СИНТЕЗ, СПЕКТРАЛЬНІ ХАРАКТРИСТИКИ ТА СТАБІЛЬНІСТЬ НОВИХ ГЕТЕРО-МЕТАЛІЧНИХ КОМПЛЕКСІВ Nd(III) ТА Co(II) З АМІНОПОЛІКАРБОНОВИМИ КИCЛОТАМИ
New heterometallic complexes of Nd(III) and Co(II) based on ethylenediaminetetraacetic and ethylenediaminedisuccinic acids have been synthesized. The complexes studied by electron absorption spectroscopy, IR-spectroscopy, and thermogravimetric analysis. The influence of a number of factors on the pr...
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V.I.Vernadsky Institute of General and Inorganic Chemistry
2022
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Репозитарії
Ukrainian Chemistry Journal| _version_ | 1871465800142946304 |
|---|---|
| author | Trunova , Elena Mishchenko , Artem Makotryk , Tamara |
| author_facet | Trunova , Elena Mishchenko , Artem Makotryk , Tamara |
| author_institution_txt_mv | [
{
"author": "Elena Trunova ",
"institution": "V. I. Vernadskii Institute of General and Inorganic Chemistry of the Ukrainian National Academy of Sciences, Akad. Palladin Avenue 32\/34, Kyiv 03142, Ukraine"
},
{
"author": "Artem Mishchenko ",
"institution": "V. I. Vernadskii Institute of General and Inorganic Chemistry of the Ukrainian National Academy of Sciences, Akad. Palladin Avenue 32\/34, Kyiv 03142, Ukraine"
},
{
"author": "Tamara Makotryk ",
"institution": "V. I. Vernadskii Institute of General and Inorganic Chemistry of the Ukrainian National Academy of Sciences, Akad. Palladin Avenue 32\/34, Kyiv 03142, Ukraine"
}
] |
| author_sort | Trunova , Elena |
| baseUrl_str | https://ucj.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-22T08:23:48Z |
| description | New heterometallic complexes of Nd(III) and Co(II) based on ethylenediaminetetraacetic and ethylenediaminedisuccinic acids have been synthesized. The complexes studied by electron absorption spectroscopy, IR-spectroscopy, and thermogravimetric analysis. The influence of a number of factors on the properties and structure of heteronuclear complexes is discussed. The spectral characteristics of homonuclear and heteronuclear complexes are compared. A theoretical analysis of the geometry of Co(II) and Nd(III) complexes with ethylenediaminesuccinic acid was carried out by the semi-empirical PM7 method. It has been shown that the f-d-complexes are of the folded type, in which the ligand-complexone realizes the maximum denticity to Nd(III), and the Co(II) coordination sphere is formed by bridging edta/edds carboxyl groups and intrasphere water molecules. The Co(II) coordination polyhedron corresponds to a distorted octahedron, and the Nd(III) coordination polyhedron corresponds to a one-capped square antiprism (C4v) with the coordination number Nd(III)=8. During study fixed that heterometallic complexes have the same structure in solutions and in the solid state. |
| doi_str_mv | 10.33609/2708-129X.88.02.2022.116-130 |
| first_indexed | 2025-09-24T17:43:43Z |
| format | Article |
| fulltext |
Неорганічна хімія
116 ISSN 2708-129X. УКР. ХІМ. ЖУРН., 2022, т. 88, No 2
УДК 541.49:[546.657+546.732]-386 doi: https://doi.org/10.33609/2708-129X.88.02.2022.116-130
SYNTHESIS, SPECTRAL CHARACTERIZATION AND STABILITY OF THE NEW
Nd (III) AND Co (II) HETEROMETALLIC COMPLEXES WITH
AMINOPOLYCARBOXYLIC ACIDS
O.K. Тrunova*, A.M. Mishchenko, T.O. Makotryk
Vernadsky Institute of general and inorganic chemistry of the Ukrainian National Academy of
Sciences, 32/34, Akad. Palladin av., 03142, Kyiv, Ukraine
* e-mail: trelkon@gmail.com
New heterometallic complexes of Nd(III) and Co(II) based on ethylenediaminetetraacetic and
ethylenediaminedisuccinic acids have been synthesized. The complexes studied by electron ab-
sorption spectroscopy, IR-spectroscopy, and thermogravimetric analysis. The influence of a
number of factors on the properties and structure of heteronuclear complexes is discussed. The
spectral characteristics of homonuclear and heteronuclear complexes are compared. A theoreti-
cal analysis of the geometry of Co(II) and Nd(III) complexes with ethylenediaminesuccinic acid
was carried out by the semi-empirical PM7 method. It has been shown that the f-d-complexes
are of the folded type, in which the ligand-complexone realizes the maximum denticity to
Nd(III), and the Co(II) coordination sphere is formed by bridging edta/edds carboxyl groups and
intrasphere water molecules. The Co(II) coordination polyhedron corresponds to a distorted oc-
tahedron, and the Nd(III) coordination polyhedron corresponds to a one-capped square anti-
prism (C4v) with the coordination number Nd(III)=8. During study fixed that heterometallic
complexes have the same structure in solutions and in the solid state.
Keywords: heterometallic complexes, cobalt, neodymium, aminopolycarboxylic acids, spectral
properties.
INTRODUCTION. The development of
modern high technologies is based on the use of
new functional materials. This requires the de-
velopment and application of new or signifi-
cantly modified known methods for their syn-
thesis, which use new precursors with high reac-
tivity, the direction of action, and economic
feasibility. In recent years, researchers have
paid attention to finding ways to create new
complex compounds that contain two metals of
different nature (heterometallic complexes) in
one internal coordination sphere. Among studies
on the targeted synthesis of heteropolynuclear
coordination compounds of lanthanides and
transition elements, heterometallic aminopoly-
carboxylate complexes are of great interest due
to their structural diversity and the expansion of
potential areas of their application. Aminopoly-
carboxylate ligands are multidentate ligands and
their important characteristics are the bridging
nature of carboxylate groups. [1-4].
In most of the works devoted to the study
of heterometallic complexes based on aminopo-
lycarboxylates, the structure of the complexes is
determined by X-ray diffraction. The number of
heteronuclear compounds of s- and d-elements
of M
І
[М
ІІ
(Hedta)(H2O)]2∙nH2O (M
І
=Ca, Mg, Sr,
Ba; М
ІІ
=Cr, Co, Cu) is known for the most
common and widely studied complex of ethyle-
nediaminetetraacetate (H4edta)[5 6]. Hetemetal-
lic lanthanide lanthanide-polyaminocarboxylate
of bismuth {{NdBi(edta)(NO3)2(H2O)7;22}nwas
synthesized, which is a 3D coordination poly-
mer [7]. Recently, heterometallic complexes of
mailto:trelkon@gmail.com
O.K. Тrunova, A.M. Mishchenko, T.O. Makotryk
ISSN 2708-129X. УКР. ХІМ. ЖУРН., 2022, т. 88, No 2 117
lanthanides with such elements as Ge, Bi with
polyaminocarboxylic acids have been studied as
precursors for the synthesis of ultrafine powders
of metal oxides and metal nanoparticles [8]. In
[9, 10], heteronuclear terbium (neodymium) -
germanium (or bismuth) compounds with
H4edta were synthesized and studied. Their
spectral and luminescent characteristics have
been studied. It has been shown that 4-f lumi-
nescence of lanthanide ions is observed in all
heteronuclear compounds. Based on the
Na[Ce(edta)] complex, a two-dimensional hete-
rometallic coordination polymer
Ce2Co3(edta)3(H2O)11·12H2O was synthesized as a
metal- ligand, in which ten Ce(III) atoms are
coordinated by six carbon- oxygen atoms, three
water molecules and four water molecules form-
ing a curved two-cap antiprism. Each of the Co
atoms bonds to two hydrated Ce atoms through
trident bridged carboxylate groups, and each
Ce(III) atom has three adjacent Co atoms. These
fragments are connected in a three-dimensional
network of water molecules between the layers
through numerous hydrogen bonds [11].
A review article [12] on the stereochemi-
stry of complexonates provides a detailed de-
scription of the spatial features of edta complex-
es with lanthanide (III) ions. All ethylenediami-
netetraacetate complexes of lanthanides are mo-
nonuclear, the ligands in all the described com-
pounds are hexadentate, and the remaining
coordination sites are occupied by water mole-
cules (2, 3 or 4). Among the structurally charac-
terized normal mononuclear complexes of lan-
thanides with edta is the isostructural series of
compounds LnеdtaM·8H2O, which includes
potassium salts with Ln
3+
= Nd, La, Gd, sodium
with Ln
3+
= Nd, Tb, Dy, Er and ammonium with
Ln
3+
= Nd, Gd. A full structural study was per-
formed for KLaеdta·8H2O, NaTbеdta·8H2O and
NaDyеdta·8H2O. For all the above complexes,
the lanthanide ion has a coordination number =
9: Ln
3+
coordinates 6 donor edta atoms and
three water molecules. Coordinated еdta
4-
anions form a curved trigonal prism with trian-
gular faces. Increasing the size of the metal
atom and the length of the Ln-N bonds promote
the attachment of three water molecules, which
are located in the symmetry of the prism.
There are very few works in the literature
on the study of heterometallic complexes of d-f
metals with еthylenediaminedisuccinic acid
(H4edds). The neodymium-zinc ethylenediami-
nedisuccinates were described in [13]. It was
shown that in heterometallic complexes the Nd3+
ion is bound to two α- and one β-carboxyl
groups and a nitrogen atom of the NH group of
the ligand, and the coordination sphere of the
Zn2+ion is formed by oxygen atoms β-carboxyl
group edds, which performs a bridging function,
and water molecules. New f-d-heterometallic
complexes Pr(III), Co(II), Zn(II) with aminopo-
lycarboxylic acids (ethylenediaminetetraacetic,
еthylenediaminedisuccinic) were synthesized
and spectroscopically characterized in [14]. It
has been shown that f-d-complexes belong to
complexes of the "folded" type, in which the
ligand-complexon realizes the maximum dentic-
ity to Pr(III), and the coordination sphere of the
3d-cation is formed by the chain carboxyl
groups of the ligands and intrasphere water mo-
lecules.
This work presents the results according
to synthesis, spectral characterization, and
stability of the heterometallic complexes Nd(III)
and Co(II) with ethylenediaminetetraacetic and
еthylenediaminedisuccinic acids in solutions
and in the solid-state.
EXPERIMENT AND DISCUSSION OF
THE RESULTS. Neodymium nitrates of
Nd(NO3)36H2O and cobalt Со(NO3)26H2O
were used for the synthesis of heterometallic
complexes with aminopolycarboxylic acids.
Ethylenediaminedisuccinic acid was obtained
by the condensation reaction of maleic acid with
ethylenediamine [15].
Synthesis, spectral characterization and stability…
118 ISSN 2708-129X. УКР. ХІМ. ЖУРН., 2022, т. 88, No 2
Ethylenediaminetetraacetic acid was
purchased from Ukrsit LLC (Kyiv) and used
without further purification.
Solutions of salts and
aminopolycarboxylic acids of the required
concentration were prepared according to the
exact sample. The concentration of metals in the
solutions was determined by complexometric
titration (0.01 M) with indicators of murexide
(for Co
2+
ions) and arsenazo 1 (for Nd
3+
ions).
The synthesis of heterometallic complexes
was carried out by the interaction of protonated
Co(II) monocomplexes with an inorganic salt of
Nd(III) («block» method):
[СоHL
1
/(L
2
) (H2O)] +Ln(NO3)3+ nH2O =
[Со(μ- L
1
/(L
2
) Nd(H2O)4]NO3 + 2HNO3
The choice of the method for the synthesis
of heterometallic complexes is determined by
the values of the thermodynamic stability
constants of mononuclear complexes (lgKst.).
When the values of lgKset. complexes of M
I
L
and M
II
L differ by several orders of magnitude,
the less stable monometallic complex serves as
a ―building block‖ for obtaining a
heterobinuclear compound by exocoordination
of additional metal ions. In other words,
mononuclear complexes act as metal chelate
ligands capable of coordinating the second
metal ion. It is worth notingthat heteronuclear
complexes based on complexones were obtained
without isolating the "building block" from the
solution.
The synthesis of heterometallic complexes
was carried out according to the
followingmethod. To 100 ml of an aqueous
solution of cobalt nitrate Со(NO3)26H2O (0.1 g-
mol) was added 200 ml of a solution containing
0.2 g-mol H4edds (H4edta) and 2 g-mol NaOH.
The resulting mixture (pH ~ 3.5) was stirred
intensively for 20 minutes, after which 100 ml
of neodymium salt solution (0.1 g-mol) was
added to the reaction mixture. The suspension
was heated in a water bath at 50 - 60
0
C for 1.5 -
2 hours and left to cool. Abundant precipitates
of the heterometallic NdCoL
1
,
2
∙nH2O
complexes (yield of heterometallic complexes
81-86%) fall out of the solutions. The
precipitate was filtered and washed with a
mixture of ethyl alcohol and acetone (1:1) and
dried to constant weight at room temperature
(202⁰С).The obtained heterometallic
complexes are sparingly soluble in water and
other polar solvents.
Investigation of the processes of
complexation of neodymium and coyulate ions
with aminoplicarboxylates in solutions at their
equimolar ratio and С=1·10
-3
mol/dm
3
was car-
ried out by the method of electron absorption
spectroscopy. Electronic spectra were recorded
on a Specord M40 spectrophotometer in 1 cm
thick quartz cuvettes in the range of 50,000 -
10,000 cm
-1
.In fig. 1 shows the electronic
absorption spectra of complexes Nd(III) and
Co(II) with edta (a) and edds (b), and in table.1
- position of the main absorption maxima of Nd
3
+
ions.
In the UV-VIS spectra of aqueous
solutions of neodymium-containing complexes
(both homo- and heterometallic) range there are
narrow bands of characteristic 4f-transitions
from the basic
4
I9/2-state of the Nd(III) ion
(Table 1.1), but for heterometallic complexes
the structure of spectra increases, increases the
intensity of absorption compared to the spectra
of homo-complexes and occurs by shifting the
maxima of the bands of the corresponding f-f-
transitions in the long-wavelength region
(∆νmax≈170-190 cm
-1
for edds and ≈78-90 cm
-1
for edta). This fact indicates the formation of
heterometallic complexes, which contain both
metals in the internal coordination sphere.
In the 4f-absorption spectra of lanthanide
complexes, thebands corresponding
tothehypersensitive transitions are subject to
O.K. Тrunova, A.M. Mishchenko, T.O. Makotryk
ISSN 2708-129X. УКР. ХІМ. ЖУРН., 2022, т. 88, No 2 119
а
b
Fig.1. UV-VIS spectra of heterometallic complexes Nd(III) and Co(II) with edta (a) and edds (b) (pH ~ 7;
С=1·10
-3
mol/dm
3
).
Table 1
Transition energies (cm-
1
) in UV-VIS spectra of Nd(III) and Co(II) complexes with
aminopolycarboxylic acids.
Transition Ndaq
3+
Ndedds/Ndedta NdCoedds/NdCoedta NdL-NdCoL
4
I9/2
2
P1/2 23064 23470/23221 23358/23300,23912 112/79
4
I9/2
4
G9/2 19560 19688/19447 19537/19537 151/90
4
I9/2
4
G7/2 19160 19264/19114 19113/19075 151/39
4
I9/2
4
G5/2 17360 17451/17234 17261/17275 190/45
4
I9/2
4
F9/2 14720 14781/14740 14712/14778 69/38
4
I9/2
4
F7/2
13480 13630/13432 13440/13477 190/45
4
I9/2
4
F5/2
12560 12743/12512 12588/12551 155/39
4
I9/2
4
F3/2
11560 11726/11513 11549/11435 177/78
the greatest influence of the ligand field, so
special attention was paid to these bands. Thus,
the absorption spectra of neodymium
compounds are characterized by two
hypersensitive transitions:
4
I9/2 →
2
P1/2
(νmax≈23350 сm
-1
) and
4
I9/2 →
4
G5/2,
2
G7/2
(νmax≈.17400 сm
-1
and 19200 сm
-1
respectively).
It is worth notingthat these bands for
ethylenediaminetetraacetate complexes of
neodymium are in the lower frequency range
than the corresponding bands for
ethylenediaminedisuccinate complexes. In this
case, the positions of νmax for Ndedta are close
to νmax in the spectra of the aquaion Ndaq
3+
,
which may indicate close symmetry of
aquacomplexes and complexonates with edta.
The Nd complexes with edds have a much
larger hypsochromic shift of the absorption
maxima of f-f transitions compared to Ndaq
3+
,
which is caused by a decrease in mutual
electron repulsion (nepheloxetic effect) due to
the presence of a chiral CH-carbon atom in the
edds molecule.
For heterometallic complexes, the
4
G5/2
transition frequency in the spectra of the
NdCoedds complex is shifted by 190 cm
-1
to the
10000 12000 14000 16000 18000 20000 22000 24000
0.00
0.02
0.04
0.06
0.08
0.10
A
b
s
o
rb
a
n
c
e
4
F
9/2
2
P
1/2
Ndedta
CoNdedta
4
F
3/2
4
F
5/2
,
2
H
9/2
4
G
5/2
,
4
G
7/2
4
S
3/2
,
4
F
7/2
2
K
13/2
,
4
G
9/2
,
4
G
7/2
4
T
1g
(
4
F)
4
T
1g
(
4
P)
,cm
-1
Coedta
10000 15000 20000 25000 30000
0.00
0.05
0.10
A
b
so
rb
a
n
c
e
Ndedds
Coedds
4
T
1g
(
4
F)
4
A
2g
(
4
F)
4
F
3/2
2
K
13/2
,
4
G
7/2
,
4
G
7/2
4
G
5/2
,
4
G
7/2
4
F
5/2
,
2
H
9/2
4
S
3/2
,
4
F
7/2
2
P
1/2
4
D
3/2
,
4
D
5/2
,
2
I
11/2
,
4
D
1/2
,
2
L
15/2
,cm-1
CoeddsNd
4
T
1g
(
4
F)
4
T
1g
(
4
P)
Synthesis, spectral characterization and stability…
120 ISSN 2708-129X. УКР. ХІМ. ЖУРН., 2022, т. 88, No 2
low-frequency region relative to the
corresponding transition to the UV-VIS spectra
Ndedds, while for NdCoedta νmax this transition
is shifted by 45 cm
-1
in the high frequency
region. In this case, for both heteronuclear
complexes, the band
4
I9/2 →
4
G5/2,
2
G7/2 does not
undergo cleavage, which is characteristic of
compounds with low symmetry [16]. In the
heteronuclear complex NdCoedta, splitting of
the
4
I9/2→
2
P1/2band is observed, which is a
consequence of the decrease in the symmetry of
the Nd (III) coordination polyhedron in the
heteronuclear complex. In the spectrum of the
complex NdCoedds for the
4
I9/2→
2
P1/2transition
only one band is observed, which indicates the
existence of one type of compound in solution.
The shift of the maximum of this band is 112
cm
-1
, which is typical for complexes with low
coordination numbers.
In the UV-VIS spectra of heterometallic
complexes, not only the change in the νmax
position of the Nd(III) ion is observed, but also
the νmax position of the Co(II) ion changes
significantly. If monometallic cobalt
complexates are characterized by the presence
in the electronic absorption spectra of d-d
transitions maxima of Со
2+
ion at 19844 cm
-1
(transition
4
T1g(
4
F)→
4
T1g(
4
P)) and 26480 cm
-1
(transition
4
T1g(
4
F)
4
A2g(
4
F)), then in the
electronic spectra of heterometallic complexes
the last transition disappears, and for the term
4
T1g(
4
F)→
4
T1g(
4
P) a significant hypsochromic
shift (CoL-NdCoL≈ -1190cm
-1
) is observed
compared to Coedds (edta). In addition, the
specified maximum for heteronuclear
compounds is split into 3 components (20999,
21233, 21657 for CoeddsNd and 20994, 21341,
21570 cm
-1
for CoedtaNd), which may indicate
a change in the coordination environment of
cobalt ions and the existence of heteronuclear
compounds of several differently coordinated
cations of Co(II). However, the position of the
d-d transitions for the Со
2+
ion in heterometallic
complexes corresponds to the octahedral
environment, regardless of the type of
aminopolycarboxylic ligand.
In order to obtain information on the
quantitative composition of metals included in
the internal coordination sphere of complexes
formed in the system Co(II) - edds - Nd(III), the
dependence of optical density on the
concentration of one of the metals at constant
concentrations of ligand and second metal and
pH ~ const (7) (Fig. 2).
Fig. 2. Composition of heterometallic complexe
CoeddsNd by the method of additives.
As seen from Fig..2, the value of optical
density relative to the concentrations of both
Со
2+
(curve 1) and Nd
3+
(curve 2) varies in the
same way: with increasing concentration of
metals from 0,5·10
-4
до 0,9·10
-4
mol/dm
3
there
is a decrease in the values of optical density,
and at CCо(II)=CNd(ІII)=1·10
-3
mol/dm
3
on both
curves there is a well-defined inflection, which
corresponds to the ratio
Cо(II):edds:Nd(ІII)=1:1:1.This clearly indicates
that the internal coordination sphere of
heterometallic complexes Co(II) and Nd(III)
with edds includes one metal of each type.
Oscillator forces (Table 2) were
determined for each of the neodymium-cobalt-
containing complexes studied, which were
determined by the method [17].As seen from
table 1.2, the strength of the oscillators of
0,4
0,42
0,44
0,46
0,48
0,5
0,52
0,5 0,6 0,7 0,8 0,9 1 1,1 1,2 1,3 1,4
C(Nd3+)
A
(C
o
2
+
)
1
2
O.K. Тrunova, A.M. Mishchenko, T.O. Makotryk
ISSN 2708-129X. УКР. ХІМ. ЖУРН., 2022, т. 88, No 2 121
Table 2
Experimental and calculated forces of oscillators (P) of transitions
4
I9/2→
2S+1
LJ of Nd(III) ion in UV-
VIS spectra and standard error of calculation (×10
6
).
Multiples
Nd(NO3)3 Ndedta Ndedds CoeddsNd CoedtaNd
Pexp. Pcalcul. Pexp. Pcalcul. Pexp. Pcalcul. Pexp. Pcalcul. Pexp. Pcalcul.
4
F3/2 3,43 2,57 3,19 2,57 3,28 2,29 2,15 2,32 1,24 1,70
4
F5/2+
2
H9/2 9,97 9,84 9,53 9,38 9,50 9,44 9,25 8,95 7,59 7,19
4
F7/2+
4
S3/2 10,81
11,0
9
9,98 10,35 10,68 10,88 9,72 10,09 7,99 8,34
4
G5/2+
2
G7/2 10,64
10,7
2
15,23 15,36 13,50 13,55 12,27 12,37 10,90 10,94
4
G7/2+
4
G9/2 6,72 5,25 7,98 5,48 6,07 5,06 6,67 4,94 4,58 3,85
4
D3/2+
4
D5/2+
2
I11/2+
4
D
1/2
9,90
11,6
7
9,82 11,86 8,49 10,11 9,54 10,49 7,21 7,44
root mean square
error
1,43 1,91 1,25 1,18 0,60
the CoeddsNd complex exceeds the strength of
the oscillators for CoedtaNd in 1.15 to 1.4
times. When comparing homonuclear
complexes, an increase in P is also observed
during the transition from edds to edta. The
values of the shift of the band maxima and the
increase in the strength of the transition
oscillators in the Nd(III) complexes with edds
and edta indicate the different nature of the
ligand field influence, which may be caused by
differences in the coordination environment of
the lanthanide ion in the corresponding
compounds.
Based on the obtained data according to
the Judd – Ofelt theory [18], the intensity
parameters Ωλ(λ = 2, 4, 6) of the neodymium
ion in the complexes were calculated (Table 3).
The parameter Ω2 and the oscillator power
of the supersensitive transition
4
I9/2→
4
G5/2+
2
G7/2
increase in the series
Nd(NO3)3<Nd(L)Co<Nd2L, which indicates a
lower local symmetry of the Nd (III) ion in the
monometallic complex , compared with
heterometal. The parameter Ω6 decreases in the
series Nd(NO3)3> Nd2L > Nd(L)Co, which may
indicate an increase in the covalence of the
neodymium-ligand bond in the transition from
Table 3
Judd-Ofelt parameters Ωλ (×10
-20
сm
2
).
Compound λ = 2 λ = 4 λ = 6
Nd(NO3)3 1,05 5,29 9,32
Nd(edta) 3,18 5,46 8,68
Nd(edds) 2,86 4,51 9,22
Co(edta)Nd 2,56 3,29 7,07
Co(edds)Nd 2,21 4,77 8,51
monometallic to heterometallic complex.
It is known that the parameter Ω2 is the
most sensitive to the immediate environment of
the lanthanide ion. The increase in the value of
this parameter contributes to both increasing the
degree of covalence of bonds with donor atoms
and reducing the symmetry of the ion
environment. The change in symmetry may be
associated with a change in the geometry of the
coordination polyhedron of lanthanides, as well
as with a change in the structure of ligands
while maintaining the geometry of the
coordination polyhedron. Nd(III) ionic solutions
are dominated by nine-coordinated aqua
complexes, the geometry of which corresponds
to a highly symmetric three-cap trigonal prism
(point symmetry group D3h) [19]. Therefore,
Synthesis, spectral characterization and stability…
122 ISSN 2708-129X. УКР. ХІМ. ЖУРН., 2022, т. 88, No 2
Nd(NO3)3 is characterized by a low value of Ω2
(1,05·10
20
cm
2
). In the case of the Ndеdta
complex, the Nd(III) environment is a one-cap
square antiprism (C4v), which is formed by two
nitrogen atoms and four oxygen atoms of the
ligand, as well as three water molecules
(coordination number = 9) [20]. The value of Ω2
for CoedtaNd compared to Ndеdta decreases
from 3,18·10
20
cm
2
to 2,56·10
20
cm
2
, which
indicates an increase in the symmetry of the
Nd(III) environment due to the curvature of its
polyhedron due to the formation of Co ions with
the Edta molecule and water molecules
simultaneously. Close values of Ω2 obtained for
the CoeddsNd complex (2,21·10
20
cm
2
) may
indicate a similar geometry of the coordination
polyhedron Nd(III) in these compounds.
Probably, the heterometallic complexs
coordination polyhedron is close to a one-cap
square antiprism (C4v) and is formed by two
nitrogen atoms, three carboxylate oxygen atoms
of the edds molecule (or four O in the case of
edta) and three (two) water molecules
(coordination number Nd(III) = 8). The shift of
the maximum of the
4
I9/2→
2
P1/2 transition band
in the synthesized heterometallic complexes to
the long-wavelength region and the increase in
the intensity of the supersensitive
4
I9/2→
4
G5/2+
2
G7/2 transition also indicates a
decrease of the coordination number in the
central ion from 9 to 8. That is, 6 places in the
inner sphere of the Nd(III) ion are occupied by
hexadent anions of complexones, and two
places are occupied by H2O molecules.
The different nature of the coordination of
complexion anions in heteronuclear complexes
is also reflected in the comparison of the degree
of covalence b
1/2
, which is determined by the
nepheloxetic effect (Table 4) [21].
As seen from table4, the covalence of the
bond in heterometallic complexes with both
edta and edds is approximately the same, but
exceeds b
½
for mononuclear complexes ~ 1.1
Table 4
Parameter of normalized electrostatic repulsion
of SNES, nepheloxetic ratio β and covalence
parameter b
½
(relative to Nd
3+
in the gas phase,
for which SNES = 88713 cm
– 1
).
Complex SNES, сm
–1
β b
½
Nd(NO3)3 86134 0.971 0.121
Ndedta 86485 0.975 0.112
Ndedds 85663 0.966 0.113
Co(edta)Nd 85882 0.968 0.126
Co(edds)Nd 85956 0.969 0.125
times, which confirms the conclusion that the
covalent component increases in the formation
of a heteronuclear complex.
The calculated values of the
nepheloxeticparameter β are close to 1, (Table
4), which may indicate high ionicity of the Nd–
O bond in both monometallic and heterometallic
complexes. But a slight increase in β values in
NdL
1,2
is associated with increasing ionicity of
the bond, and with a decrease in the
coordination number of neodymium in
comparison with hetero-complexes [22].
The general dependence of shifts of the
main maxima of the f-f transitions of the Nd
+3
ion in the synthesized heterometallic complexes
in comparison with the monometallic ones looks
as follows (Fig. 3).
Fig. 3. Diagram of shifts in UV-VIS spectra of
heterometallic complexes Nd(III)-Co(II) with
aminopolycarboxylic acids (cm
-1
), L
1
=edta, L
2
=
edds.
112
151 151
190
69
190
155
177
79
90
39 45 38 45 39
78
51
77
63 55 60
92
22
13
216
160
217 212
160 160
268
159
0
50
100
150
200
250
300
2P1/2 4G9/2 4G7/2 4G5/2 4F9/2 4F7/2 4F5/2 4F3/2
NdL2-NdCoL2
NdL1-NdCoL1
NdL1-NdZnL1
NdL2-NdZnL2
O.K. Тrunova, A.M. Mishchenko, T.O. Makotryk
ISSN 2708-129X. УКР. ХІМ. ЖУРН., 2022, т. 88, No 2 123
For the synthesized homo- and
heteronuclear lanthanide complexes with L
-4
anions of complexons, their stability constants
were calculated using the mathematical
programCLINP [23] (Table 5).
Table 5
Values of stability constants of complexes of
Nd(III) and Со(II) with aminopolycarboxylic
acids.
Complex lgKst.
[NdL
1
]
-
16,47 0,06
[NdL
2
]
-
14,4±0,05
[СоL
1
]
2
18,98± 0,06 [24]
[СоL
2
]
2-
17,19± 0,05 [25]
[NdСоL
1
]
+
20,1 0,03
[NdСоL
2
]
+
19,01 0,04
Heterometallic complexes are several
orders of magnitude more stable than the
corresponding monometallic complexes due to
the formation of additional bonds, and,
accordingly, metal cycles, with donor ligand
atoms. The higher stability of heterometallic
complexes compared to binary compounds
containing the same proton forms of the ligand
is associated with the formation of bonds of 2
cations with donor atoms edta/edds, that is, the
increase in the stability of the complexonate
occurs due to its «crosslinking». Comparison of
lgKst. complexes NdL
1,2
, CoL
1,2
and
NdCoL
1,2
shows that the difference in the
stability of heterometallic and monometallic
neodymium-containing complexes (ΔlgKNdCoL1-
NdL1=3,63; ΔlgKNdCoL2-NdL2=4,61) is several or-
ders of magnitude lower than the corresponding
difference between heterometallic and cobalt
complexes (ΔlgKNdCoL1-СоL1=1,12; ΔlgKNdCoL2-
CoL2=1,82). This is probably due to the fact, that
in the heterometallic complex the cobalt ion
forms much fewer bonds (or cycles) with the
donor atoms of complexones than the neody-
mium ion. That is, NdCoL
1,2
complexes are
«folded» type complexes, in which Co(II)
complexes will play the role of exo-coordinated
ligands in the formation of heterobinuclear
complexes, and the Co
2+
coordination sphere in
the heteronuclear compounds will be formed
only by oxygen atoms of capacious carboxyl
groups of ligands and water molecules.The sta-
bility of complexes with edds is less than that of
the corresponding complexes with edta, which
is probably due to different sizes and numbers
of chelate metallocycles, as well as to deforma-
tion of six-membered -alanine rings in ethyle-
nediamine disuccinate complexes [14].
Solid samples of synthesized
heterometallic complexes were studied by IR-
spectroscopy. IR-spectra were recorded on a
spectrophotometer Specord M-80 in the range
of 4000-400 cm
-1
in tablets with KВr. The
hydrate composition of the synthesized
complexes was determined by
thermogravimetric method. The
thermogravigrams were recorded on a
derivatograph Q - 1500°D F. Paulik, J. Paulik,
L. Erdey in the temperature range 20-500
0
C
with a heating rate of 5
0
/min in a platinum
crucible in the presence of the carrier Al2O3
(anhydrous).
The thermolysis of the studied
heterometallic complexes NdCoL
1/2
occurs in
the same way and has a stepwise character.
(Table 6).
At the first stage of thermolysis in a wide
range of temperatures (80-160
0
C) is their
dehydration, which is accompanied by
endothermic effects. In the region of 80–100
0
С,
a decrease in the mass of complexes is observed
due to the detachment of two outer-water
molecules, which is accompanied by
insignificant endothermic effects.With a further
increase of the temperature (120–180
0
С), the
removal of H2O molecules, which are part of the
internal coordination sphere of the complexes,
takes place.
Different dehydration temperatures
Synthesis, spectral characterization and stability…
124 ISSN 2708-129X. УКР. ХІМ. ЖУРН., 2022, т. 88, No 2
Table 6
Thermal stability of heterometallic complexes Nd(III) and Co(II) with aminopolycarboxylic acids.
Complex
The process of dehydration
t destruction,
0
С
t,
o
С/ thermal effect
Loss of mass, % nH2
O Сalcul. Experiment. beginning close
[NdCoL
1
]
+
105/ (endo) 4,48 4,59 2
213 485 114/ (endo)
153/ (endo)
7,51
7,51
7,59
7,54
3
2
[NdСоL
2
]
+
92/ (endo) 7,00 7,12 2
220 475 117/(endo)
155/ (endo)
7,00 7,46
3
3
Table 7
Basic oscillation frequencies in the IR spectra of homo- and heteronuclear complexes of Nd(III) and
Co(II) with aminopolycarboxylic acids and their assignment (cm
-1
).
band
assignment
Compounds
NdL
2
NdСоL
2
СоL
2
NdL
1
NdСоL
1
СоL
1
(COOH) 1719 - - 1731 - 1730
as(COO) 1592
1636 -1620
1548
1650
1583
1650,
1593
1690
1675
1560
s(COO)
1405,
1331,
1310
1410
1329
1312
1492; 1390
1319
1440, 1410
1402, 1385
1470-1358
(CH) 2878
2943,
2862
2864
2912
2990
2975
2975-2900
(М-O)
566, 598,
666
510
576,
620
687
537;603;626 700 -520
(М-N) 458 456 449 458 457
n(H2O)intra 3262 3242 3224 3220
n(H2O)inter. 3445 3454 3460 3420
indicate different structural role of water
molecules in coordination compounds, due to
the formation of a branched system of intra- and
intermolecular hydrogen bonds characteristic of
metal complexonates [26].
The five intraspherical H2O molecules,
which play different structural roles, removed at
higher temperatures (≈120
0
C and 150-190
0
C).
Probably, 3 molecules of water, which are
cleaved at lower temperatures, are bound to the
cation of 3d metal, and two molecules of H2O
are bound to the lanthanide ion, complementing
its coordination sphere to the coordination
number 8. In the area t ≈225–300
0
C destruction
occurs organic ligands with removal of carboxyl
and amino groups in the form of CO2 and NO2,
respectively. These processes are accompanied
by a number of endo- and exo-effects. Complete
decomposition of compounds ends at t ≈ 480
0
C.
To determine the nature of the binding of
metal ions to the functional groups of aminopo-
lycarboxylic acids, their IR spectra were record-
O.K. Тrunova, A.M. Mishchenko, T.O. Makotryk
ISSN 2708-129X. УКР. ХІМ. ЖУРН., 2022, т. 88, No 2 125
ed. In fig. 4 as an example, the IR spectra of the
Coedds(1) and NdeddsCo (2) complexes are
given, and Table 7 shows the main oscillation
frequencies in the IR spectra of homo- and hete-
ronuclear complexes of Nd(III) and Co(II) with
aminopolycarboxylates.
Fig. 4. IR spectra of complexes Coedds(1),
NdeddsCo (2).
In the comparative analysis of the IR-
spectra of the synthesized heteronuclear
complexes and their corresponding metal
complexonates, the main attention was paid to
the absorption bands corresponding to the
oscillations of the functional groups whose
donor centers are involved in the binding to
cations. In all IR-spectra of complexes with
aminopolycarboxylic acids for both
monometallic and heterometallic complexes
there is a wide band in the range of 3200- 3500
cm
-1
, which corresponds to the valence
vibrations of water molecules and indicates the
presence of intra- and intermolecular hydrogen
bonds. Manifestation of ν(OH) in the spectra in
the form of a doublet indicates that the studied
heterometallic complexes contain both external-
spherical water molecules and H2O molecules
occupying the intraspherical position. This
conclusion correlates well with
thermogravimetry data.
In the IR spectra of heterometallic com-
plexes the band of valence vibrations of the free
carboxyl group of aminopolycarboxylites (1731
cm
-1
for Ndedta and 1719 cm
-1
for Ndedds) dis-
appears and two split bands of strong intensity
as(COO
-
) appear in the range 1560 - 1670 cm
-1
and s(COO
-
)1350 - 1470 cm
-1
. Compared with
the IR-spectra of monometallic complexonates,
a shift of these bands to the long-wavelength
region is observed. Moreover, the bands ν of
oscillations of carboxyl groups in the spectra of
heterometallic complexes appear in the form of
doublet or triplet bands, which indicates a dif-
ferent coordination environment of complexing
metals in hetero- and homometallic compounds.
The difference in the position of the oscillation
frequencies νs and νas of COO
-
-groups
(Δ=as(COO) - s(COO)) for heterometallic amino-
polycarboxylates is ~ 200 cm
-1
and ~ 170 cm
-1
,
which indicates the presence of NdСоL
1,2
com-
plexes both monodentatically coordinated de-
protonated carboxyl groups and the bidentate-
bridging nature of their binding [27]. The
presence in the low-frequency region of the IR
spectra of the multiplet bands in the region 510–
700 cm
–1
, which belong to the M – O bond
oscillations, also indicates a different
coordination of the two cations of the carboxyl
groups of the ligands[28].
In the spectra of aminocarboxylate
complexes, there are absorption bands in the
region of 4440–460 cm
– 1
, which correspond to
ν oscillations of the M – N bond. The (M-N)
oscillation band for the NdL
1.2
Coand
NdL
1.2
complexes is singlet in nature and has
almost the same frequency, which indicates that
the Co
2+
ion is not involved in the formation of
this heterobinuclear compound. The presence of
metals in the amino groups of ligands is
indicated by the presence in the IR spectra of
the valence band of the CH groups in the region
of 292950–2800 cm
– 1
. This band is one of the
criteria for the formation of the coordination
link M-N in complexates [29]. In the IR spectra
of heterometallic complexes, the position of the
4000 3500 3000 2500 2000 1500 1000 500
0
20
40
60
80
100
(M-N)
(M-O)
s
(COO
-)
as
(COO
-)
(CH)
(H2Ointer)
2
T
ra
n
sm
it
ta
n
ce
,
%
Wavenumbers, cm–1
Coedds (1)
NdeddsCo (2)
1
(H2Ointra)
Synthesis, spectral characterization and stability…
126 ISSN 2708-129X. УКР. ХІМ. ЖУРН., 2022, т. 88, No 2
(С—Н) band does not undergo significant
changes with respect to lanthanum-containing
homometallic neodymium complexes, which
indicates the same coordination of nitrogen
atoms in heterocomplexes and NdL
1.2
. In
addition, the multiplicity of (С-Н) may
indicate the presence in the complexes of an
extensive network of intra- and intermolecular
hydrogen bonds.
Quantum-chemical calculation of dimeric
complexes of Co (II) and Nd (III) from edds of
the composition [Co2(edds)2]
2-
and
[Nd2(edds)2(H2O)4]
2-
was performed by the
semi-empirical method PM7 (Sparkle / PM7 for
lanthanides) (Fig. 5). For all complexes, the
optimized geometries correspond to the
minimum on the surface of the potential energy,
as evidenced by the absence of negative
eigenvalues in their Hessians.
The dimeric complex [Co2(edds)2]
2-
has
the symmetry of the point group C2 (Fig. 5, a).
The immediate coordination environment of
each of the Co(II) ions includes 2 nitrogen
atoms of the ethylenediamine bridge edds, 2
oxygen atoms of α-carboxyl groups and an oxy-
gen atom of β-carboxyl group. The coordination
number of the central ion is supplemented to 6
(curved octahedron) due to the axial oxygen
atom of the β-COO- group of the second ligand
molecule. There are 3 five-membered chelate
cycles in the equatorial plane of the cobalt octa-
hedron: 1 ethylenediamine (Co–N–C–C–N)and
2 glycine (Co–O–C–C–N).The plane of the six-
membered β-alanine cycle ((Co–O–C–C–C–N)
is in the axial position. The bond lengths in the
octahedron [CoO4N2] are shown in Table 8.
According to the results of the calculation, the
internuclear distance Co–Co is 6.035 Å. The
calculated structure of the [Co2(edds)2]
2-
complex almost completely coincides with the
structure of the cobalt compound with edds
C10H20CoN2NaO12 described in [30, 31].
Neodymium-containing complexes
[Nd2(edds)2(H2O)4]
2-
have a similar structure to
ethylenediamine disuccinate (Fig. 8, b). Since
low coordination numbers for lanthanides are
uncharacteristic, the coordination number of
Nd(III) ions is supplemented by 8 oxygen atoms
of two water molecules. The coordination
polyhedron [NdO6N2] is a curved
dodecahedron. The Nd–Nd internuclear distance
is 7.522 Å.
Fig. 5.Optimized structure of complex anions
[Co2(edds)2]
2-
(a) and [Nd2(edds)2(H2O)4]
2-
(b).
Taking into account the data of IR
spectroscopic studies of heterometallic
ethylenediamine disinfectants of neodymium
and quantum chemical calculations of dimeric
complexes [Nd2(edds)2(H2O)4]
2-
,we can
assumethat in the NdCoL
2
complex in the
equatorial positions relative to the Ln
3+
ion are
two nitrogen atoms and two carboxyl oxygen
atoms of the edds molecule. Thus two glycine
and one ethylenediamine cycles are formed. The
six-membered -alanine ring is located in the
axial plane of the neodymium polyhedron.The
Co
2+
ion is bound to the complex ion [Lnedds]
-
Synthesis, spectral characterization and stability…
ISSN 2708-129X. УКР. ХІМ. ЖУРН., 2022, т. 88, No 2 129
Table 8
Calculated bond lengths in polyhedra [CoO4N2]
and [NdO6N2] (Å)
Bond length Co(II) Nd(III)
M–N
1,999
1,990
2,610
2,609
M–Oα-COO
1,965
1,952
2,377
2,350
M–Oβ-COO 1,951 2,387
M–Oβ-COO* 1,971 2,420
Nd–OH2 –
2,436
2,341
* β-carboxyl group of an adjacent edds molecule.
through oxygen atoms of the β-carboxyl group,
which performs a bridging function. The
octahedral configuration of the 3-d metal is
supplemented by 3 water molecules.
In heterometallic
ethylenediaminetetraacetates NdСоL
1
, the edta-
ligand is coordinated to the Nd
3+
ion
hexadentate with the involvement of two
nitrogen atoms and four carboxylate oxygen
atoms. The nitrogen atoms of the
ethylenediamine ring and the oxygen atoms of
the two 5-membered glycine rings occupy the
equatorial plane. The coordination environment
of neodymium ions is supplemented by two
water molecules. The octahedral coordination
polyhedron of cobalt in heteronuclear
ethylenediaminetetraacetate is formed by
bridged carbon oxygen atoms of bidentate
coordinated carboxyl groups of edta anions and
three water molecules.
CONCLUSIONS. The f-d-heteronuclear
complexes of Nd(III) and Co(II) with
aminopolycarboxylic acids were obtained by the
method of «block synthesis». The complexes
were investigated in solutions and solid - state
by methods of electron absorption spectroscopy
and IR-spectroscopy. It was found that the pH
range 5.5 - 7 is the most susceptible to the
formation of heterometallic complexes with
deprotonated L
1,2
anions. In this region, the
absorption spectra of heterometallic complexes
in comparison with the spectra of monometallic
compounds are characterized by shifting and
splitting of the bands of the corresponding f-f
transitions of Nd
3+
ion and d-d transitions of
Со
2+
ion into the long-wavelength region with a
significant increase in absorption intensity. The
absorption bands of the Со
2+
ion partially
overlap with the absorption bands of the
Со
2+
ion, which is proof of the formation of
heterometallic complexes.
For the NdL
1,2
, СоL
1,2
and NdСоL
1,2
complexes, stability constants were calculated
and it was shown that heteronuclear complexes
are several orders of magnitude more stable than
mononuclear ones due to the formation of
additional bonds or metal cycles with donor
ligand atoms. The stability of
ethylenediaminedisuccinates is lower than that
of the corresponding
ethylenediaminetetraacetates due to the different
sizes and number of chelated metal cycles.
The spectrophotometric characteristics
(oscillator power, nepheloxetic effect, Judd –
Ofelt parameters) of heteronuclear complexes
are compared. It was found that the oscillator
forces in edds-based complexes are greater than
in edta-based complexes, which is explained by
differences in the structure of the coordination
environment of the lanthanide ion in the
corresponding compounds.
It is proved that f-d-complexes belong to
complexes of «folded» type, in which the
ligand-complexon realizes maximum dentance
to Nd(III), and the coordination sphere of 3-d
cation is formed by carboxyl groups edta/edds
and intraspherical water molecules. In this case,
the Со
2+
cation is in a curved octahedral
environment, and the coordination polyhedron
of the neodymium ion corresponds to a one-cap
square antiprism (C4v) with a coordination
number Ln(III) 8. In solutions and solid -
complexants have the same structure.
Synthesis, spectral characterization and stability…
130 ISSN 2708-129X. УКР. ХІМ. ЖУРН., 2022, т. 88, No 2
ACKNOWLEDGEMENTS This work was
performed with the financial support of the Na-
tional Academy of Sciences of Ukraine within
the state budget theme «Creation of new multi-
functional nanomaterials based on coordination
of compounds of 3d-metals and lanthanides
with O, N-donor ligands», State registration
number - 0119U001102
СИНТЕЗ, СПЕКТРАЛЬНІ ХАРАКТЕРИ-
СТИКИ ТА СТАБІЛЬНІСТЬ НОВИХ ГЕ-
ТЕРОМЕТАЛІЧНИХ КОМПЛЕКСІВ
Nd(III) ТА Co(II) З АМІНОПОЛІКАРБО-
НОВИМИ КИСЛОТАМИ
O. К. Трунова*, А. М. Міщенко, T. O.
Maкотрик
Інститут загальної та неорганічної хімії ім.
В. І. Вернадського НАН України,
просп. Академіка Палладіна, 32/34, Київ
03142, Україна
* e-mail: trelkon@gmail.com.
Синтезовано та охарактеризовано ме-
тодами ЕСП, ІЧ-спектроскопії, ДТА нові
гетерометалічні комплекси Nd(III) та Co(II) з
амінополікарбоновими кислотами (етиленді-
амінтетраоцтова, етилендіаміндиянтарна
кислоти). Показано, що синтез гетерометалі-
чних комплексів доцільно проводити на ос-
нові моноядерних полікарбоксилатів 3d-
металів, які виступають «будівельним бло-
ком» для отримання гетеробіядерної сполуки
з екзокоординацією іонів лантанідів. Ком-
плекси досліджено у розчинах та твердому
стані. Встановлено, що незалежно від аміно-
полікарбонової кислоти, для обох гетероме-
талічних систем спостерігається батохром-
ний зсув максимумів поглинання відносно
максимумів поглинання гомоядерних ком-
плексів. Для комплексів NdL
1,2
, СоL
1,2
та
NdСоL
1,2
розраховано константи стійкості та
показано, що гетероядерні комплекси на кі-
лька порядків стійкіші моноядерних за раху-
нок утворення додаткових зв'язків або мета-
лоциклів із донорними атомами лігандів.
Стійкість етилендиаміндисукцинатів менша,
ніж у відповідних етилендиамінтетраацета-
тів, що пов’язано з різними розмірами і кі-
лькістю хелатних металоциклів. Для над-
чутливих переходів Nd(III) (
4
I9/2→
2
P1/2 та
4
I9/2→
4
G5/2+
2
G7/2) розраховано спектральні
параметри: сила осциляторів, нефелоксетич-
ний параметр, параметри Джадда – Офельта і
ковалентності та показано, що при переході
від моно- до гетерометалічного комплексу в
ряду аква-іон Ln(III) > гомометалічний ком-
плекс > гетерометалічний комплекс зростає
ковалентность зв’язку лантанід – ліганд, а
зниженням локальної симетрії іона лантаніду
відбувається в ряду аква-іон Ln (III) < гете-
рометалічний комплекс < гомометалічний
комплекс.
Гетероядерні комплекси на кілька по-
рядків стабільніші за одноядерні за рахунок
утворення додаткових зв’язків або металаци-
клів з атомами донорного ліганду. Відзначе-
но, що стійкість комплексів з edds нижча,
ніж у відповідних комплексів з edta через
різний розмір і кількість хелатних металаци-
клів. Проведено теоретичний аналіз геомет-
рії комплексів Co(II) та Nd(III) з етилендіа-
міндіянтарною кислотою напівемпіричним
методом PM7.
Показано, що f-d-комплекси належать
до комплексів згорнутого типу, в яких лі-
ганд-комплексон реалізує максимальну ден-
татність до Nd(III), а координаційна сфера
Co(II) формується містковими карбоксиль-
ними групами edta/edds та внутрішньосфер-
ними молекулами води. Координаційний
поліедр Co(II) відповідає викривленому ок-
таедру, а координаційний поліедр Nd (III)
відповідає одношапковій квадратній антип-
ризмі (C4v) з КЧ Nd(III) =8. У розчинах та
mailto:trelkon@gmail.com
O.K. Тrunova, A.M. Mishchenko, T.O. Makotryk
ISSN 2708-129X. УКР. ХІМ. ЖУРН., 2022, т. 88, No 2 125
твердому стані гетерометалічні комплекси
мають однотипну будову.
Ключові слова: гетерометалічні комплекси,
кобальт, неодим, амінополікарбонові кисло-
ти, спектральні властивості.
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Надійшла 21.02.2022
|
| id | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-408 |
| institution | Ukrainian Chemistry Journal |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-07-23T01:07:47Z |
| publishDate | 2022 |
| publisher | V.I.Vernadsky Institute of General and Inorganic Chemistry |
| record_format | ojs |
| resource_txt_mv | ucjorgua/0b/28ad95d931bf81e76b27729708304b0b.pdf |
| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-4082026-07-22T08:23:48Z SYNTHESIS, SPECTRAL CHARACTERIZATION AND STABILITY OF THE NEW ND (III) AND CO (II) HETEROMETALLIC COMPLEXES WITH AMINOPOLYCARBOXYLIC ACIDS СИНТЕЗ, СПЕКТРАЛЬНІ ХАРАКТРИСТИКИ ТА СТАБІЛЬНІСТЬ НОВИХ ГЕТЕРО-МЕТАЛІЧНИХ КОМПЛЕКСІВ Nd(III) ТА Co(II) З АМІНОПОЛІКАРБОНОВИМИ КИCЛОТАМИ Trunova , Elena Mishchenko , Artem Makotryk , Tamara heterometallic complexes, cobalt, neodymium, aminopolycarboxylic acids, spectral properties. New heterometallic complexes of Nd(III) and Co(II) based on ethylenediaminetetraacetic and ethylenediaminedisuccinic acids have been synthesized. The complexes studied by electron absorption spectroscopy, IR-spectroscopy, and thermogravimetric analysis. The influence of a number of factors on the properties and structure of heteronuclear complexes is discussed. The spectral characteristics of homonuclear and heteronuclear complexes are compared. A theoretical analysis of the geometry of Co(II) and Nd(III) complexes with ethylenediaminesuccinic acid was carried out by the semi-empirical PM7 method. It has been shown that the f-d-complexes are of the folded type, in which the ligand-complexone realizes the maximum denticity to Nd(III), and the Co(II) coordination sphere is formed by bridging edta/edds carboxyl groups and intrasphere water molecules. The Co(II) coordination polyhedron corresponds to a distorted octahedron, and the Nd(III) coordination polyhedron corresponds to a one-capped square antiprism (C4v) with the coordination number Nd(III)=8. During study fixed that heterometallic complexes have the same structure in solutions and in the solid state. V.I.Vernadsky Institute of General and Inorganic Chemistry 2022-03-25 Article Article Inorganic Chemistry Неорганическая химия Неорганічна хімія application/pdf https://ucj.org.ua/index.php/journal/article/view/408 10.33609/2708-129X.88.02.2022.116-130 Ukrainian Chemistry Journal; Vol. 88 No. 2 (2022): Ukrainian Chemistry Journal; 116-130 Украинский химический журнал; ##issue.vol## 88 ##issue.no## 2 (2022): Ukrainian Chemistry Journal; 116-130 Український хімічний журнал; Том 88 № 2 (2022): Український хімічний журнал; 116-130 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/408/214 Copyright (c) 2022 Elena Trunova , Artem Mishchenko , Tamara Makotryk https://creativecommons.org/licenses/by-nc/4.0 |
| spellingShingle | Trunova , Elena Mishchenko , Artem Makotryk , Tamara СИНТЕЗ, СПЕКТРАЛЬНІ ХАРАКТРИСТИКИ ТА СТАБІЛЬНІСТЬ НОВИХ ГЕТЕРО-МЕТАЛІЧНИХ КОМПЛЕКСІВ Nd(III) ТА Co(II) З АМІНОПОЛІКАРБОНОВИМИ КИCЛОТАМИ |
| title | СИНТЕЗ, СПЕКТРАЛЬНІ ХАРАКТРИСТИКИ ТА СТАБІЛЬНІСТЬ НОВИХ ГЕТЕРО-МЕТАЛІЧНИХ КОМПЛЕКСІВ Nd(III) ТА Co(II) З АМІНОПОЛІКАРБОНОВИМИ КИCЛОТАМИ |
| title_alt | SYNTHESIS, SPECTRAL CHARACTERIZATION AND STABILITY OF THE NEW ND (III) AND CO (II) HETEROMETALLIC COMPLEXES WITH AMINOPOLYCARBOXYLIC ACIDS |
| title_full | СИНТЕЗ, СПЕКТРАЛЬНІ ХАРАКТРИСТИКИ ТА СТАБІЛЬНІСТЬ НОВИХ ГЕТЕРО-МЕТАЛІЧНИХ КОМПЛЕКСІВ Nd(III) ТА Co(II) З АМІНОПОЛІКАРБОНОВИМИ КИCЛОТАМИ |
| title_fullStr | СИНТЕЗ, СПЕКТРАЛЬНІ ХАРАКТРИСТИКИ ТА СТАБІЛЬНІСТЬ НОВИХ ГЕТЕРО-МЕТАЛІЧНИХ КОМПЛЕКСІВ Nd(III) ТА Co(II) З АМІНОПОЛІКАРБОНОВИМИ КИCЛОТАМИ |
| title_full_unstemmed | СИНТЕЗ, СПЕКТРАЛЬНІ ХАРАКТРИСТИКИ ТА СТАБІЛЬНІСТЬ НОВИХ ГЕТЕРО-МЕТАЛІЧНИХ КОМПЛЕКСІВ Nd(III) ТА Co(II) З АМІНОПОЛІКАРБОНОВИМИ КИCЛОТАМИ |
| title_short | СИНТЕЗ, СПЕКТРАЛЬНІ ХАРАКТРИСТИКИ ТА СТАБІЛЬНІСТЬ НОВИХ ГЕТЕРО-МЕТАЛІЧНИХ КОМПЛЕКСІВ Nd(III) ТА Co(II) З АМІНОПОЛІКАРБОНОВИМИ КИCЛОТАМИ |
| title_sort | синтез, спектральні характристики та стабільність нових гетеро-металічних комплексів nd(iii) та co(ii) з амінополікарбоновими киcлотами |
| topic_facet | heterometallic complexes cobalt neodymium aminopolycarboxylic acids spectral properties. |
| url | https://ucj.org.ua/index.php/journal/article/view/408 |
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