СИНТЕЗ ТА ДОСЛІДЖЕННЯ ЛАНТАНІД-ВМІСНИХ ГІБРИДНИХ МАТЕРІАЛІВ НА ОСНОВІ ПОЛІЕДРАЛЬНИХ ОЛІГОМЕРНИХ СИЛСЕСКВІОКСАНІВ
New hybrid materials were synthesized based on meteacroacetophenate neodymium (III) and erbium (III) and polyhedral oligomeric sissesquioxane POSS formula C24H72Cl8N8O12Si8. A warehouse has been put in place for a new synthesis. In the IR spectra of the synthesized hybrid materials in the range of 4...
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Ukrainian Chemistry Journal| _version_ | 1871465463598284800 |
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| author | Ivakha, Nadiia Berezhnytska, Oleksandra Trunova , Elena Rohovtsov, Oleksandr |
| author_facet | Ivakha, Nadiia Berezhnytska, Oleksandra Trunova , Elena Rohovtsov, Oleksandr |
| author_institution_txt_mv | [
{
"author": "Nadiia Ivakha",
"institution": "National Technical University of Ukraine «Igor Sikorsky Kyiv Polytechnic Institute», 37, Prosp. Peremohy, Kyiv, Ukraine, 03056"
},
{
"author": "Oleksandra Berezhnytska",
"institution": "V.I. Vernadsky Institute of General and Inorganic Chemistry of the NAS of Ukraine Palladin avenue 32\/34, 03142, Kyiv, Ukraine"
},
{
"author": "Elena Trunova\t",
"institution": "V.I. Vernadsky Institute of General and Inorganic Chemistry of the NAS of Ukraine Palladin avenue 32\/34, 03142, Kyiv, Ukraine"
},
{
"author": "Oleksandr Rohovtsov",
"institution": "V.I. Vernadsky Institute of General and Inorganic Chemistry of the NAS of Ukraine Palladin avenue 32\/34, 03142, Kyiv, Ukraine"
}
] |
| author_sort | Ivakha, Nadiia |
| baseUrl_str | https://ucj.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-22T08:23:43Z |
| description | New hybrid materials were synthesized based on meteacroacetophenate neodymium (III) and erbium (III) and polyhedral oligomeric sissesquioxane POSS formula C24H72Cl8N8O12Si8. A warehouse has been put in place for a new synthesis. In the IR spectra of the synthesized hybrid materials in the range of 400–650 cm–1 there are oscillation bands that correspond to the valence oscillations of the bonds (Ln-O) and (Ln-N) and the deformation oscillations of the chelate ring. The decrease in intensity compared to the spectra of Ln(mphpd)3 complexes is due to the appearance of valence oscillations of the Ln-N bond and steric difficulties that arise when the complex coordinates to the sizable siloxane molecule. An additional intense broad band appears in the IR spectra, which is characterized by fluctuations in the valence of the Si-O-Si siloxane bond with a maximum of 1050 cm-1. The presence of a wide absorption band in the range of 1500–1700 cm-1, characterized by valence oscillations of ν (CO) and ν (CC), confirms the bidentate-cyclic coordination of β-diketonates. Thus, the shape and position of the bands in the IR spectra indicate the formation of a hybrid structure of the composition POSS- [Ln (mphpd)3]4. The shape, position, displacement and splitting of the spectral bands in the electronic spectra and diffuse reflectance spectra indicate the passage of the processes of complexation and the formation of complexes of non-cubic symmetry with coordination number 8. Thus, the presence of insignificant displacements of the absorption bands indicates the invariance of the coordination environment and the geometry of the coordination polyhedron for metal complexes and hydride systems based on them. The shift of the bands of supersensitive transitions in comparison with the spectra of metal complexes indicates both additional coordination of nitrogen atoms of the silsesquioxane molecule and some deformation of the coordination polyhedron, which is due to steric difficulties. According to the set of data from thermal and spectroscopic studies, the structure of the obtained hybrid material can be represented as follows. The results of EDX analysis, the method of dynamic light scattering and microphotographs are consistent and indicate the nanodispersity of the obtained systems.
  |
| doi_str_mv | 10.33609/2708-129X.86.6.2020.74-86 |
| first_indexed | 2025-09-24T17:43:26Z |
| format | Article |
| fulltext |
Неорганічна хімія
74 ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 6
UDC 541.49:546.287:546.661:546.669:547.466 doi: 10.33609/2708-129X.86.6.2020.74-86
О.S. Berezhnytska
1,2*
, N.B. Ivakha
1, 2
, О.О. Rohovtsov
1
, О.К.Trunova
1
SYNTHESIS AND RESEARCH OF LANTHANIDE-CONTAINING HYBRID
MATERIALS BASED ON POLYHEDRAL OLIGOMERIC SILSESQUIOXANES
1 V.I.Vernadsky Institute of General and Inorganic Chemistry of NAS of Ukraine
Akad. Palladin Avenue, 32/34, Kyiv, Ukraine, 03142.
2 National Technical University of Ukraine «Igor Sikorsky Kyiv Polytechnic Institute», 37, Prosp.
Peremohy, Kyiv, Ukraine, 03056.
* e-mail: berezhnytska@gmail.com
New hybrid materials were synthesized based on meteacroacetophenate neodymium (III)
and erbium (III) and polyhedral oligomeric sissesquioxane POSS formula
C24H72Cl8N8O12Si8. A warehouse has been put in place for a new synthesis. The position
of the bands in the IR spectra indicate the formation of a hybrid structure of the compo-
sition POSS-[Ln(mphpd)3]4. The shape, position, displacement and splitting of the spec-
tral bands in the electronic spectra and diffuse reflectance spectra indicate the passage of
the processes of complexation and the formation of complexes of non-cubic symmetry
with coordination number 8. The shift of the bands of supersensitive indicates both addi-
tional coordination of nitrogen atoms of the silsesquioxane molecule and some defo r-
mation of the coordination polyhedron, which is due to steric difficulties. The results of
EDX analysis, the method of dynamic light scattering and microphotographs are con-
sistent and indicate the nanodispersity of the obtained systems.
K e y w o r d s: complexes, hybrid structure, luminescence materials, emission,
nanosystems.
INTRODUCTION High luminescent
characteristics of lanthanide compounds
have been of interest to researchers for many
years in a row. [1-4]. Oxides, salts and
complexes of lanthanides intercalated into
polymer matrices, hybrid systems, homo-
and copolymers based on monomeric metal
complexes are used as precursors of
luminescent materials. Each of these areas is
relevant. However, the requirements for
materials are growing every year:
mechanical stability, chemical inertness,
thermal stability, high emission
characteristics, etc. None of the existing
materials can fully meet the requirements.
Therefore, there is a need for targeted
synthesis of such compounds and the
establishment of composition-property
correlations. Previous studies [5, 6] have
shown the possibility of targeted synthesis of
© О.S. Berezhnytska, N.B. Ivakha, О.О. Rohovtsov, О.К.Trunova, 2020
Synthesis and research of lanthanide-containing hybrid materials…
ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 6 75
compounds with high emission
characteristics. Obtaining homopolymers on
the basis of monomeric metal complexes
allows not only to obtain chemically
homogeneous materials, but also to increase
the efficiency of luminescence tenfold. On
the other hand, the possibility of obtaining
copolymers based on industrial monomers,
such as styrene, vinylcarbazole, methyl
methacrylate allows to influence the
properties and change them by adjusting the
ratio of metal complex: monomer. It was
found that the luminescence intensity,
surface morphology and stability of the
material depend on the structure of the
industrial monomer. However, due to the
volume of organic monomer molecules, they
can shield the emitting centers while
reducing the emission intensity. In addition,
polymers are prone to agglomeration with
the formation of globular structures.
Therefore, another approach to obtaining
functional nanomaterials is of interest,
namely the synthesis of hybrid structures
based on metal complexes. The role of the
matrix is to form a spatial structure, and the
complex has special properties. Fixation of
complexes on the matrix can occur in two
ways. For example, due to the physical
interaction of components by precipitation,
spraying, sorption, microencapsulation,
dispersion, etc. complex on the media. In
this case, the functional component is
usually linked to the matrix through physical
interaction. In the formation of organo-
inorganic materials with different
morphology as an organic matrix often use
mesh polymers, in which inorganic
components act as fillers dispersed in
polymers. To obtain such systems use sol-
gel technologies [7], which allow to obtain
materials with nanodispersed inorganic
phase at the molecular level. The materials
formed by this method are polydisperse in
size and heterogeneous in chemical
composition, which of course impairs their
properties [8]. In another variant, the
complex is fixed by covalent bonds. At the
same time, a careful selection of both the
ligand and the matrix comes to the fore.
Functionalized polyhedral oligomeric
silsesquioxanes (POSS) are proposed as a
matrix. Hybrid materials based on POSS are
quite easy to synthesize, they have high
thermal and optical properties. One of the
current directions in the creation of organo-
inorganic is the selection of methods for
obtaining nanostructuring agents that are
able to be covalently attached to the matrix
at the molecular level. This approach allows
you to purposefully synthesize materials
with different ratios of components and
influence the properties of the final product
[9-11]. Octahedral POSS of the general
formula R8S8O12 [12-14] seem to be
especially promising compounds for the
creation of hybrid organo-inorganic systems.
Such molecules consist of a central
inorganic nucleus of cubic shape with a size
of ~ 1.5 nm and organic substituents R with
various reactive groups, which allows for
further modification of these compounds.
For example, the inserting into such systems
of compounds with luminescent properties
can increase the emission characteristics. In
[15] it was shown that the inserting of
nanoparticles into the POSS promotes the
growth of electroluminescence in the blue
region of the spectrum, despite the fact that
the obtained material is not a chemical
О.S. Berezhnytska, N.B. Ivakha, О.О. Rohovtsov, О.К.Trunova
76 ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 6
interaction but the intercalation of
nanoparticles in the POSS matrix. The use of
hybrid structures as materials allows to
increase the thermal stability of materials
[16-18] due to the formation of chain or
mesh structures, reduce emission quenching
processes and sensitize luminescence due to
additional covalent bonds that act as
additional linkers.
Since the molecules of the compounds
that attach to the surface of the matrix set the
properties of the materials, it is paramount to
study the properties of such compounds and
compare them with the properties of hybrid
systems based on them. Previously,
complexes of a number of lanthanides with
methacroylacetophenone have been
synthesized and described [19, 20]. Their
structure and spectral-luminescent properties
have been studied. The use of these
compounds as precursors of hybrid systems
is relevant. Therefore, this study is based on
the synthesis, establishment of the structure
and properties of the system composition
POSS-[Er(mphpd)3]4 and POSS-[Nd
(mphpd)3]4.
EXPERIMENT AND DISCUSSION OF
THE RESULTS. Synthesis of Ln (III)
complexes with methacroylacetophenone
(mphpd) was performed by the interaction of
metal salts and mphpd sodium salt at a molar
ratio of 1: 3 and pH = 8-8.5 in aqueous
solutions, a detailed method of synthesis
presented in paper [21].
POSS with the formula
C24H72Cl8N8O12Si8 was purchased and used
without further purification. Hybrid
materials were obtained by direct synthesis
by the interaction of POSS and β-diketonate
complexes of neodymium (III) and erbium
(III) in a mixture of CHCl3-C2H5OH in a
ratio of 1: 4, respectively. The synthesized
compounds were investigated by elemental
analysis, FTIR, electron and fluorescence
spectroscopy, thermal analysis, dynamic
light scattering and electron microscopy
(SEM).
The hydrate composition of the
complexes and their thermal characteristics
were determined by the DTA method.
Thermograms were recorded on a
derivatograph Q – 1500 ° D of the system F.
Paulik, J. Paulik, L. Erdey in the temperature
range 20 - 500°С with a heating rate of
5°С/min. in a platinum crucible in the
presence of a carrier (anhydrous Al2O3).
IR spectra were recorded on a Specord
M80 spectrometer in the range of 400-4000
cm
-1
in KBr pellet.
Diffuse reflection spectra in the range
300 - 1100 nm were recorded on a UV-VIS-
IR Shimadzu UV-3600 spectrophotometer.
The excitation and luminescence
spectra of solid complexes were recorded on
a spectrofluorimeter Fluorolog FL 3-22,
Horiba Jobin Yvon (Хе-lamp 450 W) with a
light filter OS 11, with their subsequent
adjustment taking into account the radiation
distribution of the xenon lamp and the
sensitivity of the photomultiplier tube. The
InGaAs (DSS-IGA020L, Electro-Optical
Systems, Inc, USA) photoresistance was
used as a radiation receiver for the IR region
when cooled to liquid nitrogen temperature.
The method of dynamic light scattering
was used to determine the particle size of
complexes dissolved in dimethylformamide
at 25°C with Zeta Sizer Malvern.
Microphotographs were recorded on a
scanning electron microscope (SEM) Tescan
Synthesis and research of lanthanide-containing hybrid materials…
ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 6 77
Mira 3.
The results of EDX analysis indicate a
uniform distribution of the metal in the
hybrid material. The content of elements
(ww,%) in the sample is: carbon 44.35,
nitrogen 4.26, oxygen 37.37, sodium 0.42,
silicon 11.93, neodymium 1.67.
In the IR spectra of the synthesized
hybrid materials in the range of 400–650
cm
–1
there are oscillation bands that
correspond to the valence oscillations of the
bonds (Ln-O) and (Ln-N) and the
deformation oscillations of the chelate ring.
The decrease in intensity compared to the
spectra of Ln(mphpd)3 complexes is due to
the appearance of valence oscillations of the
Ln-N bond and steric difficulties that arise
when the complex coordinates to the sizable
siloxane molecule. The presence of
additional bands in this region indicates both
the unevenness of the bonds in the metal
cycle and the appearance of additional
oscillations corresponding to the oscillations
of the deformation of the Si-O bond (500
cm
-1
, 660 cm
-1
). An additional intense broad
band appears in the IR spectra, which is
characterized by fluctuations in the valence
of the Si-O-Si siloxane bond with a
maximum of 1050 cm
-1
. The presence of a
wide absorption band in the range of 1500–
1700 cm
-1
, characterized by valence
oscillations of ν (CO) and ν (CC), confirms
the bidentate-cyclic coordination of β-
diketonates [22]. The wide band with the
highest frequency (~1540-1660 cm
-1
)
includes the superposition of lines consisting
of symmetric valence oscillation (C O),
valence oscillation C=C bond, ph,
asymmetric valence oscillation (С С) and
deformation oscillations of the amino group.
Fig.1 IR-spectra Nd(mphpd)3 (1),
POSS-[Nd(mphpd)3]4 (2)
Thus, the shape and position of the
bands in the IR spectra indicate the
formation of a hybrid structure of the
composition POSS- [Ln(mphpd)3]4.
The absence of bands corresponding to
the valence vibrations of water molecules
suggests that the coordination of complexes
to amino groups occurs due to the
substitution of water molecules in the
complexes.
The results of thermal analysis indicate
the absence of water molecules in the
obtained materials and high stability of
hybrid structures. The stability of hybrid
systems is proportional to the stability of
metal polymers, which indicates the
chemical rather than intermolecular
interaction of siloxane molecules with -
diketonate complexes.
In the electronic absorption spectra of
the studied systems, there are bands *
of ligand transitions and bands f-f transitions
of lanthanide ion, which are part of the com-
plexes. If in the absorption spectra of the
solutions there is a small shift in the maxima
of the absorption bands, it indicates the
О.S. Berezhnytska, N.B. Ivakha, О.О. Rohovtsov, О.К.Trunova
78 ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 6
T a b l e 1
Assignment of lines in diffuse reflectance
spectra of neodymium compounds
Transition Ndaq
3+ Nd(mphpd)3
POSS-
NdL3
4І9/2
2P1/2 23064 23255
20920
weak
4І9/2
4G9/2 19560 19520 19531
4І9/2
4G7/2 19157 19050 19065
4І9/2
4G5/2,
2G7/2
17360 17168 17240
4І9/2
4F9/2 14720 14700 14727
4І9/2
4F7/2 13513 13400 13420
4І9/2
4H9/2 12594 12470 12480
4І9/2
4F3/2 11560 11430 11470
substitution of water molecules in the
immediate coordination environment
without a significant change in the geometry
of the coordination polyhedron [23].
In the spectra of hybrid systems, a
stronger splitting of the spectral lines
corresponding to supersensitive transitions is
observed in comparison with similar bands
in the electronic spectra of complexes
(Fig.2).
Thus, the absorption band corresponding to
the transition
4
I9/4
2
S3/2,
4
F7/2 is split into 3
components, the absorption band
corresponding to the transition
4
I9/4
4
F3/2 is
split into 4 components, which indicates the
non-cubic symmetry of the ligand field and
slight deformation of the coordination
polyhedron of hybrid structures, compared
with metal complexes (Table 1). In the
[POSS-[Nd(mphpd)3]4 spectra, the
absorption band corresponding to the
4
I9/2
2
P1/2 transition is difficult to
differentiate due to the shift of the charge
transfer band due to the replacement of
T a b l e 2
Assignment of lines in diffuse reflectance
spectra of erbium compounds
Transition Er3+ Er(mphpd)3
POSS-
ErL3
4I15/2
4G11/2 26585 26309 26525
4I15/2(2G,
4F)9/2
24744 24520 24600
4I15/2
4F5/2
22378 22270 22173
4I15/2
4F7/2 20709 20538 20530
4I15/2
4H11/2 19334 19190 19250
4I15/2
4S3/2 18570 18450 18426
4I15/2
4F9/2 15452 15324 15320
4I15/2
4I9/2 12567 12488 12485
water molecules by the sizable POSS
molecule.
The half-width of the supersensitive
transition
4
I9/4
4
G5/2,
2
G7/2 is (-310 cm
-1
) and
(+270 cm
-1
), the band contains a split
shoulder, which probably indicates a high
symmetry of the ligand field, but a
significant deformation of the coordination
polyhedron. The shape and position of the
bands in the electronic spectra and diffuse
reflectance spectra of POSS- [Nd (mphpd)3]4
corresponds to the coordination number 8
[24]. The ratio of the intensities of the
absorption bands in the region of
supersensitive transitions in the spectra of
the crystalline sample at 12480 cm
-1
(
4
I9/2
4
H9/2+
4
F5/2) and 17240см
-1
(
4
I9/2
2
G7/2+
4
G5/2) for POSS-[Nd(mphpd)3]4
is 0.83, while for Nd(mphpd)3 - 0.57, and for
the aquacomplex - 1.12, which suggests a
decrease in symmetry in the case of a hybrid
system compared to the original metal
complex and an increase compared to the
aqua ion.
Synthesis and research of lanthanide-containing hybrid materials…
ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 6 79
Fig.2 – Diffuse reflectance spectra РOSS-
Er(mphpd)3 (a)and РOSS-Nd(mphpd)3 (b)
The shape and position of the bands in
electronic spectra and diffuse reflectance
spectra practically do not differ, which
indicates a similar structure of compounds in
solution and in the solid state. In the
electronic spectra and diffuse reflectance
spectra of Er(III) complexes, a set of bands
corresponding to erbium ion transitions from
the
4
I15/2 ground state is observed. The bands
4
I15/2
2
Н11/2 (520 нм) and
4
I15/2
4
G11/2 (377
nm) are the most sensitive to changes in the
ligand field (Table 2). As can be seen from
the table, the bands are shifted compared to
metal complexes in the short-wavelength
region, which indicates the deformation of
the coordination polyhedron due to the
coordination of the volume molecule of the
polyhedral oligomeric silsesquioxane. It
should be noted that compared to the bands
of the aquaion there is a slight long-
wavelength displacement. Thus, hybrid
systems occupy an intermediate position in
symmetry between aqua and metal
complexes.
The shape, position, displacement and
splitting of the spectral bands in the
electronic spectra and diffuse reflectance
spectra indicate the passage of the processes
of complexation and the formation of
complexes of non-cubic symmetry with co-
ordination number 8. Thus, the presence of
insignificant displacements of the absorption
bands indicates the invariance of the
coordination environment and the geometry
of the coordination polyhedron for metal
complexes and hydride systems based on
them. The shift of the bands of
supersensitive transitions in comparison with
the spectra of metal complexes indicates
both additional coordination of nitrogen
atoms of the silsesquioxane molecule and
some deformation of the coordination
polyhedron, which is due to steric
difficulties. According to the set of data
from thermal and spectroscopic studies, the
structure of the obtained hybrid material can
be represented as follows (Fig. 3)
The method of dynamic light scattering
shows that the studied systems are
polydisperse with a uniform distribution of
the dispersed phase in the dispersion
medium.
О.S. Berezhnytska, N.B. Ivakha, О.О. Rohovtsov, О.К.Trunova
80 ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 6
Fig.3 – Approximate structure of the hybrid
based on POSS-MPOSS[Ln(mphpd)3]4
The predominant particle radius is 20
nm, such particles in the system 97%. In the
case of monocomplexes, the particle size
was in the range of 30-50 nm. Obviously,
the formation of hybrid systems reduces the
dispersion of particles, which may be due to
the high dispersion of silsesquioxanes,
which in turn contributed to changes in
surface morphology, shape and size of
nanoparticles.
The analysis of microphotographs
confirms the conclusions made on the basis
of the method of dynamic light scattering
and testifies to the nanodispersity of the
obtained systems. Microphotographs of
hybrids (Fig. 4) differ significantly from
previously studied monomeric, metalpo-
lymeric and copolymeric compounds. In
microphotographs of metal-polymer and
copolymer powders, spherical particles were
clearly distinguished, and depending on the
structure of the industrial monomer (styrene,
vinylcarbazole) their size differed
significantly, for compounds based on
Fig.4 – SEM- Microphotographs of hybrid struc-
tures powder (a) and film (b) [РOSS-
Nd(mphpd)3]n
Synthesis and research of lanthanide-containing hybrid materials…
ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 6 81
methyl methacrylate was characterized by
the formation of a spongy structure [5, 18].
In the case of hybrid systems, we observe
significant differences from the previously
studied monomeric, metal-polymer and
copolymer compounds. Surface morphology
also corresponds to amorphous systems,
however, this is the only similarity. Loose,
spongy, layered homogeneous structure is an
intermediate between monomer complexes
and metal polymers based on methyl
methacrylate. Microphotographs of the film
indicate the absence of aggregation. It is
known that POSS molecules can be
chemically integrated into the structure of
the polymer matrix due to the interaction of
reactive POSS groups with functional groups
of monomers, oligomers and polymers that
form the polymer matrix [25]. The same
happens in the case of coordination of POSS
molecules thr functional groups to metal
complexes (Fig. 4). The difference between
microphotographs of films and powders is
due to the different morphology of the
surface. Films were obtained by
precipitation of solutions with a
concentration of 5∙10
-4
M.
If in the case of powders there is a
slight agglomeration, then this process is
absent in the films, due to both the degree of
dilution of the solutions and the stabilizing
effect of the bulk molecules of polyhedral
oligomeric silsesquioxanes.
Thus, the results of EDX analysis, the
method of dynamic light scattering and
microphotographs are consistent and
indicate the nanodispersity of the obtained
systems. The main idea of the study was to
obtain materials with high luminescent
properties, so the study of luminescent
characteristics was of considerable interest.
For effective luminescence, the energy
difference between the triplet level of the
ligand and the singlet level of the lanthanide
ion should be in the range of 2500-3500
cm
-1
. Therefore, for the experimental
determination of the energy of singlet and
triplet levels in the studied β-diketonate
complexes, the fluorescence and
phosphorescence spectra of gadolinium-
containing compounds were studied, which
allowed to calculate the energies of triplet
levels [26].
Studies have shown that for the Er(III)
ion the energy of the singlet level is 18600
cm
-1
, so the difference between the singlet
and triplet level is low, is in the range of
1100-2000 cm
-1
, which explains the low
luminescence efficiency Er(mphpd)3. It is
known that functionalized POSS molecules
are able not only to show luminescence, but
also to enhance luminescence in the blue
region. However, studies have shown that
the luminescence intensity of POSS-
[Er(mphpd)3]4, as well as the metal complex,
is low, which indicates that the main
contribution to the emission is the
coordination fragment (Fig. 5). The expected
sensitization effect was not observed, which
is due to both energy dependence and
shielding of the radiating center by the bulky
POSS molecule.
In contrast to erbium complexes, for
neodymium compounds the luminescence
intensity is quite high (Fig. 6). The
luminescence spectrum of POSS-
[Nd(mphpd)3]4 consists of three bands
corresponding to the transitions from the
excited level of the Nd(III)
4
F3/2 ion to the
base level multiples
4
I9/2 (878 and 898 nm),
О.S. Berezhnytska, N.B. Ivakha, О.О. Rohovtsov, О.К.Trunova
82 ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 6
Fig. 5. Luminescence spectra of Er(III)
compounds
4
I11/2 (1062 nm) and
4
I13/2 (1333 nm). The
absence of band splitting, which corresponds
to the transition
4
F3/2
4
I11/2, indicates a
fairly high symmetry of the complex and the
presence of a single coordination center. The
transition band
4
F3/2
4
I9/2 is split into two
components, which indicates non-cubic
symmetry of the ligand field. As can be
seen, the maxima of the transitions are
slightly shifted to the long-wavelength
region, but the band of the most intense
transition
4
F3/2
4
I11/2 is practically not
shifted, which indicates the same
coordination environment of the central ion
in both compounds. As can be seen from the
figure, the luminescence intensity of POSS-
[Nd(mphpd)3]4 is 10 times higher than for
neodymium methacrylacetophenoate (III).
Thus, obtaining hybrid systems based on
coordination compounds of lanthanides
(Nd(III), Er(III)) allows to obtain materials
with high luminescent characteristics.
CONCLUSIONS. In this work
synthesizes new hybrid systems based on the
Fig. 6. Luminescence spectra of Nd(III)
compounds
-diketonate complexes of lanthanides and
polyhedral oligomeric silsesquioxanes,
which allows to increase the thermal and
chemical resistance of materials. The
composition and structure of the synthesized
compounds are established. It is shown that
the replacement of water molecules in the
coordination environment of lanthanide
complexes by POSS functional groups
allows to obtain hybrid materials for special
purposes. It is established that the structure
of the coordination polyhedron c.a. it does
not change, but only slightly deforms.
Analysis of microphotographs and the
method of dynamic light scattering indicate
the formation of nanosystems with particles
of about 20 nm. Microphotographs of the
films indicate the stabilizing effect of POSS
molecules, which prevents agglomeration. It
is shown that these complexes exhibit high
luminescence intensity, which allows their
use as precursors of luminescent materials.
The presence of a large number of emitting
centers allows to offer these compounds as
markers for the protection of securities.
Synthesis and research of lanthanide-containing hybrid materials…
ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 6 83
ACKNOWLEDGEMENT
The team of authors would like to express
their gratitude to the colleagues of the
A.V.Bohatsky Physico-Chemical Institute of
NASU Smola S.S and Rusakova N.V.
The work is done within the theme № III-
03-12 (310E) «New inorganic compounds and
highly efficient functional materials (physico-
chemical basis of design? Heterogeneous-
heterophase synthesis, structure, properties)»
СИНТЕЗ ТА ДОСЛІДЖЕННЯ ЛАНТАНІД-
ВМІСНИХ ГІБРИДНИХ МАТЕРІАЛІВ НА
ОСНОВІ ПОЛІЕДРАЛЬНИХ ОЛІГОМЕР-
НИХ СИЛСЕСКВІОКСАНІВ
О.С. Бережницька1,2*, Н.Б. Іваха1, 2, О.О. Ро-
говцов1, О.К.Трунова1
1Інститут загальної та неорганічної хімії
ім.В.І.Вернадського НАН України, просп.
Академіка Палладіна, 32/34, Київ, 03142,
Україна
2Національний технічний університет Укра-
їни «Київський політехнічний інститут імені
Ігоря Сікорського», просп. Перемоги, 37, Ки-
їв, 03056, Україна
*е-mail: olekberez@gmail.com
Нові гібридні матеріали були синтезовані на
основі метакроїлацетофеноату неодиму(ІІІ)
та ербію (III) та поліедрального олігомерного
силсесквіоксану (POSS) загальної формули
C24H72Cl8N8O12Si8. Встановлено склад та бу-
дову синтезованих сполук. В ІЧ-спектрах
синтезованих гібридних матеріалів в
діапазоні 400–650 см–1 присутні смуги коли-
вань, що відповідають валентним коливан-
ням зв’язків (Ln-O) і (Ln-N) та
деформаційним коливанням хелатного
кільця. Зниження інтенсивності порівняно зі
спектрами комплексів Ln(mphpd)3 обумовле-
но появою валентних коливань зв'язку Ln-N
та стеричними труднощами, які виникають,
при координації молекули силоксану. В ІЧ-
спектрах з'являється додаткова інтенсивна
широка смуга, характерна для валентного
коливання зв'язку Si-O-Si з максимумом 1050
см-1. Наявність широкої смуги поглинання в
діапазоні 1500–1700 см-1, підтверджує
бідентатно-циклічну координацію β-
дикетонатів. Таким чином, форма та поло-
ження смуг в ІЧ-спектрах вказують на утво-
рення гібридної структури POSS-
[Ln(mphpd)3]4. Форма, положення, зміщення
та розщеплення спектральних смуг в ЕСП та
ЕСДВ свідчить про проходження процесів
комплексоутворення та одержання комплек-
сів некубічної симетрії з К.Ч. лантаніду 8.
Наявність незначних за величиною (до
200см-1) зміщень смуг поглинання свідчить
про незмінність координаційного оточення та
геометрії координаційного поліедру для
комплексів металів та гібридних систем на їх
основі. Зміщення смуг надчутливих перехо-
дів порівняно зі спектрами металокомплексів
лише вказує на додаткову координацію ато-
мів азоту молекули силсесквіоксану та деяку
деформацію координаційного поліедру, що
обумовлено стеричними труднощами. Ре-
зультати ЕDХ аналізу, методу динамічного
розсіяння світла та мікрофотографій добре
узгоджуються та свідчать про нанодисперс-
ність отриманих систем.
К л ю ч о в і с л о в а: комплекси, гібридні
структури, люмінесцентні матеріали, емісія,
наносистеми
СИНТЕЗ И ИССЛЕДОВАНИЕ ЛАНТАНИД-
СОДЕРЖАЩИХ ГИБРИДНЫХ МАТЕРИА-
ЛОВ НА ОСНОВЕ ПОЛИЭДРАЛЬНЫХ
ОЛИГОМЕРНЫХ СИЛСЕСКВИОКСАНОВ
А.С. Бережницкая1,2*, Н.Б. Иваха1, 2, А.А. Ро-
говцов1, Е.К.Трунова1
mailto:olekberez@gmail.com
О.S. Berezhnytska, N.B. Ivakha, О.О. Rohovtsov, О.К.Trunova
84 ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 6
1Институт общей и неорганической химии
им. В.И. Вернадского НАН Украины, просп.
Академика Палладина, 32/34, Киев, 03142,
Украина
2Национальный технический университет
Украины «Киевский политехнический инс-
титут имени Игоря Сикорского», просп.
Победы, 37, Киев, 03056, Украина
*е-mail: olekberez@gmail.com
Новые гибридные материалы были синтези-
рованы на основе метакроилацетофеноата
неодима(ІІІ) и эрбия (ІІІ), а также полиэд-
рального олигомерного силсесквиоксана
(POSS) общей формулы C24H72Cl8N8O12Si8.
Установлено состав и строение синтезиро-
ванных соединений. В ИК-спектрах синтези-
рованных гибридных материалов в диапазоне
400–650 см–1 присутствуют полосы колеба-
ний, которые отвечают валентным колебани-
ям связей (Ln-O), (Ln-N) и деформационным
колебаниям хелатного кольца. Снижение
интенсивности по сравнению со спектрами
комплексов Ln(mphpd)3 обусловлено появле-
нием валентных колебаний связи Ln-N и сте-
рическими трудностями, которые возникают
при координации силоксана. В ИК-спектрах
гибридов проявляется дополнительная ин-
тенсивная широкая полоса, характерная для
валентного колебания связи Si-O-Si, с мак-
симумом 1050 см-1. Наличие широкой поло-
сы в диапазоне1500–1700 см-1 подтверждает
бидентатно-циклическую координацию β-
дикетонатов. Таким образом, форма и поло-
жение полос в ИК-спекрах указывают на об-
разование гибридной структуры POSS-
[Ln(mphpd)3]4. Форма, положение, смещение
и расщепление спектральных полос в ЭСП и
ЭСДО свидетельствуют о прохождении про-
цессов комплексообразования и получении
комплексов некубической симметрии с К.Ч.
лантанида 8. Наличие незначительных по
величине (до 200см-1) смещений полос по-
глощения свидетельствует о неизменности
координационного окружения и геометрии
координационного полиэдра для комплексов
металлов и гибридных систем на их основе.
Смещение полос сверхчувствительных пере-
ходов по сравнению со спектрами металло-
комплексов указывает лишь на дополнитель-
ную координацию атомов нитрогена молеку-
лы силсесквиоксана и некоторую деформа-
цию координационного полиэдра, обуслов-
ленную стерическими трудностями. Резуль-
таты ЕDХ анализа, метода динамического
рассеивания света и микрофотографий хо-
рошо согласуются и свидетельствуют о на-
нодисперсности полученных систем.
К л ю ч е в ы е с л о в а: комплексы, гибрид-
ные структуры, люминесцентные материалы,
эмиссия, наносистемы.
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| id | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-181 |
| institution | Ukrainian Chemistry Journal |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-07-23T01:02:26Z |
| publishDate | 2020 |
| publisher | V.I.Vernadsky Institute of General and Inorganic Chemistry |
| record_format | ojs |
| resource_txt_mv | ucjorgua/1b/f1e0196b068a8347be9f36e0a82ed81b.pdf |
| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-1812026-07-22T08:23:43Z SYNTHESIS AND RESEARCH OF LANTHANIDE-CONTAINING HYBRID MATERIALS BASED ON POLYHEDRAL OLIGOMERIC SILSESQUIOXANES СИНТЕЗ И ИССЛЕДОВАНИЕ ЛАНТАНИД-СОДЕРЖАЩИХ ГИБРИДНЫХ МАТЕРИАЛОВ НА ОСНОВЕ ПОЛИЭДРАЛЬНЫХ ОЛИГОМЕРНЫХ СИЛСЕСКВИОКСАНОВ СИНТЕЗ ТА ДОСЛІДЖЕННЯ ЛАНТАНІД-ВМІСНИХ ГІБРИДНИХ МАТЕРІАЛІВ НА ОСНОВІ ПОЛІЕДРАЛЬНИХ ОЛІГОМЕРНИХ СИЛСЕСКВІОКСАНІВ Ivakha, Nadiia Berezhnytska, Oleksandra Trunova , Elena Rohovtsov, Oleksandr : complexes, hybrid structure, luminescence materials, emission, nanosystems. New hybrid materials were synthesized based on meteacroacetophenate neodymium (III) and erbium (III) and polyhedral oligomeric sissesquioxane POSS formula C24H72Cl8N8O12Si8. A warehouse has been put in place for a new synthesis. In the IR spectra of the synthesized hybrid materials in the range of 400–650 cm–1 there are oscillation bands that correspond to the valence oscillations of the bonds (Ln-O) and (Ln-N) and the deformation oscillations of the chelate ring. The decrease in intensity compared to the spectra of Ln(mphpd)3 complexes is due to the appearance of valence oscillations of the Ln-N bond and steric difficulties that arise when the complex coordinates to the sizable siloxane molecule. An additional intense broad band appears in the IR spectra, which is characterized by fluctuations in the valence of the Si-O-Si siloxane bond with a maximum of 1050 cm-1. The presence of a wide absorption band in the range of 1500–1700 cm-1, characterized by valence oscillations of ν (CO) and ν (CC), confirms the bidentate-cyclic coordination of β-diketonates. Thus, the shape and position of the bands in the IR spectra indicate the formation of a hybrid structure of the composition POSS- [Ln (mphpd)3]4. The shape, position, displacement and splitting of the spectral bands in the electronic spectra and diffuse reflectance spectra indicate the passage of the processes of complexation and the formation of complexes of non-cubic symmetry with coordination number 8. Thus, the presence of insignificant displacements of the absorption bands indicates the invariance of the coordination environment and the geometry of the coordination polyhedron for metal complexes and hydride systems based on them. The shift of the bands of supersensitive transitions in comparison with the spectra of metal complexes indicates both additional coordination of nitrogen atoms of the silsesquioxane molecule and some deformation of the coordination polyhedron, which is due to steric difficulties. According to the set of data from thermal and spectroscopic studies, the structure of the obtained hybrid material can be represented as follows. The results of EDX analysis, the method of dynamic light scattering and microphotographs are consistent and indicate the nanodispersity of the obtained systems.   V.I.Vernadsky Institute of General and Inorganic Chemistry 2020-07-20 Article Article Inorganic Chemistry Неорганическая химия Неорганічна хімія application/pdf https://ucj.org.ua/index.php/journal/article/view/181 10.33609/2708-129X.86.6.2020.74-86 Ukrainian Chemistry Journal; Vol. 86 No. 6 (2020): Ukrainian Chemistry Journal; 74-86 Украинский химический журнал; ##issue.vol## 86 ##issue.no## 6 (2020): Украинский химический журнал; 74-86 Український хімічний журнал; Том 86 № 6 (2020): Український хімічний журнал; 74-86 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/181/104 Copyright (c) 2020 Nadiia Ivakha, Oleksandra Berezhnytska, Elena Trunova , Oleksandr Rohovtsov https://creativecommons.org/licenses/by-nc/4.0 |
| spellingShingle | Ivakha, Nadiia Berezhnytska, Oleksandra Trunova , Elena Rohovtsov, Oleksandr СИНТЕЗ ТА ДОСЛІДЖЕННЯ ЛАНТАНІД-ВМІСНИХ ГІБРИДНИХ МАТЕРІАЛІВ НА ОСНОВІ ПОЛІЕДРАЛЬНИХ ОЛІГОМЕРНИХ СИЛСЕСКВІОКСАНІВ |
| title | СИНТЕЗ ТА ДОСЛІДЖЕННЯ ЛАНТАНІД-ВМІСНИХ ГІБРИДНИХ МАТЕРІАЛІВ НА ОСНОВІ ПОЛІЕДРАЛЬНИХ ОЛІГОМЕРНИХ СИЛСЕСКВІОКСАНІВ |
| title_alt | SYNTHESIS AND RESEARCH OF LANTHANIDE-CONTAINING HYBRID MATERIALS BASED ON POLYHEDRAL OLIGOMERIC SILSESQUIOXANES СИНТЕЗ И ИССЛЕДОВАНИЕ ЛАНТАНИД-СОДЕРЖАЩИХ ГИБРИДНЫХ МАТЕРИАЛОВ НА ОСНОВЕ ПОЛИЭДРАЛЬНЫХ ОЛИГОМЕРНЫХ СИЛСЕСКВИОКСАНОВ |
| title_full | СИНТЕЗ ТА ДОСЛІДЖЕННЯ ЛАНТАНІД-ВМІСНИХ ГІБРИДНИХ МАТЕРІАЛІВ НА ОСНОВІ ПОЛІЕДРАЛЬНИХ ОЛІГОМЕРНИХ СИЛСЕСКВІОКСАНІВ |
| title_fullStr | СИНТЕЗ ТА ДОСЛІДЖЕННЯ ЛАНТАНІД-ВМІСНИХ ГІБРИДНИХ МАТЕРІАЛІВ НА ОСНОВІ ПОЛІЕДРАЛЬНИХ ОЛІГОМЕРНИХ СИЛСЕСКВІОКСАНІВ |
| title_full_unstemmed | СИНТЕЗ ТА ДОСЛІДЖЕННЯ ЛАНТАНІД-ВМІСНИХ ГІБРИДНИХ МАТЕРІАЛІВ НА ОСНОВІ ПОЛІЕДРАЛЬНИХ ОЛІГОМЕРНИХ СИЛСЕСКВІОКСАНІВ |
| title_short | СИНТЕЗ ТА ДОСЛІДЖЕННЯ ЛАНТАНІД-ВМІСНИХ ГІБРИДНИХ МАТЕРІАЛІВ НА ОСНОВІ ПОЛІЕДРАЛЬНИХ ОЛІГОМЕРНИХ СИЛСЕСКВІОКСАНІВ |
| title_sort | синтез та дослідження лантанід-вмісних гібридних матеріалів на основі поліедральних олігомерних силсесквіоксанів |
| topic_facet | : complexes hybrid structure luminescence materials emission nanosystems. |
| url | https://ucj.org.ua/index.php/journal/article/view/181 |
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