-imidazolyl)-ethylamine 1:1 complexes with two points of binding. Individual contributions of a donor-acceptor interactions and a hydrogen bonding into a total energy of the complexes formation have been estimated. It has been shown that due to a good geometric match between the host-guest molecules the tetra-nitro substituted Zn-porphyrin has maximum binding ability towards the 1,3-diaminopropane, and the tri-nitro substituted Zn-porphyrin effectively binds the 2-(4-imidazolyl)-ethylamine.

Full text of DOI:10.1142/S1088424614500916

Journal of Porphyrins and Phthalocyanines
J. Porphyrins Phthalocyanines 2014; 18: 1–7
DOI: 10.1142/S1088424614500916
Published at http://www.worldscinet.com/jpp/
One and two point binding of organic bases molecules
by meso-nitro substituted Zn-octaethylporphyrins
a◊
a
a
Galina M. Mamardashvili* , Olga M. Kulikova , Olga V. Maltseva ,
a,b
a◊
Oscar I. Koifman and Nugzar Zh. Mamardashvili
a
G. A. Krestov Institute of Solution Chemistry of the Russian Academy of Sciences, Akademicheskaya st. 1, Ivanovo
1
53045, Russia
b
Ivanovo State University of Chemistry and Technology, Sheremetevsky av. 7, Ivanovo 153000, Russia
Received 23 July 2014
Accepted 15 September 2014
ABSTRACT: A study of complex formation of Zn-octaethylporphyrin and its mono-, di-, tri- and
tetra-nitro meso-substituted derivatives towards propylamine, 1,3-diaminopropane, 2-(4-imidazolyl)-
1
ethylamine and 1,4-diazabicyclo[2.2.2]octane was carried out by UV-vis titration method and H NMR.
It has been determined that the nitro-substituted porphyrin receptors form with 1,3-diaminopropane and
2
-(4-imidazolyl)-ethylamine 1:1 complexes with two points of binding. Individual contributions of a
donor–acceptor interactions and a hydrogen bonding into a total energy of the complexes formation have
been estimated. It has been shown that due to a good geometric match between the host–guest molecules
the tetra-nitro substituted Zn-porphyrin has maximum binding ability towards the 1,3-diaminopropane,
and the tri-nitro substituted Zn-porphyrin effectively binds the 2-(4-imidazolyl)-ethylamine.
KEYWORDS: Zn-octaethylporphyrin, meso-nitro substituted porphyrins, electron-withdrawing groups,
axial coordination, binding ability, stability constants, hydrogen bonding.
It was shown that binding ability of the Zn-porphyrins
INTRODUCTION
towards investigated imidazoles depends on the number
of nitro-groups and chemical modification of the
macrocycle increases the strength of the N-containing
small heterocyclic molecules axial binding more than an
order of magnitude.
In continuation of our research in the field of
supramolecular chemistry of porphyrins in this work we
investigated a binding ability of the Zn-porphyrins (I–V)
towards N-containing ligands [1,3-diaminopropane (L3),
Axial coordination of additional ligands by
metalloporphyrins is a main driving force of occurring
in living systems processes of molecular recognition
and self-organization. The strength of the coordination
is mainly determined by a structure of a tetrapyrrolic
macrocycle, basicity of a ligand and nature of a
solvent [1–9]. Previously, we studied one point binding
of imidazole (L1) and 1-methylimidazole (L2) by
Zn-octaethylporphyrin (I) and its mono-(II), di-(III), tri-
1
,4-diazabicyclo[2.2.2]octane (L4), 2-(4-imidazolyl)-
(IV) and tetra-nitro(V) meso-substituted derivatives by
ethylamine (L5) and propylamine (L6)] by methods of
UV-vis titration method in toluene [10]. The meso-nitro
substitution of the macrocycle is of great interest due to a
strong influence of the electron-withdrawing nitro groups
on a p-electron system of the tetrapyrrolic macrocycle.
1
UV-vis titration and H NMR. It was found that the nitro-
substituted porphyrin receptors (II-V) form with L3 and
L5 1:1 complexes with two points of binding. Individual
contributions of a donor–acceptor interactions and a
hydrogen bonding into a total energy of the complexes
formation have been estimated. The results obtained
by UV-vis titration method are in good agreement
with quantum chemical calculations performed for the
investigated complexes by BLYP/6-31G (d, p) using
◊SPP full member in good standing
*
Correspondence to: Galina M. Mamardashvili, email:galina.
mamardashvili@mail.ru, tel:+7 4932-336990, fax: +7 4932-
36237
3
Copyright © 2014 World Scientific Publishing Company

2
G.M. MAMARDASHVILI ET AL.
X1=X2=X3=X4=H
(I)
X3
X4
N
X1=X2=X3=H, X4=NO2 (II)
X1=X3=H, X2=X4=NO2 (III)
X =H, X =X =X =NO (IV)
N
Zn
N
N
X2
X1
1
2
3
4
2
I-V
X1=X2=X3=X4=NO2 (V)
H2N
N
H2N
N
HN
N
N
N
H2N
N
N
NH2
L6
L1
L2
L3
L4
L5
Structure
Gaussian software packages within density functional
theory (DFT).


DAi,l1 DAo,l2

[
[
A − B− Α]
1
.
-2
.
Kassoc.
=
=
, M
(2)

.
.
A] [B] [A] [B] [A] DAo,l1 DAi,l


2
where, l isthedecreasingwavelength, l istheincreasing
EXPERIMENTAL
1
2
wavelength, [A] is the Zn-porphyrin concentration, [B] is
Zn-5-nitro-2,3,7,8,12,13,17,18-octaethylporphyrin
the ligand concentration, DA is the maximal change of
0
(II),
Zn-5,15-dinitro-2,3,7,8,12,13,17,18-octaethylpor-
the optical density at the given wavelength, DA is the
i
phyrin(III),Zn-5,10,15-trinitro-2,3,7,8,12,13,17,18-octae-
thylporphyrin (IV) and Zn-5,10,15,20-tetranitro-2,3,
change of the optical density of the solution at a given
wavelength at a given concentration.
7,8,12,13,17,18-octaethylporphyrin (V) were obtained
1
H NMR spectra were recorded on a Brucker VC-500
according with [11, 12]. Zn-2,3,7,8,12,13,17,18-octae-
thylporphyrin (I) was obtained by complexation of
corresponding porphyrin ligand (2,3,7,8,12,13,17,18-
octaethylporphyrin) with Zinc acetate in boiling
dimethylformamide and showed the best correlation with
the spectral data presented for this compound according
with [13]. 2,3,7,8,12,13,17,18-octaethylporphyrin, the
ligands (L3–L6) and solvents (toluene and dichloro-
methane) from Sigma–Aldrich were used without further
purification. UV-vis spectra of the porphyrinates and their
evolution upon addition of the ligands were measured on
a Varian spectrophotometer Cary 100.
The UV-visible absorption spectral studies reveal
red shifted Soret and visible bands upon addition of the
ligands to a solution of the investigated metalloporphyrins
confirming that the N-containing entity of the ligands
binds to the Zn-cation of the coordination center of the
tetrapyrrolic macrocycle.
spectrometer with a working frequency of 500.17 MHz
in CDCl at 298 K, using tetramethylsilane (TMS) as the
3
internal standard.
1
H NMR of the system (II)-L3 (500.17 MHz; CDCl3;
Me Si; 298 K): d, ppm 9.85 (2H, s., Hmeso), 9.47 (1H, s.,
4
Hmeso), 4.06 (4H, m., b-CH -CH ), 3.81–3.76 (12H, m.,
2
3
b-CH -CH ), 1.90 (6H, t., b-CH -CH ), 1.77–1.74 (18H,
2
3
2
3
t., b-CH -CH ), 1.27 (2H, p., -CH -), 2.50 (2H, m.,
2
3
2
H N-CH -), 1.83 (2H, m., H N-CH -), 1.52 (2H, s.br.,
2
2
2
2
1
-
NH ), -1.68 (2H, s., -NH ). H NMR of the ligand L3: d,
ppm 1.28 (2H, p., -CH -), 2.48 (4H, m., H N-CH -), 1.02
2
2
2
2
2
(
4H, s., -NH ).
2
1
H NMR of the system (II)-L5 (500.17 MHz; CDCl3;
Me Si; 298 K): d, ppm 9.84 (2H, s., Hmeso), 9.48 (1H, s.,
4
Hmeso), 5.05 (1H, s., H ), 4.08 (4H, m., b-CH -CH ),
Im.
2
3
3
2
.80–3.78 (12H, m., b-CH -CH ), 2.39 (1H, d., H ),
2
3
Im.
.48 (2H, m., H N-CH -), 2.20 (1H, d., H ), 1.91 (6H,
2
2
Im.
t., b-CH -CH ), 1.78–1.76 (18H, t., b-CH -CH ), 1.50
2
3
2
3
The stability constants of the metalloporphyrin
1
(
2H, s.br., -NH ), 1.28 (2H, m., -CH -N-). H NMR of
2
2
complexes with the ligands in ratio of 1:1 (Kassoc.1
)
the ligand L5: d, ppm 7.90 (1H, d., H ), 7.41 (1H, d.,
Im.
and 2:1 (Kassoc.2) were calculated according with the
literature [14] based on spectrophotometric data at
two wavelengths (decreasing and increasing) using the
following relationships:
H ), 7.03 (1H, s., H ), 2.46 (2H, m., H N-CH -), 1.27
Im.
Im.
2
2
(
2H, m., -CH -N-), 0.99 (2H, s., -NH ).
2
2
RESULTS AND DISCUSSION


DAi,l1 DAo,l2

The ligands L3–L6 axial coordination by the
[
[
A − B]
1
-1
.
Kassoc.
=
=
, M
(1)

Zn-porphyrins (I–V) over a wide concentration range of
.
A] [B] [B] DAo,l1 DAi,l


2
-4
the ligands (C = 0.1 ÷ 8.0 × 10 M) is accompanied by
L
and
formation of one family of spectral curves with one set of
Copyright © 2014 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2014; 18: 2–7

ONE AND TWO POINT BINDING OF ORGANIC BASES MOLECULES BY MESO-NITRO SUBSTITUTED
3
(a)
(b)
-5
Fig. 1. (a) Changes in the UV-vis spectra of the system (II)–L6 in toluene at 20°C, C(II) = 1.0 × 10 M. (b) Binding isotherms of
-
5
the system (II)–L6 on the decreasing (400 nm) and the increasing (426 nm) waves lengths in toluene at 20°C, CZnP(II) = 1.0 × 10 M
isosbestic points in the UV-vis spectra of the reactionary
system Zn-porphyrin-ligand (ZnP–L). The details of
spectrophotometric titration upon the investigations
are described in our previous works [15–17]. Binding
isotherms of complexation have one step and saturation
of the systems ZnP–L occur at concentration ration of
the reagents on 1:1. These experimental findings indicate
formation of the single type complexes in a ratio of 1:1.
The changes in the UV-vis spectra and corresponding
binding isotherm of the system (II)–L6 are depicted in
Fig. 1 as an example.
Similarly to the binding ability of the Zn-porphyrins
(I–V) towards mono-dentate imidazoles (L1, L2) [10],
step-by-step meso-nitro substitution of a tetrapyrrolic
macrocycle leads to increasing of the porphyrinates
Fig. 2. Dependence of the stability constants of the porphyrinates
(I–V) with the ligands (L1–L3, L6) on the nature of small
N-containing organic molecules in toluene, 25°C
(I–V) binding ability towards bi-dentate ligands (L3–
L5) (Table 1, Fig. 2). Probably, meso-substitution of a
porphyrin by the electron-withdrawing groups reduces
degree of the macrocycle’s aromaticity (an electronic
effect), with one hand, and leads to the distortion of the
porphyrin macrocycle (a steric effect), on the other hand.
Joint influence of the electronic and steric effects should
reduce the strength of the Zn–N bonds of a porphyrin
coordination center and, consequently, increase the
partial positive charge on the Zn-cation. Increasing of a
charge on the cation increases its binding ability towards
investigated ligands and stability of the corresponding
complexes ZnP–L increases.
The distortion of the tetrapyrrolic macrocycle upon
meso-nitro substitution is confirmed by the calculations.
ThestartingZn-porphyrin(I)hasaplanarstructure(Fig.3).
Introduction of nitro groups into the tetrapyrrolic
macrocycle exerts a distorting effect, peaking at meso-
tetra substituted Zn-porphyrin (V). As a result, the
macrocycle adopts a conformation of distorted saddle.
Formally, the porphyrinate (V) is a dodeca-substituted
porphyrin, which has substituents in b- and meso-positions
of the macrocycle. The calculated geometrical parameters
-1
Table 1. Stability constants of 1:1 complexes (Kassoc.1, M )
between the porphyrinates (I–V) and the ligands (L1–L4, L6)
-
1
in toluene, CZnP = 1.1 × 10 M
I
II
III
IV
V
L1
L2
L3
L4
L5
21,400
28,000
15,200
41,900
79,800
45,800
88,700
188,000
295,000
328,500
783,000
293,000
114,000
129,000
180,000 265,000
100,000 481,000
225,000 248,000
163,000 201,000
a
1750
62,800
19,100
80,500
26,800
165,000
96,200
L6
16,000
a
Due to a poor solubility of the ligand L5 in toluene corres-
ponding stability constants were determined for solutions in
dichloromethane; the error in determining the stability constants
was 5–7%.
Copyright © 2014 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2014; 18: 3–7

4
G.M. MAMARDASHVILI ET AL.
Fig. 3. Optimized structures of the porphyrinates (I) and (V)
Table 2. Interatomic spacing’s (Å) of the porphyrinates (I–V)
of the complexes could be explained by a supplementary
hydrogen bonding between the macrocycles meso-nitro
group and one of the ligand’s amino group in addition to
the donor–acceptor interaction between the Zn-cation of
the macrocycles and another amino group of the ligand.
Formation of the complexes with two points of binding is
C-C
C-CN
C -C
C-Cmeso
N-Zn
N
meso
I
1.38
1.38
1.38
1.38
1.39
1.47
1.46
1.47
1.47
1.47
1.39
1.40
1.40
1.41
1.41
6.95
6.87
6.79
6.86
6.87
2.03
2.04
2.05
2.02
2.01
II
III
IV
V
1
also confirmed by the H NMR. It was established that in
the spectrum of the complex (II)-L3 a signal of protons
of one part of the ligand’s amino groups is broadened and
down-field shifted (D ≈ 0.50 ppm) due to of the hydrogen
bond’s formation and a signal of protons of another part of
the amino groups is up-field shifted (D ≈ 2.7 ppm) due to
of the shielding effect of ring current of the tetrapyrrolic
macrocycle. These experimental findings, according to
the data [18], suggest formation of the complexes with
two points of binding occurring with hydrogen bonds
formation. Expected structure of complex (II)–L3, which
is also confirmed by quantum-chemical calculations is
presented in Fig. 4 as an example.
In the works [18–20] devoted to the two-point binding
between porphyrinates with carboxyl and hydroxyl
groups and molecules of various amino acids and
nicotine the individual contributions of donor–acceptor
interactions and hydrogen bonding to the total energy
of axial complexes formation were evaluated. Taking
into account a possibility of hydrogen bonding with
participation of nitro group’s O-atom and H-atom of
propylamine’s amino group [21], using the approach
[18–20] we determined individual contributions of the
donor–acceptor interactions and hydrogen bonding to
the total energy of axial complexes formation between
the porphyrinates (II–V) and the bi-dentate ligand L3
of the porphyrinates (I–V) are presented in Table 2. The
steric interactionbetweenthe b-alkylsubstituentshydrogen
atoms and the meso-nitro groups is the main determinant
of the porphyrin molecule conformational behavior. A
dihedral angle between the intra-cyclic N-atoms and
conventional plane passing through the meso-C atoms is
the main characteristic of the tetrapyrrolic macrocycle
distortion. In going from the porphyrinate (I) to the
porphyrinate (V) the angle ranges from 1.20° to 33.00°.
It should be noted that upon step-by-step meso-
nitro substitution of the macrocycle the calculated
enthalpies of axial complexes ZnP–L formation in a
gas phase (Table 3) increases in the same sequence as
the experimental thermodynamic data obtained from the
stability constants in toluene (Table 4).
If in the range of the porphyrinates (I–V) the stability
of their axial complexes with the ligands L1, L2 and L6
increases by in an average an order of magnitude, in the
case of the complexes with L3, the stability is 50 times
higher (Table 1). This significant increasing in stability
Table 3. The calculated enthalpies of axial complexes ZnP–L formation in the gas phase
-
1
-1
-1
a
-1
-1
a
H (ZnP), (kcal.mol ) H (ZnP-L6), (kcal.mol )
D H°, (kcal.mol )
H (ZnP-L3), (kcal.mol )
D H°, (kcal.mol )
f
f
g
f
g
I
84.5
91.8
48.1
55.0
62.7
77.7
90.3
-18.4
-18.8
-19.3
-19.6
-21.9
103.9
107.4
113.8
128.7
141.9
-11.9
-15.7
-17.6
-17.8
-19.6
II
III
IV
100.1
115.3
130.2
V
a
The enthalpies of chemical reactions in ideal hypothetical gas phase according with the Hess law calculated on the basis of PM3-
enthalpies of the reagents formation.
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J. Porphyrins Phthalocyanines 2014; 18: 4–7

ONE AND TWO POINT BINDING OF ORGANIC BASES MOLECULES BY MESO-NITRO SUBSTITUTED
Table 4. Energies of ZnP–L complexes formation
5
-
1 a
-1 a
HB
-1 b
ZnP
-DGZnP-L3 kJ.mol
-DGZnP-L6 kJ.mol
-DG ZnP-L3, kJ.mol
I
24.12
26.58
28.51
32.40
33.61
23.97
24.41
25.25
28.41
29.14
0
II
2.17
3.26
3.99
III
IV
V
4.47
a
b
The total energy of ZnP–L complexes formation (DG = -RTlnK ). The energy
assoc.
HB
of hydrogenbonding in the complexes ZnP–L3 (DG
= DGZnP-L3 -DGZnP-L6).
ZnP-L3
N
H
H
H2N
O
N
O
N
Zn
N
N
N
(a)
(b)
Fig. 4. Expected structure of the complex (II)–L3 (a); calculated structure of the complex (II)–L3 (b)
Fig. 6. The contributions of the donor–acceptor interactions
Fig. 5. The contributions of the donor–acceptor interactions
(
DGZnP-L) and the hydrogen binding (DGHB) to the total energy
(
DGZn-L) and the hydrogen binding (DGHB) to the total energy
of axial complexes formation between the porphyrinates (II–V)
and the bi-dentate ligand L5
of axial complexes formation between the porphyrinates (II–V)
and the bi-dentate ligand L3
broadened and down-field shifted (D ≈ 0.50 ppm) due to
of the hydrogen bond’s formation and signals of protons
of the imidazolyl fragment of the ligand are up-field
shifted (Dmax ≈ 5.0 ppm) due to of the shielding effect of
ring current of the tetrapyrrolic macrocycle. Individual
contributions of the donor–acceptor interactions and
hydrogen bonding to the total energy of corresponding
axial complexes formation are depicted in Fig. 6. Unlike
the complexation with the ligand L3, upon complexation
of the porphyrinates (II–V) with the ligand L5 the
hydrogen bonding contribution to the total energy of
(
Table 4, Fig. 5). The porphyrinates (II–V) complexation
with the mono-dentate ligand L6 were used as comparison
systems. It was established that upon increasing of nitro
groups’ number in the macrocycle occurs increasing of
the axial coordination (DGZn-L) and hydrogen bonding
(DG ) energies (Fig. 5).
HB
Similarly was investigated binding ability of the
porphyrinates (II–V) towards the ligand L5. It was found
out that in the H NMR spectrum of the complex (II)–
L5 a signal of protons of the ligand’s amino group is
1
Copyright © 2014 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2014; 18: 5–7

6
G.M. MAMARDASHVILI ET AL.
Fig. 7. Binding isotherms of the system (II)–L4 on the decreasing (400 nm) and the increasing (426 nm) waves lengths in toluene
-
5
at 20°C, C(II) = 3.0 × 10 M
axial complexes formation reduces in going from the
meso-mono substituted porphyrinate (II) to the meso-
tetra substituted porphyrinate (V).
CONCLUSION
In summary, the study of complex formation of the
Zn-octaethylporphyrin and its mono-, di-, tri- and tetra-
nitro meso-substituted derivatives towards propylamine,
In general, it should be noted that the meso-tetra
substituted porphyrinate (V) has maximum binding
ability towards the ligand L3. The meso-three substituted
porphyrinate (IV) is more suitable for effective binding
of the ligand L5. Therefore, by chemical modification of
the Zn-octaethylporphyrin meso-positions, it is possible to
develop tetrapyrrolic receptors containing different shapes
forselectivebindingofguestmoleculesbyagoodgeometric
match of the ligand size to the size of the receptor.
Investigation of metalloporphyrins’ ability to form
complexes of different stoichiometry by complexation
with poly-dentate substrates is of grate interest from the
pointofviewofpolyfunctionalsupramolecularassemblies’
creation.Wehavepreviouslyestablishedthatcomplexation
of meso-unsubstituted Zn-octaalkylporphyrins with cyclic
bidentate ligand L4 proceeds in two stages [22, 23]. In the
field of low concentrations of the ligand occurs formation
of the complexes in ratio of 2:1. Under conditions of
the ligand’s excess the 2:1 complexes turn into the 1:1
complexes.
1,3-diaminopropane, 2-(4-imidazolyl)-ethylamine and
1
,4-diazabicyclo[2.2.2]octane by the methods of UV-vis
1
titration and H NMR showed that the nitro-substituted
porphyrin receptors form with 1,3-diaminopropane
and 2-(4-imidazolyl)-ethylamine 1:1 complexes with
two points of binding. Individual contributions of the
donor–acceptor interactions and hydrogen bonding into
the total energy of the complexes formation have been
estimated. It has been shown that the tetra-nitro substituted
Zn-porphyrin has maximum binding ability towards
the 1,3-diaminopropane, and the tri-nitro substituted
Zn-porphyrin effectively binds the 2-(4-imidazolyl)-
ethylamine. Therefore, step-by-step meso-nitro substitu-
tion of the Zn-octaethylporphyrin allows developing
tetrapyrrolic receptors of different shapes for selective
binding of substrates by a good geometric match of the
host–guest molecules. These experimental findings provide
good insight into the biological molecular recognition
performed by proteins and enzymes. Taking into account
the fact that the processes are accompanied by a clear
and easily identifiable response in the UV-vis spectra,
these porphyrins with several active sites in the molecule
could also find effective using as molecular optical
sensing devices, in which the strong absorption or intense
fluorescence signals of the porphyrin core can respond
sensitively to a biologically active substrate binding.
In this work we studied the ligand’s L4 axial
coordination by the porphyrinates (II–V). It was found
that among the investigated nitro-porphyrinates only the
least spatially distorted mono-substituted porphyrinate
(
II) interacts with the ligand L4 in two stages (Fig. 7)
9
-2
to form 2:1 (Kassoc.2 = 5.2 × 10 M ) and 1:1 complexes.
Over a wide concentration range of the ligand (C =
0
L
-
4
÷ 8 × 10 M) the porphyrinates (III–V) interact
with the ligand L4 in one stage with formation of 1:1
complexes. These experimental findings confirm our
previous conclusion [24] that only spatially undistorted
Zn-porphyrins are capable of the bidentate ligands two-
point binding.
Acknowledgements
This work was supported by the Russian Scientific
Foundation (Project No. 14-13-00232).
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J. Porphyrins Phthalocyanines 2014; 18: 6–7

ONE AND TWO POINT BINDING OF ORGANIC BASES MOLECULES BY MESO-NITRO SUBSTITUTED
7
Supporting information
<To be completed by author(s)>> Figures S1–S3
are given in the supplementary material. This material is
available free of charge via the Internet at http://www.
worldscinet.com/jpp/jpp.shtml.
11. Gong L and Dolphin D. Can. J. Chem. 1985; 63:
01.
4
<
1
1
1
1
1
2. Watanabe E, Nishimura S, Ogoshi H andYoshida Z.
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