INVESTIGATION OF NEW POLYMER COMPLEXES BASED ON Yb(III) β-DIKETONATES
The metal polymers based on mono- and heteroligand β-diketonate complexes of Yb(III) with 2,7-dimethyl-octen-1-dione-3,5, 2,6-dimethyl-heptene-1-dione-3, 5 and with phenanthroline was synthesized. It has been defined that the coordination environment of the central ion remains unchanged during radic...
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| author | Ivakha , Nadiia Berezhnytska, Oleksandra Rohovtsov , Oleksandr Trunova, Olena Smola, Serhii |
| author_facet | Ivakha , Nadiia Berezhnytska, Oleksandra Rohovtsov , Oleksandr Trunova, Olena Smola, Serhii |
| author_institution_txt_mv | [
{
"author": "Nadiia Ivakha ",
"institution": "V.I.Vernadsky Institute of General and Inorganic Chemistry of NAS of Ukraine, Akad. Palladin Avenue, 32\/34, Kyiv, Ukraine, 03142"
},
{
"author": "Oleksandra Berezhnytska",
"institution": "V.I.Vernadsky Institute of General and Inorganic Chemistry of NAS of Ukraine, Akad. Palladin Avenue, 32\/34, Kyiv, Ukraine, 03142"
},
{
"author": "Oleksandr Rohovtsov ",
"institution": "V.I.Vernadsky Institute of General and Inorganic Chemistry of NAS of Ukraine, Akad. Palladin Avenue, 32\/34, Kyiv, Ukraine, 03142"
},
{
"author": "Olena Trunova",
"institution": "V.I.Vernadsky Institute of General and Inorganic Chemistry of NAS of Ukraine, Akad. Palladin Avenue, 32\/34, Kyiv, Ukraine, 03142"
},
{
"author": "Serhii Smola",
"institution": "A.V. Bogatsky Physico-chemical Institute National Academy of Sciences of Ukraine"
}
] |
| author_sort | Ivakha , Nadiia |
| baseUrl_str | https://ucj.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-22T08:23:49Z |
| description | The metal polymers based on mono- and heteroligand β-diketonate complexes of Yb(III) with 2,7-dimethyl-octen-1-dione-3,5, 2,6-dimethyl-heptene-1-dione-3, 5 and with phenanthroline was synthesized. It has been defined that the coordination environment of the central ion remains unchanged during radical polymerization. The shape and position of the bands in the electronic absorption spectra are similar to the corresponding monomeric β-diketonate metal complexes, and slight shifts indicate deformation of the elementary unit of the metal polymer during the formation of the polymer chain. It is shown that the polymerization process lead to an increasing in the thermal stability of polymer complexes in comparison with monomeric analogues. An increase in the emission of metal polymers in comparison with monomeric complexes was established by the method of luminescent spectroscopy, which is due to energy, steric, and structural-mechanical factors. |
| doi_str_mv | 10.33609/2708-129X.88.05.2022.3-14 |
| first_indexed | 2025-09-24T17:43:45Z |
| format | Article |
| fulltext |
33
УДК 546.650+547.1’13+541.64+543.426 doi: 10.33609/2708-129X.88.05.2022.3-14
INVESTIGATION OF NEW POLYMER COMPLEXES BASED
ON Yb(III) β-DIKETONATES
N. Ivakha1,2*, O. Berezhnytska1,2, O. Rohovtsov1, S. Smola3, O. Trunova1
1 V.I. Vernadsky Institute of General and Inorganic Chemistry of the National Academy of Sciences
of Ukraine, 32/34 Academic Palladin ave., Kyiv, 03142, Ukraine
2 National Technical University of Ukraine «Igor Sikorsky Kyiv Polytechnic Institute», Peremohy
ave., 37, 03056 Kyiv, Ukraine
3 A.V. Bogatsky Physico-Chemical Institute NASU, 86, Lustdorf road, Odessa, 65000, Ukraine
e-mail: ivakhanadiia@gmail.com
The metal polymers based on mono- and heteroligand β-diketonate complexes of Yb(III)
with 2,7-dimethyl-octen-1-dione-3,5, 2,6-dimethyl-heptene-1-dione-3, 5 and with phenan-
throline was synthesized. It has been defined that the coordination environment of the central
ion remains unchanged during radical polymerization. The shape and position of the bands
in the electronic absorption spectra are similar to the corresponding monomeric β-diketonate
metal complexes, and slight shifts indicate deformation of the elementary unit of the metal
polymer during the formation of the polymer chain. It is shown that the polymerization pro-
cess lead to an increasing in the thermal stability of polymer complexes in comparison with
monomeric analogues. An increase in the emission of metal polymers in comparison with
monomeric complexes was established by the method of luminescent spectroscopy, which is
due to energy, steric, and structural-mechanical factors.
Keywords: unsaturated β-diketones, complexes, ytterbium, polymerization, lumines-
cence.
INTRODUCTION. In the modern world,
it is difficult to overestimate the role of
polymeric materials in industrial production
and it is almost impossible to find industries
where they are not used. However, the
requirements for the characteristics of such
materials are constantly growing, so the efforts
of many scientists are aimed at searching for
and developing polymer compounds with
fundamentally new or improved physical and
chemical properties (thermal, conductive,
magnetic, luminescent, etc.).
In this regard, directions for obtaining
composite, hybrid materials, as well as orga-
nometallic compounds with improved cha-
racteristics are developing at an ultrafast pace
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[1–5]. Common to these areas is that due to
the combination of components of different
nature in the compounds (as a rule, organic
and inorganic parts), there is a significant im-
provement in the final characteristics of the
synthesized materials due to the synergistic
effect. This makes it possible to obtain a large
number of new compounds, varying both their
qualitative and quantitative composition over a
wide range, depending on the requirements for
such products.
The synthesis of organometallic com-
pounds has been the most important direction
in coordination chemistry for several decades.
If ligands with a double bond, which can en-
ter into polymerization reactions, are used
as initial components, then this is also one of
the ways to obtain polymeric materials [6, 7].
It is important to note that with this method
of synthesis, all units will be interconnected by
strong covalent bonds (unlike supramolecular
compounds), which will make it possible to
evenly distribute the metal over the polymer
matrix and expect an improvement in the per-
formance of such a material.
Metal complexes acting as monomers dur-
ing polymerization should have high thermal
stability, solubility, and stability in organic sol-
vents. In this regard, unsaturated β-diketonate
complexes with metals of various nature (both
3d and 4f metals) are promising, on the basis
of which both metal polymers and copolymers
with predictable functional characteristics can
be synthesized.
The most demanded today are materi-
als with luminescent properties [8–10]. It is
known that lanthanides often act as active
centers in such compounds, which can emit
both in the visible (Eu, Sm, Tb) and infrared
(Nd, Er, Yb) regions. It is the last group that is
of the greatest interest, since it is the least stu-
died, however, interest in such developments
is constantly growing given their prospects in
production (as components in optoelectronics,
for the protection of securities, in the medical
industry, etc.) [11–13].
Since the use of monomeric luminescent
materials is limited by a number of disadvan-
tages (insufficient thermal stability, suscep-
tibility to aggregation, difficulty in obtaining
film materials), the synthesis and preparation
of polymer compounds based on them seems
even more reasonable, since it makes it po-
ssible to overcome them, and sometimes (for
example, in the case of obtaining copolymers)
also significantly reduce the cost of the process,
without losing useful properties. In addition,
an effective approach in the development of
lanthanide-based luminescent compounds is
the preparation of mixed-ligand β-diketonate
systems, which becomes possible due to the
high coordination capacity of the Ln(III) atom
[14, 15].
Therefore, the purpose of this work is to
obtain and study the physicochemical char-
acteristics of new polymer compounds based
on monomeric ytterbium β-diketonate com-
plexes (Yb(dmhpd)3∙2H2O, Yb(dmhpd)3∙Phen,
Yb(dmod)3∙2H2O, Yb(dmod)3∙Phen) as pre-
cursors of efficient luminescent materials.
EXPERIMENT AND DISCUSSION OF
THE RESULTS. In the work, homopolymeri-
zation of the synthesized Yb(III) β-diketo-
nate complexes was carried out by a radical
mechanism according to the method [16].
Mono- and mixed-ligand complexes of Yb(I-
II) with 2,7-dimethyl-octene-1-dione-3,5 and
2,6-dimethyl-heptene-1-dione-3,5 were used
as starting materials (Fig. 1) . The synthesis of
complexes is described in [17].
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2,6-dimethyl-heptene-1-dione-3,5 (Hdmhpd) 2,7-dimethyl-octene-1-dione-3,5 (Hdmod)
Figure 1. – Structure formulas and names of β-diketonate ligands.
Since the polymerization of β-diketonates
of lanthanides occurs according to the same
mechanism as the polymerization of vinyl
monomers, azobisisobutyronitrile (AIBN)
was used as the initiator of radical polymeri-
zation, and the polymerization temperature
was 80°C.
The synthesized compounds were investi-
gated by IR spectroscopy, diffuse reflectance
spectra (DRS), thermogravimetry and lumi-
nescence analysis.
IR spectra were recorded on a Specord M80
spectrometer in the region of 400–4000 cm-1
in КВr tablets.
Diffuse reflectance spectra in the range of
300–1100 nm were recorded on a Shimadzu
UV-3600 UV-VIS-IR spectrophotometer.
The hydrate composition of the synthe-
sized compounds and their thermal stability
were determined by the DTA method. Ther-
mograms were recorded on a Q-1500 °D deri-
vatograph of the F. Paulik, J. Paulik, L. Erdey
system in the temperature range of 20–500 °С
with a heating rate of 5°С/min in a platinum
crucible in the presence of a carrier (anhy-
drous Al2O3). The excitation and luminescence
spectra of solid complexes were recorded on a
Fluorolog FL 3–22 spectrofluorimeter, Horiba
Jobin Yvon (Xe-lamp 450 W) using an OS 11
filter, followed by their correction taking into
account the radiation distribution of the xenon
lamp and the sensitivity of the photomultipli-
er. An InGaAs photoresistor (DSS-IGA020L,
Electro-Optical Systems, Inc, USA, (cooled to
liquid nitrogen temperature) was used as a ra-
diation detector for the IR region.
In order to determine the method of coor-
dination of ligands to the metal ion during the
polymerization of Yb(III) complexes, studies
were carried out by the method of IR spec-
troscopy. The results of the study of IR spectra
are presented in Table 1, where, taking into ac-
count the literature data, the vibration bands
were assigned [18].
Table 1. – Assignment of oscillation frequencies in IR spectra.
compound ν(Ln–O) + δch.ring ν(Ln–N) νas (С С) νs (С О) ν (C=O) ν (C=C)
[Yb(dmhpd)3]n 419, 426, 484, 511 – 1537 1578 – 1659w
[Yb(dmhpd)3⋅Phen]n 417, 429, 475, 515 468 1535 1577 – 1653w
[Yb(dmod)3]n 421, 435, 481, 511 – 1542 1581 – 166w
[Yb(dmod)3⋅Phen]n 419, 439, 474, 518 465 1544 1584 – 1663w
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The IR spectra of the investigated polymer
compounds showed that the shape and posi-
tion of the characteristic vibration bands are
similar to those of the corresponding mono-
mer complexes, i.e. they do not depend on the
length of the hydrocarbon radical. The inten-
sity of the bands is significantly lower, which
is due to the increase in molecular weight and
indirectly indicates the formation of a polymer
structure. The C-O and C-C vibration bands
undergo only a slight shift to the low-frequen-
cy region, but their position clearly indicates
the bidentate-cyclic coordination of β-dike-
tonate ligands to ytterbium [19]. It should be
noted that the vibration band corresponding to
the C=C double bond almost completely dis-
appears in the case of polymer samples, which
also indicates the polymerization of complexes.
The presence of insignificant shoulders in this
range indicates the remains of terminal dou-
ble bonds in polymer molecules. Oscillation
bands observed for the studied samples in the
region of 400–600 cm-1 indicate the presence
of a metal-oxygen bond. Thus, confirming the
invariance of the structure of the elementary
links of the polymer molecule. It is difficult to
draw conclusions about changes in the Yb-O
bond based on the IR spectra, since in this
range the sum of fluctuations of both the M-O
bond and deformational vibrations of the che-
late ring is observed [18]. However, it should
be noted that these bands are more ordered
in the case of polymer monoligand complex-
es compared to their monomer counterparts,
which may be due to a more strong structure
of the polymer chain.
For polymers obtained on the basis of
mixed ligand complexes, in addition to the
above-mentioned vibration bands, we also ob-
serve a band corresponding to the Yb-N bond
(465, 468 cm-1). Its presence confirms that
the hetero-ligand complexes (HLC) molecule
is part of the elementary link of the polymer
chain without undergoing changes in its struc-
ture.
In the region of 3200–3600 cm-1 in the IR
spectra of all synthesized ytterbium metallopo-
lymers, there is a weak wide band of oscilla-
tions, which may indicate the presence of wa-
ter in the samples. Presumably, this may be due
to both the moisture content of the sample and
the presence of water molecules in the voids of
the metal polymer.
In order to identify the hydrate composition
and thermal stability of the investigated com-
pounds, analysis by DTA was carried out. The
study of thermal destruction of metal-polymer
samples is carried out not only for the purpose
of obtaining new heat-resistant materials, but
also to determine correlations between their
structure and properties. The results of their
study are given in table. 2.
Table 2. – Results of thermogravimetric analysis.
Compound
dehydration process
tstart of decomposition,oС
t, oС / thermal effect Δm, %
[Yb(dmhpd)3]n 124/ endo 2,1 325
[Yb(dmhpd)3⋅Phen]n 131/ endo 1,6 371
[Yb(dmod)3]n 135/ endo 1,8 343
[Yb(dmod)3⋅Phen]n 134/ endo 1,5 358
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Comparing the thermograms of polymer
compounds with the corresponding thermo-
grams of metal complexes, some differences
can be noted. For all studied polymer samples
in the temperature range of 110–150 °С, as well
as for monomer complexes, we observe a loss
of mass, but in the case of polymers, its value
is insignificant (Δm = 1.5–2.1%). This may in-
dicate that water molecules are not included in
the structure of the macromolecule. However,
taking into account the rather high values of
the dehydration temperature, we can conclude
about the presence of occluded water, that is,
water distributed in the cavities of the polymer
molecule. Such a structure is caused by the
polymerization process at low temperatures.
Another feature of the thermal decomposition
of metallopolymers is that the temperature of
the start of destruction increases by 10–15 °C
in the studied monoligand samples compared
to their monomer counterparts [20]. For hete-
roligand polymers, the temperature of the be-
ginning of the destruction of the structure of
macromolecules is 358–371 °С, which indi-
cates the greatest thermal stability among the
studied systems. This can be explained by a de-
crease in the mobility of bonds in the polymer
molecule with the formation of mesh struc-
tures. With increasing temperature, a wide
exoeffect is observed on the thermograms of
monoligand samples, which can be attribut-
ed to the destruction of the polymer chain.
For mixed-ligand polymer compounds above
350 °С, a number of minor thermal effects are
noted, which can be associated with both the
rearrangement in the structure of the meta-
llopolymer and the destruction of their mac-
romolecules.
The process of thermal decomposition of
Yb(III) metal polymers is similar for different
ligands, but comparing the thermograms of
mono- and heteroligand samples, one should
note an increase in the thermal stability of the
latter.
Since the remains of the samples after ther-
molysis up to 500 °C are 48–54%, this may
indicate the incomplete destruction of poly-
mer molecules at a given temperature due to
the progress of structuring reactions in paral-
lel with the thermal decomposition reactions,
and, consequently, the high thermal stability of
the presented samples.
To determine the structure of the elemen-
tary unit of the metal polymer molecule, the
synthesized compounds were studied by dif-
fuse reflection spectroscopy. On the figure 2
have shown the diffusive reflectance spectra
of dimethyloctenedione polymer complexes
in comparison with their monomeric counter-
parts. In the near ultraviolet (200-400 nm) re-
gion (Fig. 2a), there are bands associated with
π→π* transitions. In this range, for the mono-
meric monoligand complex, an extended band
(λmax = 288 nm) is observed, corresponding to
electronic π→π* transitions from the ground
(S0) to the excited state (S1) of the ligand mo-
lecule.
For the polymer analogue of the Yb(III)
complex, this band broadens and splits into
two components (λmax = 268 and 290 nm),
which can be a confirmation of polymeriza-
tion. As for the heteroligand compounds of
ytterbium dimethyloctenedionate, this band
is broadened, split and significantly shifted
to the region of high energies (λmax = 257
and 347 nm for [Yb(dmokd)3•Phen]n), which
may be due to the overlap of the bands π→π*
transition and charge transfer bands from the
ligand to the metal. The shape and position of
this band for metal-polymer compounds also
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INVESTIGATION OF NEW POLYMER COMPLEXES BASED ON Yb(III) β-DIKETONATESINORGANIC CHEMISTRY
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INVESTIGATION OF NEW POLYMER COMPLEXES BASED ON Yb(III) β-DIKETONATESINORGANIC CHEMISTRY
confirms the formation of a polymer struc-
ture.
As is known, the electronic spectra of ytter-
bium compounds (Fig. 2b) are characterized
by one transition 2F7/2 →2F5/2 of the Yb(III) ion
from the ground state.
The maxima of these transitions for the
studied metallopolymers are shown in Table 3.
а b
Figure 2. – DRS of mono- and polymer compounds of ytterbium(III).
Table 3. – Positions of transition maxima in the DRS of Yb(III) metallopolymers.
Compound λmax, nm Compound λmax, nm
Yb(dmhpd)3·2H2O 10270 Yb(dmokd)3·2H2O 10255
[Yb(dmhpd)3·2H2O]n 10290 [Yb(dmokd)3·2H2O]n 10280
Yb(dmhpd)3·Phen 10265 Yb(dmokd)3·Phen 10250
[Yb(dmhpd)3·Phen]n 10275 [Yb(dmokd)3·Phen]n 10288
For all Yb(III) compounds, a slight shift of
the band (~20–40 cm–1) to the short wavelength
region is observed in comparison with mono-
meric metal complexes, which has a slight
deformation of the polyhedron during poly-
merization and, probably, indicates an increase
in the bond metal with a ligand. It should be
noted that the shape and position of the bands
in the DRS of ytterbium polymers practically
do not differ from their monomeric counter-
parts, which indicates the same structure of the
molecule of the complex and the correspond-
ing elementary units of the polymer chain.
That is, the geometry and structure of the coor-
dination polyhedron of the structural units of
the macromolecule does not change during the
polymerization of the complexes (Fig. 3). Thus,
based on the results of the study and drawing
an analogy with the previously studied metal
complexes [20, 21], we can conclude that the
coordination polyhedron of the polymer unit
is a square antiprism:
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R=-CH(CH3)2; -CH2CH(CH3)2.
Figure 3. – Scheme of structure of Yb (III) poly-
complexes.
Thus, according to the totality of the ana-
lyzes performed, it was found that the com-
position of the polymers corresponds to the
formulas [Yb(β-dik)3]n and [Yb(β-dik)3∙Phen]n
(β-dik = dmhpd, dmod).
As is known, ytterbium complexes are ca-
pable of exhibiting 4-f luminescence in the
near IR range. Regarding the information on
the emission characteristics of polymers con-
taining compounds Yb(III) in their composi-
tion, they usually concern materials obtained
by metal intercalation into the polymer matrix
of industrial monomers [22]. The number of
works on the study of the luminescent pro-
perties of polymers, in which each metal ion
is associated with the organic component by
chemical bonds and is uniformly distributed
in the macromolecule, is still limited. Of par-
ticular interest are the emission properties of
the synthesized polymer compounds. In or-
der to select metal complexes, precursors of
luminescent materials, a comparative analysis
of the luminescent characteristics of Yb(III)
monomeric and metal-polymer β-diketonate
complexes was carried out.
To record the luminescence spectra of the
synthesized compounds in the solid state,
the excitation spectra of [Yb(dmhpd)3]n and
[Yb(dmhpd)3∙Phen]n were recorded. One band
with a maximum at λmax = 365 nm and 361
nm, respectively, is identified in the excitation
spectra of the compounds under study. Excita-
tion to the maxima of these [Yb(dmhpd)3]n
and [Yb(dmhpd)3∙Phen]n bands causes emis-
sion due to the transition of an electron from
the triplet level of the ligand to the singlet level
of the lanthanide ion.
In fig. 4 shows the luminescence spectra
of polymer compounds of ytterbium with di-
methylheptendione.
Figure 4. – Luminescence spectra of ytterbium
polydimethylheptendionates.
It is known that the Yb(III) ion has one
transition from the excited level 2F5/2 → 2F7/2
(λmax = 981 nm and 985 nm, respectively).
The shape and position of the presented bands
do not differ significantly. As can be seen from
the figure, the relative emission intensity of
[Yb(dmhpd)3]n is 1.5 times higher than the
relative intensity of the monomer analogue
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INVESTIGATION OF NEW POLYMER COMPLEXES BASED ON Yb(III) β-DIKETONATESINORGANIC CHEMISTRY
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INVESTIGATION OF NEW POLYMER COMPLEXES BASED ON Yb(III) β-DIKETONATESINORGANIC CHEMISTRY
Yb(dmhpd)3. This is due to a decrease in con-
centration quenching and, as a result, non-ra-
diative losses.
The emission intensity of mixed ligand
complexes [Yb(dmhpd)3∙Phen]n is 3–3.5 ti-
mes higher than that of monoligand analogs
Yb(dmhpd)3∙Phen. This is due to the replace-
ment of water molecules in the nearest coordi-
nation environment and the additional anten-
na effect of the phenathroline molecule.
On fig. 5 shows the photoluminescence
spectra of polymeric derivatives of dimethy-
loctenedione complexes ytterbium. The ex-
citation of these samples λexc=361 nm leads to
intense 4-f radiation. The shape and position
of the band maxima are similar to dimethyl-
heptenedionates. As can be seen from the fi-
gure, the band is split into 2 components, and
the maxima are observed at 984 and 985 nm
for [Yb(dmod)3]n and [Yb(dmod)3∙Phen]n, re-
spectively.
Figure 5. – Luminescence spectra of ytterbium
polydimethyloctenedionates.
However, there is some difference in the
properties of the complexes based on the gi-
ven ligands of these systems. Thus, the rela-
tive emission intensity of the metallopolymer
[Yb(dmоd)3]n is 1.5 times less than that of the
monomer. A comparative analysis of mono-
meric and metallopolymer complexes of yt-
terbium with different ligands indicates high-
er emission properties of compounds based
on dimethyloctenedione, which is due to the
longer length of the hydrocarbon radical and
the increase in the covalency of the bond [20].
In addition, this may be due to the low degree of
polymerization of dmhpd-based compounds
due to rapid chain breakage, and, as a result,
the formation of several oligomeric forms that
will cause concentration quenching. This fact
is confirmed by the half-width and splitting of
the emission band.
It is known that the spectral lines have a cer-
tain width - the larger, the wider the gap. All
spectra were recorded at the same slit width,
except for [Yb(dmod)3∙Phen]n. It was possible
to register a qualitative spectrum only with
an increase in the width of the slit, which re-
sulted in the expansion of the emission band
and its significant splitting. In this case, the
radiation intensity of [Yb(dmod)3∙Phen]n is
3 times higher than the radiation intensity of
Yb(dmod)3∙2Н2О. A significant antenna effect
of the phenatrolin molecule due to addition-
al energy transfer, luminescence sensitization,
and the formation of a more strong structure
of such compounds contribute to an increase
in emission characteristics. It should also be
noted that the addition of phenatrolin, which
replaces H2O molecules in the nearest coor-
dination environment of the lanthanide ion,
neutralizes the additional quenching effect of
water molecules.
The studies performed have shown that the
nature of the substituents in the ligand mo-
lecules and the length of the hydrocarbon ra-
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N. Ivakha, O. Berezhnytska, O. Rohovtsov, S. Smola, O. Trunova UCJ № 5 / Vol. 88
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N. Ivakha, O. Berezhnytska, O. Rohovtsov, S. Smola, O. Trunova UCJ № 5 / Vol. 88
dical have a significant effect on the emission
properties of metal complexes.
Figure 6. – Luminescence spectra of ytter-
bium metalopolymers.
Figure 6 shows the luminescence spectra of
Yb(III) metal polymers with aromatic (mphpd)
and aliphatic substituents. The maximum emis-
sion intensity is characteristic of the yterbium
metal polymer with dimethyloctenedione. The
relative emission intensity of [Yb(dmod)3]n is
2.2 and 2.7 times higher than the emission in-
tensity of [Yb(dmhpd)3]n and [Yb(mphpd)3]n,
respectively. The large difference in the energy
of the triplet level of the ligand and the reso-
nance level of the lanthanide, the steric factor,
and the shielding of the emitting ion by bulky
ligand molecules cause the low emission of
complexes with aromatic substituents.
For heteroligand metal polymers with phe-
nantrolin (Fig. 7), this dependence is more
noticeable. In this case, a similar dependence
is observed: the relative intensity of the lumi-
nescence of the HLC increases in the series:
[Yb(mphpd)3·Phen]n<[Yb(dmhpd)3·Phen]n
<[Yb(dmod)3·Phen]n.
Figure 7. – Luminescence spectra of hetero-
ligand ytterbium metal polymers.
Based on the data of luminescent analysis,
it can be concluded that heteroligand poly-
mer complexes based on β-diketones with ali-
phatic substituents can be the most effective
precursors of luminescent materials emitted
in the NIR region. The use of their analogs
with aromatic components is less reasonable,
since bulky structural units shield the emitting
centers, thus reducing the emission characte-
ristics of the compounds.
CONCLUSIONS. In this work, for the first
time, metalopolymer samples based on ytterbi-
um (III) dimethylheptenedionate and dimethy-
loctenedionate, and polymer compounds of
their heteroligand derivatives, were obtained
by radical polymerization. Their structure,
thermal and luminescent properties have been
studied. It has been determined by DRS and IR
spectroscopy that the structure of the elemen-
tary unit of the polymer chain of the obtained
polycomplexes does not undergo significant
changes during polymerization. The ligands
are coordinated to the metal in a bidentate-cy-
clic manner, and the shape of the coordination
12 ISSN 2708-129X. Укр. хім. журн., 2022
INVESTIGATION OF NEW POLYMER COMPLEXES BASED ON Yb(III) β-DIKETONATESINORGANIC CHEMISTRY
12 ISSN 2708-129X. Укр. хім. журн., 2022
INVESTIGATION OF NEW POLYMER COMPLEXES BASED ON Yb(III) β-DIKETONATESINORGANIC CHEMISTRY
polyhedron corresponds to a square anti-
prism. Thermogravimetric studies have shown
a significant increase in the thermal stability
of the studied compounds compared to their
monomeric counterparts, which is associated
with the formation of a more stable polymer
structure with a system of branched bonds.
At the same time, heteroligand metal poly-
mers demonstrated the highest thermal stabi-
lity. An analysis of the luminescent properties
showed that all polymers exhibit effective IR
luminescence, while its relative intensity var-
ies in the series [Yb(dmhpd)3]n <[Yb(dmod)3]n
<[Yb(dmhpd)3∙Phen]n<[Yb(dmod)3∙Phen]n.
Comparison of the emission characteristics of
the studied compounds with metal polymers
based on methacrylacetophenoates and ter-
bium showed that the use of aliphatic β-dike-
tones with a linear structure as initial ligands
in order to obtain mixed-ligand systems and
polymeric materials on their basis seems to be
the most promising. A high relative emission
intensity is characteristic of heteroligand com-
plexes; therefore, they can be proposed as pre-
cursors of luminescent materials.
AKNOWLEDGEMENT. The work was
carried out with the financial support
of the National Academy of Sciences of
Ukraine within the state budget topic 322E "Cre-
ation of new hybrid, composite and polymer
materials doped with coordination compounds
of 3d- and 4f- metals based on β-diketonate and
carboxylate acyclic ligands". The state registra-
tion number of the work is 0122U001299.
We express our gratitude to the Department
of Chemistry of High Molecular Weight T.G.
Shevchenko Kyiv National University and per-
sonally to its head I.O. Savchenko for help in
the synthesis of metallopolymeric compounds.
ДОСЛІДЖЕННЯ НОВИХ ПОЛІМЕРНИХ КОМП-
ЛЕКСІВ НА ОСНОВІ β-ДИКЕТОНАТІВ Yb(III)
Н. Б. Іваха1,2*, О. С. Бережницька1,2,
О. О. Роговцов1, С. Смола3, 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
України “Київський політехнічний інсти-
тут імені Ігоря Сікорського”, просп. Пере-
моги, 37, Київ 03056, Україна
3 Фізико-хімічний Інститут імені О. В. Бо-
гатського НАН України, вул. Люстдорфська
дорога, 86, Одеса 65080, Україна
e-mail: ivakhanadiia@gmail.com
Методом радикальної полімеризації
одержано металополімери на основі моно-
та змішанолігандних β-дикетонатних комп-
лексів Yb(III) з 2,7-диметил-октен-1-діо-
ном-3,5 та 2,6-диметил-гептен-1-діоном-3,5
та фенантроліном. За допомогою комплек-
су фізико-хімічних методів аналізу вста-
новлено, що будова елементарної ланки не
зазнає суттєвих змін порівняно з вихідни-
ми молекулами β-дикетонатів. Термічний
аналіз показав значне підвищення темпе-
ратури початку розкладання металополі-
мерних сполук відносно їхніх мономерних
аналогів. Методом люмінесцентної спект-
роскопії встановлено, що досліджувані
зразки проявляють інтенсивну ІЧ-люмінес-
ценцію. Зростання емісійних властивостей
металополімерів зумовлено зменшенням
обмінних взаємодій за рахунок утворення
впорядкованої структури, а у випадку змі-
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N. Ivakha, O. Berezhnytska, O. Rohovtsov, S. Smola, O. Trunova UCJ № 5 / Vol. 88
13https://ucj.org.ua
N. Ivakha, O. Berezhnytska, O. Rohovtsov, S. Smola, O. Trunova UCJ № 5 / Vol. 88
шанолігандних сполук – унаслідок додат-
кового переносу енергії та сенсибілізації
люмінесценції.
Ключові слова: ненасичені β-дикетони,
комплекси, ітербій, полімеризація, люмі-
несценція.
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Стаття надійшла 07.06.2022.
|
| id | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-447 |
| institution | Ukrainian Chemistry Journal |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-07-23T01:08:10Z |
| publishDate | 2022 |
| publisher | V.I.Vernadsky Institute of General and Inorganic Chemistry |
| record_format | ojs |
| resource_txt_mv | ucjorgua/63/2b3cad87d530fcd20fda6fd4bbc9c763.pdf |
| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-4472026-07-22T08:23:49Z INVESTIGATION OF NEW POLYMER COMPLEXES BASED ON Yb(III) β-DIKETONATES Ivakha , Nadiia Berezhnytska, Oleksandra Rohovtsov , Oleksandr Trunova, Olena Smola, Serhii unsaturated β-diketones, complexes, ytterbium, polymerization, luminescence. The metal polymers based on mono- and heteroligand β-diketonate complexes of Yb(III) with 2,7-dimethyl-octen-1-dione-3,5, 2,6-dimethyl-heptene-1-dione-3, 5 and with phenanthroline was synthesized. It has been defined that the coordination environment of the central ion remains unchanged during radical polymerization. The shape and position of the bands in the electronic absorption spectra are similar to the corresponding monomeric β-diketonate metal complexes, and slight shifts indicate deformation of the elementary unit of the metal polymer during the formation of the polymer chain. It is shown that the polymerization process lead to an increasing in the thermal stability of polymer complexes in comparison with monomeric analogues. An increase in the emission of metal polymers in comparison with monomeric complexes was established by the method of luminescent spectroscopy, which is due to energy, steric, and structural-mechanical factors. V.I.Vernadsky Institute of General and Inorganic Chemistry 2022-06-24 Article Article Inorganic Chemistry Неорганическая химия Неорганічна хімія application/pdf https://ucj.org.ua/index.php/journal/article/view/447 10.33609/2708-129X.88.05.2022.3-14 Ukrainian Chemistry Journal; Vol. 88 No. 5 (2022): Ukrainian Chemistry Journal; 3-14 Украинский химический журнал; ##issue.vol## 88 ##issue.no## 5 (2022): Ukrainian Chemistry Journal; 3-14 Український хімічний журнал; Том 88 № 5 (2022): Український хімічний журнал; 3-14 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/447/225 Copyright (c) 2022 Nadiia Ivakha , Oleksandra Berezhnytska, Oleksandr Rohovtsov , Olena Trunova, Serhii Smola https://creativecommons.org/licenses/by-nc/4.0 |
| spellingShingle | Ivakha , Nadiia Berezhnytska, Oleksandra Rohovtsov , Oleksandr Trunova, Olena Smola, Serhii INVESTIGATION OF NEW POLYMER COMPLEXES BASED ON Yb(III) β-DIKETONATES |
| title | INVESTIGATION OF NEW POLYMER COMPLEXES BASED ON Yb(III) β-DIKETONATES |
| title_full | INVESTIGATION OF NEW POLYMER COMPLEXES BASED ON Yb(III) β-DIKETONATES |
| title_fullStr | INVESTIGATION OF NEW POLYMER COMPLEXES BASED ON Yb(III) β-DIKETONATES |
| title_full_unstemmed | INVESTIGATION OF NEW POLYMER COMPLEXES BASED ON Yb(III) β-DIKETONATES |
| title_short | INVESTIGATION OF NEW POLYMER COMPLEXES BASED ON Yb(III) β-DIKETONATES |
| title_sort | investigation of new polymer complexes based on yb(iii) β-diketonates |
| topic_facet | unsaturated β-diketones complexes ytterbium polymerization luminescence. |
| url | https://ucj.org.ua/index.php/journal/article/view/447 |
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