КООРДИНАЦІЙНІ СПОЛУКИ Gd3+ та Dy3+ З ДЕЯКИМИ β-ДИКЕТОНАМИ
New complexes of Dy (III) and Gd (III) with b-diketones containing unsaturated and aryl substituents were synthesized. Metal polymers based on synthesized complexes were obtained by the method of radical polymerization. The composition and structure of synthesized complexes and metal polymers are es...
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| author | Berezhnytska , Оeksandra Rohovtsov , Oleksandr Horbenko , Artur Fedorov , Yaroslav Trunova , Olena Chyhyrynets , Olena Smola , Sergey |
| author_facet | Berezhnytska , Оeksandra Rohovtsov , Oleksandr Horbenko , Artur Fedorov , Yaroslav Trunova , Olena Chyhyrynets , Olena Smola , Sergey |
| author_institution_txt_mv | [
{
"author": " Оeksandra Berezhnytska ",
"institution": "V.I.Vernadsky Institute of General and Inorganic Chemistry of NAS of Ukraine"
},
{
"author": "Oleksandr Rohovtsov ",
"institution": "V.I.Vernadsky Institute of General and Inorganic Chemistry of NAS of Ukraine"
},
{
"author": "Artur Horbenko ",
"institution": "V.I.Vernadsky Institute of General and Inorganic Chemistry of NAS of Ukraine"
},
{
"author": "Yaroslav Fedorov ",
"institution": "V.I.Vernadsky Institute of General and Inorganic Chemistry of NAS of Ukraine"
},
{
"author": "Olena Trunova ",
"institution": "V.I.Vernadsky Institute of General and Inorganic Chemistry of NAS of Ukraine"
},
{
"author": "Olena Chyhyrynets ",
"institution": "National Technical University of Ukraine «Igor Sikorsky Kyiv Polytechnic Institute»"
},
{
"author": "Sergey Smola ",
"institution": "A.V. Bogatsky Physico-Chemical Institute NASU, Odessa, Ukraine"
}
] |
| author_sort | Berezhnytska , Оeksandra |
| baseUrl_str | https://ucj.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-22T08:23:46Z |
| description | New complexes of Dy (III) and Gd (III) with b-diketones containing unsaturated and aryl substituents were synthesized. Metal polymers based on synthesized complexes were obtained by the method of radical polymerization. The composition and structure of synthesized complexes and metal polymers are established. It is shown that during polymerization the coordination environment of the central ion remains unchanged. The spectral-luminescent characteristics of the synthesized compounds were studied. The presence of water molecules in the immediate coordination environment causes a low intensity of emission of monomeric dysprosium complexes. In the luminescence spectra of metal polymers, there are bands magnetic dipole transition (4F9 → 6H15/2) and electric dipole transition (4F9 → 6H13/2). The close energies of the triplet level of the ligand and the resonant level of the dysprosium ion cause low emission characteristics of the synthesized dysprosium complexes. |
| doi_str_mv | 10.33609/2708-129X.87.06.2021.97-120 |
| first_indexed | 2025-09-24T17:43:39Z |
| format | Article |
| fulltext |
97
УДК 54-386; 546.662; 546.664 doi: 10.33609/2708-129X.87.06.2021.97-120
THE COORDINATION COMPOUNDS Gd (III) AND Dy(III) WITH SOME
β-DIKETONES
О. S. Berezhnytska1,2, A. E. Horbenko1, O. O. Rohovtsov1, S. S. Smola3, Ya. V. Fedorov1,
O. E. Chygyrynets2, О. К. Trunova1
1 V.I.Vernadsky Institute of General and Inorganic Chemistry of NAS of Ukraine, Akad. Palladin
Avenue, 32/34, Kyiv 03142, Ukraine.
2 National Technical University of Ukraine «Igor Sikorsky Kyiv Polytechnic Institute», 37, Peremohy
Avenue, Kyiv 03056, Ukraine.
3 A.V. Bogatsky Physico-Chemical Institute NASU, Lyustdorfska doroha St., 86, Odessa, Ukraine
* e-mail: berezhnytska@gmail.com
New complexes of Dy (III) and Gd (III) with b-diketones containing unsaturated and aryl
substituents were synthesized. Metal polymers based on synthesized complexes were obtained
by the method of radical polymerization. The composition and structure of synthesized com-
plexes and metal polymers are established. It is shown that during polymerization the coor-
dination environment of the central ion remains unchanged. The spectral-luminescent cha
racteristics of the synthesized compounds were studied. The presence of water molecules in
the immediate coordination environment causes a low intensity of emission of monomeric
dysprosium complexes. In the luminescence spectra of metal polymers, there are bands mag-
netic dipole transition (4F9 → 6H15/2) and electric dipole transition (4F9 → 6H13/2). The close
energies of the triplet level of the ligand and the resonant level of the dysprosium ion cause
low emission characteristics of the synthesized dysprosium complexes.
Key words: lanthanides, complexes, luminescence properties, metalopolymer, gadolini-
um, dysprosium, β-diketones.
INTRODUCTION. High luminescence
[1–6], magnetic activity [7–11], and the pos-
sibility of using as bioactive materials [12–13]
and telecommunication devices [14–16] are
responsible for the continuing interest in co-
ordination compounds of lanthanides.Highly
volatile stable complexes of lanthanides with a
mononuclear structure play a significant role
as precursors for the gas-phase synthesis of
thin-film materials [17–18].
One of the most important factors influenc-
ing the properties is the correct selection of li-
gand systems makes it possible to avoid nonra-
diative energy losses during the transition from
the singlet to the triplet level. Only at mini-
mum phosphorescence and fluorescence en-
ergies can maximum luminescence intensities
be achieved [19–22]. Therefore, the difference
in the triplet energy level of the ligand and the
resonance energy level of the lanthanide ion
THE COORDINATION COMPOUNDS Gd (III) AND Dy(III) WITH SOME β-DIKETONES
98 ISSN 2708-129X. Укр. хім. журн., 2021
INORGANIC CHEMISTRY
is of great importance. In general, the energy
of the resonance level of the metal should be
somewhat lower than the energy of the triplet
level of the ligand, which neutralizes the non-
radiative deactivation of the resonance level
together with a high probability and efficiency
of the emitting transition. The overwhelming
majority of studies in this area are on lantha-
nide complexes emitting in the visible region
of the spectrum, in particular, Eu(III), Tb(III),
Sm(III), Nd(III), Yb(III) [12, 20, 22–26]. Al-
though dysprosium compounds (III) are also
capable of emitting in the visible region of the
spectrum, such studies are limited due to the
complexity of the ligand selection. Such is due
to the rather high energy of the resonance le
vel of the dysprosium ion compared to Eu (III)
and Sm (III). Some works considered the pos-
sibility of using dysprosium complexes in the
creation of white light emitters for optoelec-
tronics. It could be realized by doping or titrat-
ing dysprosium complexes with complexes of
other metals, or by mixed-ligand complexa-
tion. Thus, in the work use, bimetallic Dy: Eu
complexes and trimetallic Dy: Gd: Eu com-
plexes emit white light. Doping of gadolinium
complexes with dysprosium complexes or Dy \
Eu Dy \ Sm HMC allowed the authors to ob-
tain white light [15, 27–28]. In particular, the
work showed the possibility of transition from
yellow through white to blue light [29, 30].
In addition, complexes of these metals can
be used as contrast agents for MRI diagnos-
tics. The Gd3+ and Dy3+ ions, having an opti-
mal contrast enhancement in comparison with
other paramagnetic ions, are highly toxic in the
free state (10 mg / kg of body weight) [31]. To-
day, the chemical compounds DTPA (diethy
lenetriaminepentaacetic acid), DTPA-BMA
(gadodiamide), DOTA (tetraazocyclododeca-
netetraacetic acid), HP-DO3A (2-hydroxypro-
pyltetraazododecanetriacetic acid) and, other
derivatives are used as ligand systems. Their
complexes with metals have paramagnetic prop-
erties, are low-molecular water-soluble, hydro-
philic contrast agents that are excreted from the
body by the kidneys [31–33]. The main problem
of creating paramagnetic contrast agents is to
find the optimal balance of high paramagnetic
properties and toxicity. The ideal contrast para
magnetic should have the maximum relaxing
ability in the practical absence of toxicity [34,
35]. For the rejection of macromolecular con-
trast agents, it is possible to create a significant
improvement in the relaxation efficiency of
low-molecular-weight compounds [36, 37]. In
addition, polymeric systems based on non-sca
ling b-diketonates of lanthanides (Gd (III) and
Dy (III) can be used as a precursor for rejecting
contrast talkers to compete with other active
materials. cell link in the molecule ligand.
It is unlikely that in the low-molecular state,
β-diketones could be used as precursors for
obtaining contrast agents because they are bi-
dentate ligands. However, polymer systems
based on them can compete with existing ma-
terials. The presence of a final double bond in
the ligand molecule makes it an active mono-
mer in polymerization reactions. Thus, metal
complexes based on unsaturated β-diketones
are active monomers in free radical polymeri
zation reactions [38, 39].
According to the literature data, it could
be pointed the areas of high scientific and
technological interests of this investigations:
1 – the using both mono- and heterometallic
complexes Gd (III) and Dy (III); 2 – doping of
gadolinium complexes by complexes of other
metals emitted in the visible and nearest-IR
spectral regions.
О. S. Berezhnytska, A. E. Horbenko, O. O. Rohovtsov, S. S. Smola, Ya. V. Fedorov, O. E. Chygyrynets, О. К. Trunova
99https://ucj.org.ua
UCJ № 6 / Vol. 87
In this regard, in this work, we performed
the synthesis, studies of the structure and
properties of-diketonate complexes of Gd (III)
and Dy (III) with unsaturated β-diketones and
metal polymers based on them.
EXPERIMENT AND DISCUSSION OF THE
RESULTS. As starting compounds were se-
lected β-diketonate ligands (2-methyl-5-phe-
nylpentan 1-3,5, -dion (mphrd) (2-me-
thyl-5-biphenyl penten 1-3,5, -dione (mbphd)
are shown in sсheme 1.
Sсheme 1. Structure of the ligands.
To a three-necked reactor cooled with a
mixture of ice and sodium chloride, equipped
with a magnetic stirrer, a reflux condenser and
a dropping funnel containing 0,5 moles of sodi-
um metal (11,5 g) and, 300 cm3 of dry diethyl
ether, was added dropwise a solution of 0,5 mol
(99 cm3) of biphenylketone and 0,5 mol (63 cm3)
of methacrylic acid ethyl ester. As a result of the
reaction, a yellow precipitate fell out:
The synthesis of ligands was performed by
Kleisen condensation according to the scheme
presented in Fig. The method of ligand synthe-
sis is described earlier [38, 40].
For the synthesis of β-diketonate complex-
es Gd (III) and Dy (III) was used dysprosium
acetate (III) Dy(CH3COO)3∙4H2O (c.p), gado-
linium nitrate (III) Gd(NO3)3∙5H2O (c.p), so-
dium hydroxide NaOH (c.p).
Scheme 2. Synthesis scheme of ligands.
The synthesis of complexes was performed
by the interaction of aqueous solutions of metal
salts with an aqueous solution of a sodium salt
of the corresponding ligand at a molar ratio of
reagents 1: 3 (pH 8–9) at room temperature.
Dy(CH3COO)3 + 3NaL → DeL3 + 3CH3COONa
Gd(NO3)3+ 3NaL → GdL3 + 3NaNO3
L= mphpd, mbphpd.
THE COORDINATION COMPOUNDS Gd (III) AND Dy(III) WITH SOME β-DIKETONES
100 ISSN 2708-129X. Укр. хім. журн., 2021
INORGANIC CHEMISTRY
The resulting precipitates of the complexes
were separated from the mother liquor by cen-
trifugation, washed with water, and dried in a
vacuum desiccator over anhydrous CaCl2. All
synthesized complexes were yellowish.
A feature of the synthesis and purification
of β-diketonates of lanthanides Ln(β-dik)3 is
the need to carry out all operations at room
temperature, since with an increase in tempe
rature, partial oligomerization of the complex-
es occurs (due to the presence of a reactive C=C
double bond in ligand molecules), significantly
worsens their solubility. Therefore, recrystalli-
zation and additional purification of the com-
plexes by vacuum sublimation were not carried
out, although the volatility of the complexes is
high enough, which was confirmed by the re-
sults of thermal analysis.
Metal polymers of gadolinium and dyspro-
sium were obtained by the method of thermal-
ly initiated radical polymerization. Polyme
rization was carried out at 80° C in a DMF
solution at a monomer (tris-diketone) concen-
tration of 0.3 mol/dm3 and an AIBN initiator
concentration of 0.003 mol/dm3. The obtained
metal polymers were precipitated from solu-
tions with isopropanol [26, 38].
The synthesized compounds were investi-
gated by elemental analysis, FTIR, electron and
fluorescence spectroscopy, thermal analysis,
dynamic light scattering, and electron micro
scopy (SEM).
Quantum-chemical calculations of ligand
molecules and metal complexes were carried
out. The geometry of β-diketone molecules
and their complexes with dysprosium and
gadolinium was calculated using the MO-
PAC2016 program. For the calculation, the
PM7 method was chosen, which better shows
the long-range interaction of atoms in a mol-
ecule, makes it possible to more accurately
predict the crystal structure and heats of the
formation of solids. In addition, the PM7 me
thod calculates hydrogen bonds in more de-
tail, which makes it possible to better describe
non-covalent interactions. The use of PM7 in
combination with the SPARKLE model, in
which the lanthanide atom is represented as
a point charge [41–42], makes it possible to
obtain reliable data on the geometry of lan-
thanide complexes with both aliphatic and
aromatic ligands.
The estimation of the enthalpy of forma-
tion of complexes was carried out on the ba-
sis of the calculated values for ligands and the
corresponding values for metal complexes.
The energy gap between the upper filled mo-
lecular orbital (HOMO) and the lower vacant
molecular orbital (LUMO) was calculated.
For each ligand and complex, the total energy,
dipole moment, and ionization potential were
given. The populations on the atomic orbitals
and the charges on the atoms of the ligand
molecules and the corresponding complexes
with gadolinium and dysprosium were cal-
culated. This allows us to conclude about the
localization of the electron density and bond
saturation.
Quantum-chemical calculations of ligand
molecules and metal complexes based on them
were carried out. The geometric structure of
the ligand molecule was first optimized by the
molecular mechanics method MM+ using the
HyperChem program, then the resulting ge-
ometric structure was the initial one for opti-
mization of the molecule geometry based on
the SPARKLE PM7 model in the MOPAC2016
program. As a result of calculations, the fol-
lowing geometrically optimized structures
were obtained (Fig.1).
О. S. Berezhnytska, A. E. Horbenko, O. O. Rohovtsov, S. S. Smola, Ya. V. Fedorov, O. E. Chygyrynets, О. К. Trunova
101https://ucj.org.ua
UCJ № 6 / Vol. 87
а
b
Fig. 1. Geometrically optimized structural formulas of β-diketones (a – mphpd, b – mbphpd).
There were calculated the base energy
characteristics of the ligand molecules using
the SPARKLE PM7 model: the enthalpy of for-
mation, the total energy of the molecule and
bond lengths, the parameters of the electron
populations of the ligands (Table 1).
Table 1
Characteristics of the structure and electronic populations of β-diketone
molecules and β-diketone molecules.
Estimated parameter mphpd mbphpd
Total energy (еВ) -2225,898 -3001,148
Heat of formation (kJ / mol) -187,341 -119,148
The dipole moment 2,179 2,526
THE COORDINATION COMPOUNDS Gd (III) AND Dy(III) WITH SOME β-DIKETONES
102 ISSN 2708-129X. Укр. хім. журн., 2021
INORGANIC CHEMISTRY
Ehomo(еV) -10,227 -9,561
Elumo(еV) -0,697 -1,061
Energy gap 9,53 8,5
Ionization potential (еV) 10,227 9,473
Bond lenght (Å)
СRCO - R 1,48175 1,4824
СRCO - O 1,20643 1,20565
СRCO – CCH2 1,50965 1,50799
CCH2 – CCO 1,51066 1,5115
CCO - O 1,20514 1,2051
CCO – CC-CH2 1,48905 1,4891
Atomic unit of charge:
Q СRCO /QCR 0,4832/-0,1651 0,4953/ -0,1693
QСRCO / QO 0,4832/-0,4296 0,4953/-0,4460
QCCH2 / QCCO -0,4988/ 0,4734 -0,501/0,4814
Q CCO /QO 0,4734/-0,4309 0,4814/-0,4311
QCCO – QCC-CH2 0,4734/ -0,0605 0,4814/ -0,0406
Analyzing the value of the heats of forma-
tion of ligands, we see that the process of forma-
tion of molecules is exothermic, we observed
this in the process of synthesis. As mentioned
above, while mixing the starting reagents, the
reaction mixture was heated. With an increase
in the volume of the ligand, upon going from
phenolic to biphenyl substituent, the heat of
formation increases from -187.341 kJ/mol
(mphpd) to -119.148 kJ/mol (mbphpd). The
dipole moment for mbphpd (2.526) is slight-
ly higher than for mphpd (2.179), which may
be due to the different distribution of electron
charges in the biphenyl molecule. The bond
lengths in both molecules are comparable, as
expected, due to the same nature of the sub-
stituents. The negative charge in both ligands is
concentrated on oxygen atoms. Having calcu-
lated the energies of the highest filled molecular
orbital (ЕHOMO) and the lowest vacant molecular
orbital (ЕLUMO), we can conclude that these com-
plexes will exhibit weak electron-withdrawing
properties, for mphpd and mbphpd ELUMO =
-0.697 eV and -1.061 eV, respectively.
The performed quantum-chemical calcu-
lations made it possible to geometrically opti-
mize the molecules of β-diketonate complexes
of gadolinium and dysprosium (Fig.2)
As can be seen from Fig. and fig. all pre-
sented complex compounds have a non-pla-
nar structure, and the ligands are located in
different planes. All ligands are bidentate and
are coordinated to the central ion (c.i) by two
oxygen atoms, which is consistent with pre-
vious studies and literature data. Comparing
the average bond lengths of lanthanides - oxy-
gen, we see that in dysprosium complexes it is
less - 2.2241 Å versus 2.2381 Å for gadolinium
complexes (Table 1). Such a change in the bond
length can be explained both by the effect of
lanthanide compression and by different popu
lations of orbitals.
Table 1
О. S. Berezhnytska, A. E. Horbenko, O. O. Rohovtsov, S. S. Smola, Ya. V. Fedorov, O. E. Chygyrynets, О. К. Trunova
103https://ucj.org.ua
UCJ № 6 / Vol. 87
а
b
Fig. 2. Geometrically structure of β-diketonate complexes of Gd(mphpd)3 ∙ 2H2O (a) and Gd(mbphpd)3
∙ 2H2O (b).
THE COORDINATION COMPOUNDS Gd (III) AND Dy(III) WITH SOME β-DIKETONES
104 ISSN 2708-129X. Укр. хім. журн., 2021
INORGANIC CHEMISTRY
а
b
Fig. 3. Geometrically structure of β-diketonate complexes of Dy(mphpd)3 ∙ 2H2O (a) and Dy(mbphpd)3
∙ 2H2O (b).
О. S. Berezhnytska, A. E. Horbenko, O. O. Rohovtsov, S. S. Smola, Ya. V. Fedorov, O. E. Chygyrynets, О. К. Trunova
105https://ucj.org.ua
UCJ № 6 / Vol. 87
Analyzing the value of the heats of formation
of complexes, it can be noted that negative values
are observed for complexes based on mphpd,
and positive for complexes of Gd and Dy with
mbphpd - +106.474 and +185.622 kJ/mol,
respectively. For the complexes Gd(mbphpd)3
∙ 2H2O and Dy(mbphpd)3 ∙ 2H2O, we have a
positive value of the heats of formation, indi-
cating that the formation of complexes occurs
with heat absorption, that is, the process is en-
dothermic.
As can be seen from the energies of the high-
est filled molecular orbital (EHOMO) and the
lowest vacant molecular orbital (ELUMO), the
complexes exhibit electron-withdrawing prop-
erties. EHOMO behaves like an electron donor,
while ELUMO behaves like an acceptor. The
difference between the energies of EHOMO
and ELUMO represents the HOMO-LUMO
energy gap. If a molecule has a small energy
gap, it shows high reactivity.
The ionization potential and the parameters
of the electron affinity were determined using
the energies of ЕHOMO and ELUMO, namely,
I = -EHOMO and A = -ELUMO, where I is the ioni
zation energy and A is the electron affinity.
In ionization by potential, a physical quanti-
ty is understood, which is determined by the
ratio of the smallest energy required for the
single ionization of an atom (or molecule) in
the ground state to the charge of an electron.
Ionization potential is a measure of ionization
energy equal to the work of detachment of an
electron from an atom or molecule and cha
racterizes the bond strength of an electron in
an atom or molecule.
As can be seen from the table, all calcu-
lated parameters correlate quite well in the
case of pairs of complexes with the same li
gands, namely: Gd(mphpd)3 and Dy(mphpd)3,
Gd(mbphpd)3 and Dy(mbphpd)3. Somewhat
lower values of the series parameters for dys-
prosium complexes, including the length of the
lanthanide-oxygen bond, which is determined
both by the different electronic structure of c.i.
and by a decrease in the ionic radius of the lat-
ter. All calculated parameters of the complexes
are shown in table 2.
Table 2
Characteristics of the structure and electronic populations of complexes.
Estimated parameter Gd(mphpd)3 Gd(mbphpd)3 Dy(mphpd)3 Dy(mbphpd)3
Total energy (eV) -6675,884 -8230,603 -6675,479 -8872,074
Heat of formation (kJ / mol) - 105,962 106,474 -26,744 185,622
The dipole moment 0,696 0,576 0,723 0,572
Ehomo(еV) -9,249 -8,932 -9,244 -8,929
Elumo(еV) -0,548 -0,868 -0,558 -0,872
Energy gap 8,701 8,064 8,686 8,057
Ionization potential (eV) 9,249 8,931 9,244 8,929
Electron affinity (eV) 0,548 0,868 0,558 0,872
Hardness (eV) 4,3505 4,032 4,343 4,0285
Softness (eV) 0,23 0,248 0,2302 0,248
Bond length lav О-Ln (Ǻ) 2,2355 2,2454 2,2266 2,2242
THE COORDINATION COMPOUNDS Gd (III) AND Dy(III) WITH SOME β-DIKETONES
106 ISSN 2708-129X. Укр. хім. журн., 2021
INORGANIC CHEMISTRY
The elimination of adsorbed water occurs
at 700C, further dehydration of dysprosium
and gadolinium complexes with methacroyl
acetophenone Ln(mphpd)3 occurs at tempe
ratures of 1650C and 1900C, respectively, and
is accompanied by significant endoeffects. At
the same time, there is a loss of sample mass by
4.4% (mop = 4.7%) for Dy(mphpd)3 and 4.6%
for Gd(mphpd)3 (mop = 4.8%), which corre-
sponds to the elimination of two coordinated
water molecules. Endoeffects at temperatures of
1980C (Dy(mphpd)3) and 1890C (Gd(mphpd)3)
are due to the melting of the complexes (the
weight loss in this case is 2% and 1.8%, respec-
tively). A further increase in temperature is ac-
companied by small exoeffects (2350C for Dy
and 2420C for Gd) and an insignificant weight
loss, which corresponds to the polymerization
of the complexes. With a further increase in
temperature (> 2400C) in both compounds,
the destruction of the complex occurs by the
elimination of one molecule of methacroylace-
tophenone, which is accompanied by exother-
mic effects at 275 and 2780C, respectively [43].
In the temperature range 285–5000C, the
thermal destruction of both complexes pro-
ceeds with the generation of heat; the ther-
mogram contains exoeffects at 293, 332, 380,
4420C for Dy(mphpd)3; 305, 345, 3800C for
Gd(mphpd)3) and a significant loss in the mass
of the samples, which is due to the decomposi-
tion of organic fragments of the molecule. The
total weight loss in the investigated tempera-
ture range for both complexes is ~ 80%. The
general view of the thermograms of complexes
based on mbphpd is practically the same. The
only difference are in the lower dehydration
temperature of complexes 1500С (Dy(mbph-
pd)3 and 1650С - Gd(mbphpd)3. The results of
elemental analysis and DTA made it possible
to establish that the composition of the synthe-
sized complexes corresponds to the formula
LnL3∙2H2O Ln = Gd, Dy, L = mphpd, mbphpd.
Thermograms of methalopolymers dif-
fer significantly. A significant endoeffect at
175–1850C is due to the elimination of water
molecules, which are located in the cavities of
the metalopolymer. Upon further heating, we
observe an exoeffect at 3500C and a significant
weight loss (∆m≈30%), which may be due to
the destruction of the metalopolymer struc-
ture. Endoeffect at 4400C may be due to steric
rearrangements in the polymer structure. Fur-
ther heating of the sample is accompanied by
small exoeffects at 480 and 4900C with practi-
cally no change in its weight, which indicates
the stability of the polymer at high tempera-
tures and the absence of destruction of the po
lymer structure.
The investigating of the results of thermal
analysis, we can say that the dehydration of all
synthesized monomeric complexes with aryl
substituents occurs in the range 120–1300C,
which indicates the outer-sphere coordination
of water molecules. Minor endoeffects in the
region of 195–2070C are due to the melting
of the complexes (the weight loss is insignifi-
cant, up to 2.5%). An increase in temperature
is accompanied by a number of exoeffects in
the range 240–2900C, which corresponds to
the elimination of one ligand molecule, the
weight loss, in this case, is in the range of
24–28%, which is in good agreement with the
theoretically calculated). Further exoeffects af-
ter 3000C correspond to the destruction of the
organic part of the molecule, and a significant
loss of mass. In general, the weight loss in the
investigated temperature range is 75–85%. The
decomposition mechanism for similar coor-
dination compounds was described in detail
О. S. Berezhnytska, A. E. Horbenko, O. O. Rohovtsov, S. S. Smola, Ya. V. Fedorov, O. E. Chygyrynets, О. К. Trunova
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UCJ № 6 / Vol. 87
by the authors earlier [43-45]. Weight loss in
this temperature range is accompanied by an
insignificant endoeffect and corresponds to
two coordinated water molecules, together
with elemental analysis allows us to state that
the composition of monomeric complexes cor-
responds to the formula LnL3 ∙ 2H2O, where
Ln = Gd(III), Dy(III) L = mphpd, mbphhd.
IR spectra were recorded on a Specord M80
spectrometer in the range of 400-4000 cm-1 in
KBr pellet. There are bands of symmetric and
asymmetric stretching vibrations of the bond
ν (C-O) and ν (C-C) in the IR spectra of the
synthesized metal β-diketonates in the range
of 1500–1700 cm-1. Since there is delocaliza-
tion of the electron density in the diketonate
fragment, the stretching vibration bands also
occupy an intermediate place between the
stretching vibrations of single CO and CC
and double C=O and C=C bonds [45–47]. It
is known that a band with a higher frequency
(~ 1575–1590 cm-1) corresponds to a symmet-
ric stretching vibration of the bond (CO), and
with a lower frequency (~ 1520–1555 cm-1) –
to an asymmetric stretching vibration of a
bond (CC). However, quite often these bands
are observed as one wide line split into several
components.
Table 3
Characteristic frequencies in IR spectra of Dy and Gd complexes with β-diketones (cm-1).
Complex ν(М-O)
+δhel.ring
νas(СО) νas(СС) νs(CO) νs(CC)+
νs(CPh)
ν(Н2О)
Dy(mphpd)3 415,422, 438,
475, 520
1427 1555 1590 1640, 1660 3230 3414
[Dy(mphpd)3]n 410, 425,
485, 515
1430 1560 1590 1640 3380
Gd(mphpd)3 415,420,433,
473, 518
1440 1540, 1557 1595 1645, 1652 3350
[Gd(mphpd)3]n 412, 425,
490, 515
1445 1550 1590 1658 3380
Dy(mbphhd)3 456, 470,
489, 520
1403, 1415 1542, 1560 1610 1680 3425
[Dy(mbphhd)3]n 450, 468,
470, 480, 515
1410 1550 1610 1670 3420
Gd(mbphhd)3 455, 462,
478, 490, 514
1405 1540, 1560 1612 1675 3430
[Gd(mbphhd)3]n 455, 470,
485,500, 520
1400 1550 1605 1670 3430
Some inequality of ties, despite the deloca
lized system, is still present. This is especially
noticeable in the region of 400–600 cm-1, it is
here that there are stretching vibrations of the
M-O bond and deformation vibrations of a care-
less ring. Therefore, in this region of the spec-
trum, there is a significant number, mainly of
low- intensity bands. This is due to the different
THE COORDINATION COMPOUNDS Gd (III) AND Dy(III) WITH SOME β-DIKETONES
108 ISSN 2708-129X. Укр. хім. журн., 2021
INORGANIC CHEMISTRY
nature of the bonds, the electronic structure of
the complexing ion, and the influence of the
substituent in the diketonate fragment. For the
same reason, in the 1400-1600 cm-1 region, we
observe an insignificant splitting of the spectral
lines assigned to νas(CC) and νs(CO). However,
this inequality of bonds is not significant; there-
fore, it is inappropriate to speak of a significant
deformation of the coordination polyhedron.
For all synthesized complexes in the region
of 3200–3400 cm-1, a broadband is observed,
which corresponds to valence vibrations of
coordinated water molecules. Unfortunately,
based on the results of IR spectra, it is impos-
sible to separate coordinated and adsorbed
water molecules, however, based on the width
of this band, we can confidently conclude that
the synthesized compounds are not hydroxo
complexes, this fact is also confirmed by their
rather high solubility in organic solvents, in
particular, DMSO, DMF, chloroform.
In general, the IR spectra of metal poly-
mers table 3 are similar to the corresponding
monomeric complexes, but there is an insignif-
icant long-wavelength shift of the bands cor-
responding to characteristic vibrations, which
suggests a weakening of the metal-ligand bond
for polymers as compared to the monomeric
complex. For polymers, the MO stretching vi-
bration bands have already been split into se
veral components, confirming a more ordered
structure of metal polymers as compared to
the monomeric complex.
Thus, the shape and position of the bands in
the IR spectra of monomeric and metal-poly
mer complexes of gadolinium and dysprosium
are characteristic of bidentate-coordinated
β-diketonate ligands with delocalized π-bonds
in the chelate rings (Table 3). The displacement
of the position of the bands of metal polymers
compared to monomers to the low-frequency
region indicates a weakening of the metal-li-
gand bond, which is due to a higher part of
covalence. Taking into account the data of IR
spectroscopy and DTA, the schematic struc-
ture of complexes of lanthanides with β-dike-
tones (for example, methacroylacetophenone)
can be depicted as follows:
Ln = Gd3+, Dy3+
In the diffuse reflectance and electronic
absorption spectra of the synthesized gado-
linium and dysprosium compounds, there are
broadened bands in the range of 230–400 cm-1,
which can be attributed to the π→π* electronic
transitions from the ground (S0) to the excited
state (S1) of ligand molecules. The shift (70–
100 nm) and broadening of this band, in com-
parison with its position for free ligands, may
indicate both the realization of the complexa-
tion process and the influence of the electronic
structure of the metal and substituents in the
dicarbonyl fragment, as well as the superposi-
tion of the π→π* bands the electronic transi-
tion and the charge transfer band from the li-
gand to the metal, the different nature of these
transitions (Fig. 4). The lower intensity of the
band of metallopolymers compared to mono
mers is due to the shielding of neighboring
molecules by polymer fragments due to their
larger size compared to monomeric systems.
Since the main transitions of the gadolinium
ion are observed in the UV region, it is impos-
О. S. Berezhnytska, A. E. Horbenko, O. O. Rohovtsov, S. S. Smola, Ya. V. Fedorov, O. E. Chygyrynets, О. К. Trunova
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UCJ № 6 / Vol. 87
sible to identify them for these compounds,
since they overlap with the intense charge
transfer band from the metal to the ligand. The
shape of the band in both monomeric gadoli
nium complexes is the same, but in the case of
the biphenyl substituent, we observe a shift of
the band by 20 nm, which is due to different
energies of the ligands and, accordingly, diffe
rent positions of the charge transfer band. The
broadening of the band for metal polymers is
due to exchange interactions in the polymer;
however, it should be noted that the position
of the maxima in the monomer and polymer
are unchanged, and an insignificant shift by
2–4 nm is due to additional exchange interac-
tions in the polymer structure.
The similar shape and position of this band
both in the diffuse reflectance spectra of the
compounds and in the EAS indicates the simi-
larity of the structure of the complexes in solu-
tion and in the polycrystalline state. In the dif-
fusion reflection spectra of dysprosium coordi-
nation compounds, a set of bands with 6H13/2 of
the main multiplet is observed Table 4.
Fig. 4. Reflectance spectra of gadolinium complexes.
Table 4
The energy of the transition in the reflective spectra of the dysprosium (ІІІ)
coordination compounds.
Transition Dy(mphpd)3 [Dy(mphpd)3]n Dy(mbphpd)3 [Dy(mbphpd)3]n
6Н13/2→
6F3/2 756 757 757,763 758
6Н13/2→
6F5/2 806 808 807 810
6Н13/2→
6F7/2 906 909 907 910
6Н13/2→
6F9/2,
6Н7/2 1097 1099 1100 1100
6Н13/2→
6F11/2,
6Н9/2 1287 1289 1289 1290
6Н13/2→
6F13/2, Н11/2 1697 1700 1699 1702
THE COORDINATION COMPOUNDS Gd (III) AND Dy(III) WITH SOME β-DIKETONES
110 ISSN 2708-129X. Укр. хім. журн., 2021
INORGANIC CHEMISTRY
The shape and position of the bands in the
diffuse reflectance spectra of monomeric and
polymer complexes are similar (Fig.5) indi-
cate a similar structure of the coordination
polyhedron in monomeric and metal-polymer
complexes. An insignificant shift of the bands
to longer wavelengths, and in some places their
broadening indicates a weakening of the bond
of the central ion with the ligand in polymers,
and on the presence of exchange interactions
in the macromolecules of the metal chelating
agents. Schematically, the structure of the ele
mentary unit of metal polymers could be de-
picted as follows:
Ln=Gd, Dy; R=C6H5, C12H9
Fig. 5. Diffuse reflection spectra of dysprosium compounds.
Unfortunately, the method of electron spect
roscopy does not allow one to establish the
symmetry or structure of the coordination
polyhedron for the studied coordination com-
pounds. However, based on previous studies of
similar complexes of europium, neodymium,
samarium, and the ability to the splitting of
spectral lines, such complexes have non-cubic
symmetry of the ligand field.
Therefore, in order to determine the ener
gy of the singlet and triplet levels of the liga
nds, the fluorescence and phosphorescence
spectra of gadolinium-containing complexes
were studied (Fig. 6).The excitation and lu-
minescence 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
О. S. Berezhnytska, A. E. Horbenko, O. O. Rohovtsov, S. S. Smola, Ya. V. Fedorov, O. E. Chygyrynets, О. К. Trunova
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UCJ № 6 / Vol. 87
adjustment taking into account the radiation
distribution of the xenon lamp and the sensi-
tivity 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 li
quid nitrogen temperature.
In general, ligand energies can be deter-
mined by recording the phosphorescence and
fluorescence spectra of gadolinium, lantha-
num, and lutetium complexes, which is due to
the empty (lanthanum), half-filled (gadolini-
um), and completely filled (lutetium) f shell of
these ions. For methacroylacetophenone, we
recorded the fluorescence spectra of both the
ligand itself and all the above complexes based
on it. The results obtained are in good agree-
ment with each other, and the obtained energy
value is the same in all cases.
Subsequently, to establish the energy of
the singlet and triplet levels of the ligand, we
chose the Gd (III) complexes, which is due
to several reasons, namely: the high position
of the resonance level of Gd3+ (32000 cm-1) in
comparison with the triplet level of the ligands,
prevents energy transfer from the organic part
of the complex to the lanthanide ion and the
presence of a heavy paramagnetic ion increase
the efficiency of intersystem conversion due to
mixing of singlet and triplet levels («paramag-
netic effect») and, as a consequence, the ratio
of the phosphorescence quantum yield to the
fluorescence quantum yield (> 100).
Fig. 6. Fluorescence (a) and phosphorescence spectra of the Gd(mphpd)3 complex (CHCl3 solution,
λ = 380 nm).
The fluorescence spectrum of Gd(mphpd)3
contains one structureless diffuse band with
maxima at 450, 467, and 482 nm. The phospho-
rescence spectrum of the Gd(mphpd)3 com-
plex is a broad band with two maxima at 505
and 515 nm. It was found that for gadolinium
methacroylacetophenonate, the energies of the
singlet S1 and triplet T1 levels are 22150 cm-1
and 19520 cm-1, respectively (table 5). Simi-
lar studies were carried out for all gadolinium
complexes. It should be noted that the similarity
between the excitation and fluorescence spec-
tra for complexes with mphpd and mbphpd,
which is associated with the same nature of the
substituents in the diketonate fragment. The
fluorescence spectrum of the polymer sample
THE COORDINATION COMPOUNDS Gd (III) AND Dy(III) WITH SOME β-DIKETONES
112 ISSN 2708-129X. Укр. хім. журн., 2021
INORGANIC CHEMISTRY
[Gd(mphpd)3]n (Fig.7). Contains one diffuse
band with maxima at 431, 447, 461 nm. The
position of the maxima in the [Gd (mphpd)3]n
phosphorescence spectrum (Fig.7) At 419 nm
(shoulder), 449 nm, and 484 nm indicates that
the energies of the singlet levels of the mono-
meric and metal-polymer complexes are close.
Comparing the energy of the levels for the
monomeric and polymer complexes of gado-
linium (Table 5), it can be seen that polymeri
zation causes an increase in the energy of ex-
citing levels by ~ 1300 cm-1, which is associated
with the delocalization of the electron density
in the ligand molecule.
For gadolinium complexes with mbphpd,
we also recorded the fluorescence and phos-
phorescence spectra, as well as excitation and
emission spectra (Fig. 6). The calculated ener
gies of the singlet and triplet levels of all ligands
are given in the table 5.
Table 5
Calculated energies of the singlet and triplet levels of the studied ligand systems.
Compounds ES1,cm-1 EТ1, cm-1
Gd(mphpd)3 22150 19520
[Gd(mphpd)3]n 23400 20800
Gd(mbphpd)3 22360 19960
[Gd(mbphpd)3]n 23580 21300
Fig. 7. Exitation (λem. = 453 nm (1) and emission at 293K (2) [Gd(mphpd)3]n (λex. = 380 nm) (a) and
77K (3) of Gd(mbphpd)3 (b) (CHCl3, λex. = 380 nm).
Considering the close energies of the triplet
levels of the ligand systems and the resonance
level of Dy3+ (21000 cm-1), low emission cha
racteristics should be expected. The recorded
emission spectra confirm this assumption. As
can be seen from Fig. 8b, the intrinsic lumines-
cence intensity of the ligand is rather high and
is observed in the visible region of the spec-
trum next to the characteristic emission band
of dysprosium.
Taking into account the excitation spec-
trum (Fig. 8a), it is advisable to record the
emission spectra with exciting different wave-
lengths. As can be seen from Fig. 8b, upon ex-
О. S. Berezhnytska, A. E. Horbenko, O. O. Rohovtsov, S. S. Smola, Ya. V. Fedorov, O. E. Chygyrynets, О. К. Trunova
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UCJ № 6 / Vol. 87
citation at a wavelength of 375 nm, a broad
band is present in the emission spectrum,
which corresponds to the intrinsic emission
of the ligand. At λ = 329 nm, we observe a
decrease in the emission of the ligand, but
the appearance of emission bands of the
dysprosium ion. For the Dy3+ ion, the char-
acteristic emission c transitions 4F5/2 → 6HJ/2;
J = 9, 11, 13, 15. So with a maximum (λem =
479–482 nm corresponds to 4F9 → 6H15/2 mag-
netic dipole transition and the band λem =
572–574 nm (yellow-light) is characteristic of
4F9 → 6H13/2 electric dipole transition. Thus,
the excitation wavelength has a significant
effect on the emission characteristics of me
tal complexes. In this regard, it is necessary
to choose the correct excitation wavelength,
which will reduce the luminescence intensity
of the ligand and increase the metal complex.
Unfortunately, for monomeric complexes
with both ligands, the emission spectra could
not be recorded for high ligand fluorescence.
Fig. 8а. Exitation spectra of polymers (ligand
and complexes).
Fig. 8b. Emission spectra of polymer ligand and
complexes at other exatation.
Fig. 8c. Emission spectra of complexes λex=
329 нм ([Dy(mphpd)3]n) λex.=355 нм ([Dy(mbph-
pd)3]n).
Comparing the emission spectra of meta
lopolymers with various ligands in Fig. 8c, it
can be seen that the introduction of large aryl
substituents probably has a negative effect
on the emission characteristics of the com-
pounds. Through the shielding of the emit-
ting centers, and a low energy gap between
the levels.
It is known that by changing the particle
size or surface morphology, one can complete-
ly change their properties, which makes it pos-
sible to obtain systems of a given composition
with predictable properties. A change in the
THE COORDINATION COMPOUNDS Gd (III) AND Dy(III) WITH SOME β-DIKETONES
114 ISSN 2708-129X. Укр. хім. журн., 2021
INORGANIC CHEMISTRY
dispersion can also have affect on the lumi-
nescent characteristics of the complexes. The
method of dynamic light scattering makes it
possible to establish the dispersion and stabili-
ty of dispersed systems in solution. The method
of dynamic light scattering was used to deter-
mine the particle size of complexes dissolved
in dimethylformamide at 25 °C with Zeta
Sizer Malvern. The studies carried out have
shown that the obtained systems are rough
polydisperse systems, the reproducibility of
the results is low. Micrographs were record-
ed to establish the surface morphology. Mi-
crophotographs were recorded on a scanning
electron microscope (SEM) Tescan Mira 3.
For polymer complexes, as in most cases, the
characteristic larger particle size is due to ag-
glomeration. When passing from a monomer-
ic to a polymer sample, the surface morpholo-
gy remains unchanged, the structure is layered.
The surface structure of monomeric complexes
is not uniform, which indicates the presence of
agglomerated particles, and, as a consequence,
an increase in the size of individual groups. In
general, photomicrographs of test samples are
similar to those previously described.
Fig. 9. SEM microphoto of the povders Gd(mbphpd)3 (а), [Gd(mbphpd)3]n (b) scale label 100nm,
500nm, 2 micron, 1 micron.
a
b
О. S. Berezhnytska, A. E. Horbenko, O. O. Rohovtsov, S. S. Smola, Ya. V. Fedorov, O. E. Chygyrynets, О. К. Trunova
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UCJ № 6 / Vol. 87
Conclusion
It was established the hydration composi-
tion, the structure and symmetry of the nea
rest coordination environment of the central
atom in coordination compounds GD (III)
and Dy(III) with β-diketones. The spectral-lu-
minescent characteristics of obtained mono-
and poly dysprosium complexes exhibit a low
luminescence intensity in the visible region of
the spectrum, connected with close energies
the triplet level of the ligand, and the singlet
level of the emitting ion. It is shown that at
different excitation wavelengths presence dif-
ferent emission characteristics. The resulting
systems are coarsely dispersed amorphous
powders with a layered structure.
Acknowledgments
This work was supported by funding
from the National Academy of Sciences
of Ukraine (318 E – program), «Crea-
tion of new multifunctional nanoma-
terials based on coordination compounds of
3d-metals and lanthanides with O, N-donor
ligands».
The authors are grateful to Professor Irina
Savchenko of the Macromolecular Chemis-
try Department of the Faculty of Chemistry
of the National Taras Shevchenko University
of Kyiv for help in the synthesis of metal po
lymers.
КООРДИНАЦІЙНІ СПОЛУКИ GD3+ ТА DY3+
З ДЕЯКИМИ β-ДИКЕТОНАМИ
О. С. Бережницька, А. Е. Горбенко,
О. О. Роговцов, С. С. Смола,
Я. В. Федоров, О. Е. Чигиринець,
О. К. Трунова
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
3Фізико-хімічний Інститут імені О. В. Бо-
гатського НАН України, вул. Люстдорф-
ська дорога, 86, Одеса 65080, Україна
Синтезовано нові комплекси Dy(ІІІ) та
Gd(ІІІ) з β-дикетонами, що містять нена-
сичені та арильні замісники. Виконано
квантово-хімічні розрахунки молекул лі-
гандів і металокомплексів. Розраховано
основні енергетичні характеристики мо-
лекул лігандів: ентальпія утворення, пов-
на енергія молекули та довжини зв’язків,
параметри електронної заселеності ліган-
дів. Розраховані енергії вищої заповненої
молекулярної орбіталі (ЕHOMO) і нижчої
вакантної молекулярної орбіталі (ЕLUMO)
свідчать про слабкі електроноакцепторні
властивості комплексів.
Методом радикальної полімеризації от-
римано металополімери на основі синте-
зованих комплексів. Встановлено склад та
будову синтезованих комплексів та метало-
полімерів. Показано, що при полімеризації
THE COORDINATION COMPOUNDS Gd (III) AND Dy(III) WITH SOME β-DIKETONES
116 ISSN 2708-129X. Укр. хім. журн., 2021
INORGANIC CHEMISTRY
координаційне оточення центрального іона
залишається незмінним. Ліганди коорди-
нуються до центральних іонів бідентатно-
хелатно, утворюючи трис-комплекси. К.ч.
іонів гадолінію (ІІІ) та диспрозію (ІІІ) до-
рівнює 8, координаційна сфера доповню-
ється двома молекулами води. Досліджено
спектрально-люмінесцентні характери-
стики синтезованих сполук. Визначено
енергії триплетного рівня мономерних та
полімерних лігандів. Наявність молекул
води в найближчому координаційному
оточенні зумовлює низьку інтенсивність
емісії мономерних комплексів диспрозію.
В спектрах люмінесценції металополімерів
присутні смуги magnetic dipole transition
(4F9 → 6H15/2) and electric dipole transition
(4F9 → 6H13/2). Близькі енергії триплетного
рівня ліганду та резонансного рівня іона
диспрозію зумовлюють невисокі емісійні
характеристики синтезованих комплек-
сів диспрозію. Дослідження морфології та
дисперсності наносистемы, отриманих на
основі синтезованих сполук, свідчить про
великий розмір часток та полідисперсність,
що зумовлено наявністю громіздких заміс-
ників та агломерації. Структура поверхні
частинок є шаруватою.
Ключові слова: лантаніди, комплекси,
люмінесцентні властивості, металополіме-
ри, гадоліній, диспрозій, β-дикетони.
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Стаття надійшла 01.07.2021.
|
| id | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-324 |
| institution | Ukrainian Chemistry Journal |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-07-23T01:06:39Z |
| publishDate | 2021 |
| publisher | V.I.Vernadsky Institute of General and Inorganic Chemistry |
| record_format | ojs |
| resource_txt_mv | ucjorgua/a6/708049311d368d661c31f2cb78f743a6.pdf |
| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-3242026-07-22T08:23:46Z THE COORDINATION COMPOUNDS Gd (III) AND Dy(III) WITH SOME β-DIKETONES КООРДИНАЦІЙНІ СПОЛУКИ Gd3+ та Dy3+ З ДЕЯКИМИ β-ДИКЕТОНАМИ Berezhnytska , Оeksandra Rohovtsov , Oleksandr Horbenko , Artur Fedorov , Yaroslav Trunova , Olena Chyhyrynets , Olena Smola , Sergey lanthanides, complexes, luminescence properties, metalopolymer, gadolinium, dysprosium, β-diketones. New complexes of Dy (III) and Gd (III) with b-diketones containing unsaturated and aryl substituents were synthesized. Metal polymers based on synthesized complexes were obtained by the method of radical polymerization. The composition and structure of synthesized complexes and metal polymers are established. It is shown that during polymerization the coordination environment of the central ion remains unchanged. The spectral-luminescent characteristics of the synthesized compounds were studied. The presence of water molecules in the immediate coordination environment causes a low intensity of emission of monomeric dysprosium complexes. In the luminescence spectra of metal polymers, there are bands magnetic dipole transition (4F9 → 6H15/2) and electric dipole transition (4F9 → 6H13/2). The close energies of the triplet level of the ligand and the resonant level of the dysprosium ion cause low emission characteristics of the synthesized dysprosium complexes. V.I.Vernadsky Institute of General and Inorganic Chemistry 2021-07-26 Article Article Inorganic Chemistry Неорганическая химия Неорганічна хімія application/pdf https://ucj.org.ua/index.php/journal/article/view/324 10.33609/2708-129X.87.06.2021.97-120 Ukrainian Chemistry Journal; Vol. 87 No. 6 (2021): Ukrainian Chemistry Journal; 97-120 Украинский химический журнал; ##issue.vol## 87 ##issue.no## 6 (2021): Ukrainian Chemistry Journal; 97-120 Український хімічний журнал; Том 87 № 6 (2021): Український хімічний журнал; 97-120 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/324/175 Copyright (c) 2021 Оeksandra Berezhnytska , Oleksandr Rohovtsov , Artur Horbenko , Yaroslav Fedorov , Olena Trunova , Olena Chyhyrynets , Sergey Smola https://creativecommons.org/licenses/by-nc/4.0 |
| spellingShingle | Berezhnytska , Оeksandra Rohovtsov , Oleksandr Horbenko , Artur Fedorov , Yaroslav Trunova , Olena Chyhyrynets , Olena Smola , Sergey КООРДИНАЦІЙНІ СПОЛУКИ Gd3+ та Dy3+ З ДЕЯКИМИ β-ДИКЕТОНАМИ |
| title | КООРДИНАЦІЙНІ СПОЛУКИ Gd3+ та Dy3+ З ДЕЯКИМИ β-ДИКЕТОНАМИ |
| title_alt | THE COORDINATION COMPOUNDS Gd (III) AND Dy(III) WITH SOME β-DIKETONES |
| title_full | КООРДИНАЦІЙНІ СПОЛУКИ Gd3+ та Dy3+ З ДЕЯКИМИ β-ДИКЕТОНАМИ |
| title_fullStr | КООРДИНАЦІЙНІ СПОЛУКИ Gd3+ та Dy3+ З ДЕЯКИМИ β-ДИКЕТОНАМИ |
| title_full_unstemmed | КООРДИНАЦІЙНІ СПОЛУКИ Gd3+ та Dy3+ З ДЕЯКИМИ β-ДИКЕТОНАМИ |
| title_short | КООРДИНАЦІЙНІ СПОЛУКИ Gd3+ та Dy3+ З ДЕЯКИМИ β-ДИКЕТОНАМИ |
| title_sort | координаційні сполуки gd3+ та dy3+ з деякими β-дикетонами |
| topic_facet | lanthanides complexes luminescence properties metalopolymer gadolinium dysprosium β-diketones. |
| url | https://ucj.org.ua/index.php/journal/article/view/324 |
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