CATION EFFECT ON THERMAL STABILITY AND LUMINESCENT PROPERTIES OF BINUCLEAR RARE EARTH ANIONIC COMPLEXES WITH BISCARBACYLAMIDOPHOSPHATE
A series of new binuclear anionic coordination compounds of yttrium (III) and europium (III) with bis-carbacylamidophosphate ligand tetramethyl N,N′-(2,2,3,3,4,4-hexafluoro-1,5-dioxopentane-1,5-diyl)bis(phosphoramidate) and six different cations has been obtained with an aim to study t...
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| Дата: | 2025 |
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| Автори: | , , , , , , |
| Формат: | Стаття |
| Мова: | Англійська |
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V.I.Vernadsky Institute of General and Inorganic Chemistry
2025
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Репозитарії
Ukrainian Chemistry Journal| _version_ | 1871466183411105792 |
|---|---|
| author | Kariaka, Nataliia Trush, Viktor Amirkhanov, Volodymyr Fesych, Igor Gnatyuk, Olena Gnatyuk, Ivan Dovbeshko, Galyna |
| author_facet | Kariaka, Nataliia Trush, Viktor Amirkhanov, Volodymyr Fesych, Igor Gnatyuk, Olena Gnatyuk, Ivan Dovbeshko, Galyna |
| author_institution_txt_mv | [
{
"author": "Nataliia Kariaka",
"institution": "Faculty of Chemistry, Taras Shevchenko National University of Kyiv"
},
{
"author": "Viktor Trush",
"institution": "Faculty of Chemistry, Taras Shevchenko National University of Kyiv"
},
{
"author": "Volodymyr Amirkhanov",
"institution": "Faculty of Chemistry, Taras Shevchenko National University of Kyiv"
},
{
"author": "Igor Fesych",
"institution": "TarasShevchenkoNationalUniversityofKyiv: Kyiv, UA "
},
{
"author": "Olena Gnatyuk",
"institution": "InstituteofPhysicsofNationalAcademyofSciencesofUkraine: Kyiv, UA"
},
{
"author": "Ivan Gnatyuk",
"institution": "InstituteofPhysicsofNationalAcademyofSciencesofUkraine: Kyiv, UA"
},
{
"author": "Galyna Dovbeshko",
"institution": "InstituteofPhysicsofNationalAcademyofSciencesofUkraine: Kyiv, UA"
}
] |
| author_sort | Kariaka, Nataliia |
| baseUrl_str | https://ucj.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-22T08:23:56Z |
| description | A series of new binuclear anionic coordination compounds of yttrium (III) and europium (III) with bis-carbacylamidophosphate ligand tetramethyl N,N′-(2,2,3,3,4,4-hexafluoro-1,5-dioxopentane-1,5-diyl)bis(phosphoramidate) and six different cations has been obtained with an aim to study the cation influence on the thermal and spectral properties of the complexes. The synthesis of coordination compounds was carried out using standard techniques based on the exchange reaction between lanthanide nitrates and the sodium or triethylammonium salt of the ligand in non-aqueous solutions. The complexes’ composition was established by means of elemental and thermal gravimetric analyses as well as 1H NMR spectroscopy. The chelating type of metal binding with participation of both chelating cores of the bis-carbacylamidophosphate was confirmed by IR spectroscopy. It was shown that the cation nature greatly influences the properties of complexes, such as solubility, thermal stability, and luminescence characteristics, as well as determines the degree of the complexes’ hydration. The europium (III) complexes exhibit f-f emission, which is sensitized by the ligands. The luminescence intensity, bands splitting, and bands intensity ratios, as well as luminescence decay time and intrinsic quantum yield, were found to be strongly dependent on the cation in the complexes under study. The red/orange ratio for the europium (III) complexes varies from 2.6 to 7.6, the luminescence decay time varies from 0.76 to 2.74 ms, and the intrinsic quantum yield varies from 24 to 90 %. The temperature of decomposition varies in the range near 155–190 °C, depending on the cation. The manuscript contributes to the studies of influence of outer sphere interactions on the luminescence of lanthanides’ complexes, which is important for design of luminescent compounds with suitable for practical application properties. |
| doi_str_mv | 10.33609/2708-129X.91.11.2025.22-34 |
| first_indexed | 2026-03-12T15:49:41Z |
| format | Article |
| fulltext |
22 ISSN 2708-129X. Укр. хім. журн., 2025
UDC 546.3+543.4+543.572 doi: 10.33609/2708-129X.91.11.2025.22-34
CATION EFFECT ON THERMAL STABILITY AND LUMINESCENT
PROPERTIES OF BINUCLEAR RARE EARTH ANIONIC COMPLEXES
WITH BISCARBACYLAMIDOPHOSPHATE.
Nataliia Kariaka1,*, Viktor Trush1, Igor Fesych1, Olena Gnatyuk2,
Ivan Gnatyuk2, Galyna Dovbeshko2, Volodymyr Amirkhanov1
1Taras Shevchenko National University of Kyiv, Department of Chemistry,
64 Volodymyrska str., 01601 Kyiv, Ukraine;
2 Department of Physics of Biological Systems, Institute of Physics of the National
Academy of Sciences of Ukraine,
46 Prospekt Nauki, 03028 Kyiv, Ukraine
e-mail: natka04@i.ua
A series of new binuclear anionic coordination compounds of yttrium (III) and europium (III)
with bis-carbacylamidophosphate ligand tetramethyl N,N′-(2,2,3,3,4,4-hexafluoro-1,5-dioxo
pentane-1,5-diyl)bis(phosphoramidate) and six different cations has been obtained with an aim
to study the cation influence on the thermal and spectral properties of the complexes. The synthe-
sis of coordination compounds was carried out using standard techniques based on the exchange
reaction between lanthanide nitrates and the sodium or triethylammonium salt of the ligand in
non-aqueous solutions. The complexes’ composition was established by means of elemental and
thermal gravimetric analyses as well as 1H NMR spectroscopy. The chelating type of metal bin
ding with participation of both chelating cores of the bis-carbacylamidophosphate was confirmed
by IR spectroscopy. It was shown that the cation nature greatly influences the properties of comp
lexes, such as solubility, thermal stability, and luminescence characteristics, as well as determines
the degree of the complexes’ hydration. The europium (III) complexes exhibit f-f emission, which
is sensitized by the ligands. The luminescence intensity, bands splitting, and bands intensity ratios,
as well as luminescence decay time and intrinsic quantum yield, were found to be strongly de-
pendent on the cation in the complexes under study. The red/orange ratio for the europium (III)
complexes varies from 2.6 to 7.6, the luminescence decay time varies from 0.76 to 2.74 ms, and
the intrinsic quantum yield varies from 24 to 90 %. The temperature of decomposition varies in
the range near 155–190 °C, depending on the cation. The manuscript contributes to the studies
of influence of outer sphere interactions on the luminescence of lanthanides’ complexes, which is
important for design of luminescent compounds with suitable for practical application properties.
Key words: rare earth element, bis-carbacylamidophosphate, coordination compounds, lumi
nescence, thermal gravimetric analysis.
23https://ucj.org.ua
Nataliia Kariaka, Viktor Trush, Igor Fesych, Olena Gnatyuk, Ivan Gnatyuk, Galyna Dovbeshko, Volodymyr Amirkhanov UCJ № 11 / Vol. 91
INTRODUCTION. Coordination com
pounds of lanthanides are objects of inten
sive research due to their specific spectral and
magnetic properties, which are of interest for
modern technologies [1–6]. Organic ligands
in the coordination compounds of lanthanides
play an important role, being used to enhance
or modulate properties of LnIII ions as well as
to adjust other useful properties of compounds
such as solubility, conductivity, biological ac-
tivity, etc. An additional significant effect on
luminescent and magnetic properties of lan-
thanides can result from outer-spherical ions
and intermolecular interactions in the comp
lex [7–13]. Such an influence occurs due to
changes in the geometry and electronic pro
perties of the ligand. As a result, the geometry
of the coordination polyhedron of the lantha-
nide, the “rigidity” of the complex, or the ener
gy of the triplet state of the ligand can vary.
These affect the efficiency of energy transfer
from the ligand to the metal as well as the ef-
ficiency of excited states deactivation. The in-
fluence of the second coordination domain on
the photophysical properties of LnIII coordina-
tion compounds is difficult to predict, and the
relationships found are often not well under-
stood. Therefore, research aimed at a deeper
understanding of the mechanisms of influence
of the second coordination sphere of lantha-
nide complexes on their properties is relevant.
The knowledge gained will make it possible to
design and improve the photophysical charac-
teristics of electromagnetic radiation conver
ters based on lanthanide complexes.
This study is devoted to the synthesis and in-
vestigation of new anionic binuclear rare earth
complexes of general formula (Cation)2Ln2L4
(where Ln = Y, Eu) with biscarbacylamidophos-
phate ligand H2L (Figure 1) and different cati
ons ([Cation2]
2+ = [Na2]
2+, [Cs2]
2+, [(NH4)2]
2+,
[(NMe4)2]
2+, [NaNEt4]
2+, and [(HNEt3)2]
2+).
Different radii and different nature of the cati-
ons cause different polarizability and affect the
possibility of hydrogen bond formation and
their strength, thus can significantly affect the
geometry of the complex, spectral properties,
and ability to crystallize.
Fig. 1. The structural formula of H2L
EXPERIMENT AND DISCUSSION OF
THE RESULTS.
Synthesis of the complexes.
The H2L and its sodium salt were synthe-
sized and identified as described earlier [14, 15].
The complexes were obtained according to the
following schemes:
2Ln(NO3)3×6H2O + 4Na2L = Na2[Ln2L4]·3H2O + 6NaNO3 + 6H2O
2Ln(NO3)3×6H2O + 4Cs2L = Cs2[Ln2L4]·H2O + 6CsNO3 + 6H2O
2Ln(NO3)3×6H2O + 4Na2L + 2NH4NO3= (NH4)2[Ln2L4]·4H2O + 8NaNO3 + 6H2O
2Ln(NO3)3×6H2O + 4Na2L + 2NMe4Cl = (NMe4)2[Ln2L4]·H2O + 6NaNO3 + 2NaCl + 6H2O
2Ln(NO3)3×6H2O + 4Na2L + NEt4Cl = NEt4[NaLn2L4]·H2O + 6NaNO3 + NaCl + 6H2O
2Ln(NO3)3×6H2O + 4H2L + 8NEt3 = (HNEt3)2[Ln2L4]·3H2O + 6HNEt3NO3 + 6H2O
Ln = Eu, Y.
24 ISSN 2708-129X. Укр. хім. журн., 2025
CATION EFFECT ON THERMAL STABILITY AND LUMINESCENT PROPERTIES OF BINUCLEAR RARE EARTH
ANIONIC COMPLEXES WITH BISCARBACYLAMIDOPHOSPHATEINORGANIC CHEMISTRY
To obtain Na2[Ln2L4]·3H2O and Cs2[Ln2L4]·
·H2O the mixture of hydrated rare earth nit
rates (0.2 mmol) and triethyl orthoformate
(1.2 mmol) were dissolved in acetone (4 mL)
upon refluxing and heating to acetone boi
ling temperature. Separately, Na2L or Cs2L
(0.4 mmol) were dissolved in a mixture of
acetone and 2‑propanol (1:1, 10 mL) upon
heating. The obtained solutions were mixed,
refluxed upon heating for a minute and left to
cool down to the room temperature. Then, the
precipitation of NaNO3 or CsNO3 was filtered
off and the clear solution was left at room con-
ditions for slow evaporation of the solvents.
In few days, when the majority of the solvent
was evaporated, the precipitation of the target
complexes appeared. It was, filtered off, washed
with 2-propanol and left on air to dry for a day
and then for 8 hours in drying closet at 40 °C.
The yield of the complexes was 70–76 %.
The complexes (NH4)2[Ln2L4]·4H2O,
(NMe4)2[Ln2L4]·H2O, and NEt4[NaLn2L4]·H2O
were obtained in a similar way as described
above by combining three solutions at the ini-
tial stage. The NH4NO3 was dissolved in etha-
nol, while NMe4Cl and NEt4Cl were dissolved
in 2-propanol. The yield of the complexes was
57–75 %.
To obtain (HNEt3)2[Ln2L4]·3H2O the solu-
tion of mixture of hydrated rare earth nit
rates (0.2 mmol) and triethyl orthoformate
(1.2 mmol) in acetone was combined with
the solution of mixture of H2L (0.4 mmol,
0.18166 g) and NEt3 (0.8 mmol, 0.111 ml) in
2-propanol. The obtained final solution was
refluxed upon heating for a minute, then,
cooled down to the room temperature and
left to stand in air for slow evaporation of the
solvents. The polycrystalline precipitate of the
target complexes appeared in two days. It was
filtered off, washed with 2-propanol and dried
as described above. The yield of the complexes
was near 80 %.
The obtained compounds are polycrystalline
or amorphous powders, which are stable in air
and have different solubility depending on the
outer-sphere cations. All the complexes are so
luble in methanol and insoluble in 2-propanol.
The compounds Сs2[Ln2L4]·H2O, (NH4)2[Ln2L4]·
·4H2O and (NMe4)2[Ln2L4]·H2O are soluble
in water, while the rest of the obtained comp
lexes (Na2[Ln2L4]·3H2O, NEt4[NaLn2L4]·H2O,
and (HNEt3)2[Ln2L4]·3H2O) do not dissolve
in water. All the obtained complexes, except
of (NMe4)2[Ln2L4]·H2O are slightly soluble in
acetone. The complexes (HNEt3)2[Ln2L4]·3H2O
are soluble in dichloromethane as well.
Compound Na2[Y2L4]·3H2O
(Na2Y2C36H54N8P8O35F24). Elemental anal.
Calcd (%): H 2.61%, C 20.72%, N 5.37%;
found H 2.46%, C 21.54%, N 5.47%. NMR - 1H
(DMSO-d6): [L]- 3.56 (d) 48H; 31P (DM-
SO-d6): 10.74 (s)
Compound Na2[Eu2L4]·3H2O
(Na2Eu2C36H54N8P8O35F24). Elemental anal.
Calcd (%): H 2.46%, C 19.54%, N 5.06%; found
H 2.26%, C 19.50%, N 5.31%.
Compound Cs2[Y2L4]·H2O
(Cs2Y2C36H50N8P8O33F24). Elemental anal.
Calcd (%): H 2.22%, C 19.05%, N 4.94%;
found H 2.12%, C 18.88%, N 5.04%. NMR - 1H
(DMSO-d6): [L]- 3.56 (d) 48H; 31P (DMSO-d6):
10.57 (s).
Compound Cs2[Eu2L4]·H2O
(Cs2Eu2C36H50N8P8O33F24). Elemental anal.
Calcd (%): H 2.10%, C 18.04%, N 4.68%; found
H 2.06%, C 17.81%, N 4.80%.
Compound (NH4)2[Y2L4]·4H2O
(Y2C36H64N10P8O36F24). Elemental anal. Calcd
(%): H 3.08%, C 20.64%, N 6.69%; found
25https://ucj.org.ua
Nataliia Kariaka, Viktor Trush, Igor Fesych, Olena Gnatyuk, Ivan Gnatyuk, Galyna Dovbeshko, Volodymyr Amirkhanov UCJ № 11 / Vol. 91
H 2.99%, C 21.46%, N 6.85%. NMR - 1H
(DMSO-d6): [L]- 3.55 (d) 48H, [NH4]
+ 7.12
(m) 8H; 31P (DMSO-d6): 10.57 (s)
Compound (NH4)2[Eu2L4]·4H2O
(Eu2C36H64N10P8O36F24). Elemental anal.
Calcd (%): H 2.91%, C 19.47%, N 6.31%; found
H 2.68%, C 19.74%, N 6.46%.
Compound (NMe4)2[Y2L4]·H2O
(Y2C44H74N10P8O33F24). Elemental anal.
Calcd(%): H 3.46%, C 24.55%, N 6.51%; found
H 3.37%, C 24.28%, N 6.62%. NMR - 1H
(DMSO-d6): [L]- 3.54 (d) 48H, [NMe4]
+ 3.08
(s) 24H; 31P (DMSO-d6): 10.99 (s).
Compound (NMe4)2[Eu2L4]·H2O
(Eu2C44H74N10P8O33F24). Elemental anal. Calcd
(%): H 3.27%, C 23.19%, N 6.15%; found H
3.22%, C 22.90%, N 6.24%.
Compound NEt4[NaY2L4]·H2O
(NaY2C44H70N9P8O33F24). Elemental anal.
Calcd (%): H 3.27%, C 24.49%, N 5.84%;
found H 3.24%, C 24.18%, N 5.97%. NMR - 1H
(DMSO-d6): [L]- 3.56 (d) 48H, [NEt4]
+ 1.14
(m) 12H, 3.18 (m) 8H; 31P (DMSO-d6): 10.74
(s).
Compound NEt4[NaEu2L4]·H2O
(NaEu2C44H70N9P8O33F24). Elemental anal.
Calcd (%): H 3.09%, C 23.14%, N 5.52%; found
H 3.08%, C 22.90%, N 5.60%.
Compound (HNEt3)2[Y2L4]·3H2O
(Y2C48H86N10P8O35F24). Elemental anal.
Calcd (%): H 3.86%, C 25.68%, N 6.24%;
found H 3.76%, C 25.96%, N 6.41%. NMR - 1H
(DMSO-d6): [L]- 3.57 (d) 48H, [HNEt3]
+
1.15 (m) 18H, 3.13 (m) 12H; 31P (DMSO-d6):
10.96 (s).
Compound (HNEt3)2[Eu2L4]·3H2O
(Eu2C48H86N10P8O35F24). Elemental anal. Calcd
(%): H 3.66%, C 24.31%, N 5.91%; found H
3.55%, C 24.36%, N 6.09%.
Methods
Elemental analysis was performed on a Per-
kin-Elmer 2400 CHN elemental analyzer.
The thermal stabilities of the complexes
have been studied on a derivatograph Met-
tler-Toledo TGA/DSC 3+ STARe System and
on a synchronous TG / DTA analyzer Shimad-
zu DTG-60H in the temperature range up to
600 °C in argon atmosphere with a heating rate
equal to 5 °C/min.
1H and 31P NMR spectra for solutions
in dimethyl sulfoxide were obtained on an
AVANCE 400 Bruker NMR spectrometer at
room temperature.
Infrared spectra were recorded using a
TENSOR 27 (Bruker) infrared spectrometer
with an ATR attachment, which was developed
specifically for the study of solid and powdery
samples. All spectra were recorded in the wide
spectral region from 4000 to 400 cm-1. For
spectra processing, the Opus 8.0 program was
used. All spectra were baselined and norma
lized by the intensity of a band near 1600 cm-1.
Diffuse reflection spectra were recorded on
a Shimadzu UV-2600і spectrometer.
The luminescence spectra and lumines-
cence decay time were measured using a spect
rofluorometer FS5 (Edinburgh Instruments).
It is a high-tech, all-in-one solution that allows
the measurement of fluorescence spectra, UV
and visible absorption spectra, and fluores-
cence decay times. This system has a guaran-
teed signal-to-noise ratio of > 6000:1 at 350 nm
excitation and 397 nm emission, with an inte-
gration time of 1 s. A special vertically inclined
and linearly positioned solid sample holder
was used to record the spectra to maximize the
signal from the sample. The fluorescence decay
times were measured using the Time-Correla
ted Single-Photon Counting Technique, which
26 ISSN 2708-129X. Укр. хім. журн., 2025
CATION EFFECT ON THERMAL STABILITY AND LUMINESCENT PROPERTIES OF BINUCLEAR RARE EARTH
ANIONIC COMPLEXES WITH BISCARBACYLAMIDOPHOSPHATEINORGANIC CHEMISTRY
is a quantum-based, highly sensitive method
that is less sensitive to noise. This allows the
measurement of decay times of less than 30 ps.
The resolution of the TCSPC matrix is 305 ps.
The continuous light source was a 150W xe-
non arc lamp. For fluorescence decay time, the
EPL laser at 375 nm was used. The spectra were
measured using identical conditions for each
sample.
Spectroscopic studies of the complexes
IR and NMR spectroscopy
The 1H NMR spectroscopy of the diamag-
netic YIII complexes allowed establishing the
ratio between the organic cations and the li-
gand’s protons. The 1H NMR spectra of the
complexes contain the doublet signal of methy
late groups of [L]2- at 3.54–3.57 ppm. This sig-
nal is shifted compared to the spectrum of
H2L (3.74 ppm [15]) towards the high field.
The signal of the amide proton is absent in
the spectra of the complexes, confirming the
ligands’ deprotonated form in the complex
compositions. The residual solvent 2-propa
nol can be observed in the 1H NMR spectra
of Na2[Y2L4]·3H2O and (NH4)2[Y2L4]·4H2O.
The 31P NMR spectrum of each YIII complex
contains a singlet band with the maximum in
the range 10.57–10.99 ppm. This testifies the
equivalence of the phosphorus atoms in the
composition of the complexes, and also con-
firms their individuality.
IR spectra of all the complexes are very simi
lar to each other (Figure 2). In the high wave-
length part of the spectra, one can observe a se-
ries of narrow ν(CH) bands in the region 3060–
2830 cm-1 and broad bands ν(OH) in the region
3600–3200 cm-1. The latter has different intensi-
ty depending on the complex and appears due
to the presence of the small amount of moisture
and residual 2‑propanol solvent in the samples.
A band ν(NH) at near 3250 cm-1 is also ob-
served for the complexes (NH4)2[Ln2L4]·4H2O
and (HNEt3)2[Ln2L4]·3H2O due to respective
cations’ vibrations. The ν(NH) band of the li-
gand is not observed in the IR spectra of the
coordination compounds, confirming the
double deprotonated form of the ligands in the
complexes’ composition. There are numerous
narrow bands in the region 1800–400 cm-1
of the IR spectra of the complexes. The most
intense are bands of C=O valence vibrations
(at near 1600 cm-1), P=O valence vibrations
(at near 1250 cm-1), and POC deformational
vibrations (at near 1030 cm-1). The bands of
C=O and P=O valence vibrations are shifted
significantly towards lower frequencies com-
pared to the spectrum of H2L (Table 1), in-
dicating coordination of both carbonyl and
phosphoryl oxygen atoms to the metals. The
blue shift of ν(PN) band results from distribu-
tion of electron density in the ligands’ chela
ting cores OCNPO.
Table 1.
Positions of the main characteristic bands
in the IR spectra of the complexes.
Compound/
Assignment of bands ν(C=O) ν(P=O) ν(P-N)
H2L [15] 1746 1212 877
Na2[Y2L4]·3H2O 1603 1149 964
Na2[Eu2L4]·3H2O 1606 1147 962
Cs2[Y2L4]·H2O 1598 1154 961
Cs2[Eu2L4]·H2O 1597 1154 960
(NH4)2[Y2L4]·4H2O 1605 1155 959
(NH4)2[Eu2L4]·4H2O 1602 1158 959
(NMe4)2[Y2L4]·H2O 1615 1160 965
(NMe4)2[Eu2L4]·H2O 1612 1158 963
NEt4[NaY2L4]· H2O 1604 1152 963
NEt4[NaEu2L4]·H2O 1611 1159 963
(HNEt3)2[Y2L4]·3H2O 1607 1149 963
(HNEt3)2[Eu2L4]·3H2O 1607 1148 963
27https://ucj.org.ua
Nataliia Kariaka, Viktor Trush, Igor Fesych, Olena Gnatyuk, Ivan Gnatyuk, Galyna Dovbeshko, Volodymyr Amirkhanov UCJ № 11 / Vol. 91
Fig. 2. IR spectra of Na2[Eu2L4]·3H2O (a), Сs2[Eu2L4]·H2O (b), (NH4)2[Eu2L4]·4H2O (c),
(NMe4)2[Eu2L4]·H2O (d), NEt4[NaEu2L4]·H2O (e), and (HNEt3)2[Eu2L4]·3H2O (f).
The diffuse reflectance spectra of the comp
lexes.
The diffuse reflectance spectra of the syn-
thesized compounds were measured in the
UV region and are presented in Figure 3. The
broad band of the ligands’ absorption is ob-
served in the 220–340 nm region with a maxi-
mum near 250 nm. The EuIII f-f transitions are
also observed in the long-wavelength part of
the spectra.
Fig. 3. Diffuse reflectance spectra of Na2[Eu2L4]·3H2O (black line), Сs2[Eu2L4]·H2O (red line),
(NH4)2[Eu2L4]·4H2O (green line), (NMe4)2[Eu2L4]·H2O (blue line),
NEt4[NaEu2L4]·H2O (light blue line), and (HNEt3)2[Eu2L4]·3H2O ) (pink line).
28 ISSN 2708-129X. Укр. хім. журн., 2025
CATION EFFECT ON THERMAL STABILITY AND LUMINESCENT PROPERTIES OF BINUCLEAR RARE EARTH
ANIONIC COMPLEXES WITH BISCARBACYLAMIDOPHOSPHATEINORGANIC CHEMISTRY
Luminescence spectroscopy.
All the obtained europium complexes exhi
bit red emission under UV lamp irradiation.
The luminescence excitation spectra (Figure 4)
were recorded by monitoring the emission of
5D0→7F2 transition. The spectra consist of a
broad band of the ligands’ absorption in the
region 230–280 nm and numerous f-f transi-
tions of the EuIII ion. The identical conditions
of measurements of the compounds’ excita-
tion spectra allow us to roughly compare
the intensity of EuIII emission. The intensi-
ty of bands is the highest in the spectrum of
(NMe4)2[Eu2L4]·H2O and the lowest in the
spectrum of (HNEt3)2[Eu2L4]·3H2O. The band
of transition 7F0→5L6 dominates in the ex-
citation spectra of all the obtained europium
complexes. From the intensity ratio between li-
gand absorption band and the band of 7F0→5L6
transition one can conclude that the most effi-
cient sensitization of EuIII emission by the lig-
ands takes place in the Сs2[Eu2L4]·H2O and the
lowest sensitization efficiency is observed for
Na2[Eu2L4]·3H2O.
Fig. 4. Luminescence excitation spectra (emission at 611,4-612 nm) of Na2[Eu2L4]·3H2O (black line),
Сs2[Eu2L4]·H2O (red line), (NH4)2[Eu2L4]·4H2O (green line), (NMe4)2[Eu2L4]·H2O (blue line),
NEt4[NaEu2L4]·H2O (light blue line), and (HNEt3)2[Eu2L4]·3H2O ) (pink line).
Upon excitation by UV light, the comple
xes exhibit typical EuIII ion f-f emission with
narrow bands assigned to transitions 5D0→7Fj
(j=0-4) (Figure 5). The emission spectra re-
corded upon excitation of the complexes into
EuIII f-f transition and the ligands’ absorption
bands are identical. It was found that the ca
tions’ nature significantly affects the splitting
of f-f transition bands in luminescence spect
ra, their positions, and the ratio of their inten-
sities. The weak band of transition 5D0→7F0 is
observed for all the obtained europium comp
lexes. The observation of this transition is an
indication that the EuIII ion occupies a site
with Cnv, Cn, or Cs symmetry [16]. The maxi
mum of the band of 5D0→7F0 transition va
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Nataliia Kariaka, Viktor Trush, Igor Fesych, Olena Gnatyuk, Ivan Gnatyuk, Galyna Dovbeshko, Volodymyr Amirkhanov UCJ № 11 / Vol. 91
ries depending on the cation from 577.9 nm
(for (NMe4)2[Eu2L4]·H2O) to 578.9 nm (for
Na2[Eu2L4]·3H2O and (NH4)2[Eu2L4]·4H2O).
The transition 5D0→7F1 appears in the comp
lexes’ emission spectra as a band with diffe
rent splitting. There are two separated bands
in the region of 5D0→7F1 transition obser
ved for Сs2[Eu2L4]·H2O, (NMe4)2[Eu2L4]·H2O
and NEt4[NaEu2L4]·H2O. The spectrum of
(NH4)2[Eu2L4]·4H2O exhibits three compo-
nents in this region, pointing to the lower EuIII
site symmetry in this complex compared to the
previously mentioned three compounds. For
Na2[Eu2L4]·3H2O and (HNEt3)2[Eu2L4]·3H2O
the band of 5D0→7F1 transition is broadened.
The band of hypersensitive transition 5D0→7F2
is the most intensive in all the recorded emis-
sion spectra; however differs by splitting de-
pending on the cation. The biggest number of
components of the 5D0→7F2 band is observed for
Сs2[Eu2L4]·H2O and (NH4)2[Eu2L4]·4H2O. The
relative integral intensities ratio I(5D0→7F2)/
I(5D0→7F1), so-called ratio, varies much (from
2.6 to 7.6) depending on the cation (Table 2).
The highest values of red/orange ratio are ob-
served for the complexes Сs2[Eu2L4]·H2O and
(NH4)2[Eu2L4]·4H2O. Thus, the lowest symmet
ry of the EuIII ion coordination environment
can be concluded for these two compounds.
A known feature of many mononuclear tet
rakis-complexes with CAPh ligands is the high
intensity of transition 5D0→7F4 [9, 17]. The
nature of this phenomenon was explained by
the presence of the P=O group in the ligand
structure, which is more polarizable compared
to the C=O one. However, the dependence of
this band’s intensity on the cation nature of
the tetrakis-complexes has not been explained
yet and requires further studies. Among ob-
tained in this work binuclear EuIII tetrakis-
complexes only two – (NMe4)2[Eu2L4]·H2O and
NEt4[NaEu2L4]·H2O – exhibit a high intensity
of transition 5D0→7F4. The contribution of this
band to the total integral intensity of the spect
ra of the two mentioned complexes is more
than 30%. While for the rest of the obtained
compounds, the contribution of 5D0→7F4 band
equals only 17–23%.
Table 2.
Some photoluminescence characteristics of the complexes (Cation)2[Eu2L4].
(Cation)2 = Na2 Сs2 (NH4)2 (NMe4)2 NEt4Na (HNEt3)2
Ph
ot
ol
um
in
es
ce
nc
e
in
te
ns
ity
di
st
ri
bu
tio
n
(%
) 5D0→7F0
0.19 0.15 0.15 0.08 0.10 0.24
5D0→7F1
12.25 9.26 10.06 16.35 16.59 15.63
5D0→7F2
66.20 70.37 67.56 42.64 43.66 59.23
5D0→7F3
1.79 2.76 2.77 3.51 3.41 1.48
5D0→7F4
19.57 17.46 19.46 37.42 36.24 23.42
I(5D0→7F2)/
I(5D0→7F1)
5.4 7.6 6.7 2.6 2.6 3.8
τRAD (ms) 2.48 1.87 2.03 3.31 3.36 3.16
τobs (ms) 1.33 1.69 1.57 2.74 1.91 0.76
QLn
Ln (%) 54 90 77 83 57 24
30 ISSN 2708-129X. Укр. хім. журн., 2025
CATION EFFECT ON THERMAL STABILITY AND LUMINESCENT PROPERTIES OF BINUCLEAR RARE EARTH
ANIONIC COMPLEXES WITH BISCARBACYLAMIDOPHOSPHATEINORGANIC CHEMISTRY
Fig. 5. Normalized luminescence spectra of Na2[Eu2L4]·3H2O (black line), Сs2[Eu2L4]·H2O (red line),
(NH4)2[Eu2L4]·4H2O (green line), (NMe4)2[Eu2L4]·H2O (blue line), NEt4[NaEu2L4]·H2O (light blue line),
and (HNEt3)2[Eu2L4]·3H2O) (pink line) measured at 300 K and λexc = 394 nm.
The luminescence decay times were measured
for the europium complexes by monitoring the
emission of 5D0→7F2 transition and excitation at
a wavelength of 372 nm, which corresponds to
the f-f transition of the EuIII ion. The obtained
decay curves were fitted by a monoexponential
function and yielded values of τobs equal to 0.76–
2.74 ms, depending on the cation (Table 3). The
radiative lifetime of 5D0 state τRAD was estimated
from emission data using the following equation:
τRAD = 1/(AMD,0·n
3·(Itot/IMD)) [18, 19], with AMD,0
being equal to 14.65 s−1, n considered to be 1.5
and (Itot/IMD) the ratio of the total integrated
emission from the Eu(5D0) level to the integra
ted intensity of MD transition 5D0→7F1 [20, 21].
The 5D0 intrinsic quantum yield (QLn
Ln) for
the europium complexes was estimated from
the emission spectrum and measured 5D0 life-
time: QLn
Ln = τobs ∕ τRAD. The obtained values of
τRAD agree with the values of red/orange ratios,
being changed in the opposite way. The valu
es of τobs are not directly proportional to τRAD,
which results in very different QLn
Ln for the
studied complexes. The lowest intrinsic quan-
tum yield was found for (HNEt3)2[Eu2L4]·3H2O.
This can be evidence of efficient quenching of
EuIII f-f emission due to the non-rigid structure
of the complex and high-energy vibrations of
the cations. The complexes Сs2[Eu2L4]·H2O and
(NMe4)2[Eu2L4]·H2O demonstrated the highest
intrinsic quantum yield.
Thermal gravimetric studies of the complexes.
The thermal gravimetric studies of the YIII
complexes (Figure 6) have shown that the
main weight loss of the samples takes place at
a temperature close to 200 °C. However, some
minor weight losses preceded the compounds’
decomposition for the majority of the samples
studied. One can observe for Na2[Y2L4]·3H2O
and (NH4)2[Y2L4]·4H2O two small weight losses.
The first one takes place at a temperature below
100 °C and is connected with the evaporation of
31https://ucj.org.ua
Nataliia Kariaka, Viktor Trush, Igor Fesych, Olena Gnatyuk, Ivan Gnatyuk, Galyna Dovbeshko, Volodymyr Amirkhanov UCJ № 11 / Vol. 91
Fig. 6. Thermal gravimetric analysis of of Na2[Eu2L4]·3H2O (a), Сs2[Eu2L4]·H2O (b),
(NH4)2[Eu2L4]·4H2O (c), (NMe4)2[Eu2L4]·H2O (d), NEt4[NaEu2L4]·H2O (e),
and (HNEt3)2[Eu2L4]·3H2O (f).
a
c
e
b
d
f
32 ISSN 2708-129X. Укр. хім. журн., 2025
CATION EFFECT ON THERMAL STABILITY AND LUMINESCENT PROPERTIES OF BINUCLEAR RARE EARTH
ANIONIC COMPLEXES WITH BISCARBACYLAMIDOPHOSPHATEINORGANIC CHEMISTRY
residues of 2-propanol solvent, which was used
for the synthesis of complexes. This conclu-
sion correlates with the NMR spectra of these
complexes. The second weight loss at a tempe
rature higher than 100 °C can be due to evapo-
ration of water molecules. Earlier, it was shown
that a molecule of water can be encapsulated
into the negatively charged environment of the
ligand fluorine and carbonyl oxygen atoms of
the helicate structure of lanthanide binuclear
tetrakis-complexes with [L]2- [14]. Also, water
molecules tend to bind the outersphere sodi-
um cation in Na[NaNd2L4(H2O)]·2H2O [14].
For the compounds NEt4[NaY2L4]·H2O and
(HNEt3)2[Y2L4]·3H2O, one can observe a small
weight loss, which is accompanied by an endo-
thermic effect at 65 and 67 °C, respectively. As
there is no organic solvent in the complexes,
which was confirmed by 1H NMR analysis, the
observed weight loss was assigned to the water
molecules evaporation. Evaporation of solvents
is followed by decomposition of organic part
of the complexes, which takes place at 200 °C
for the Сs2[Eu2L4]·H2O, (NMe4)2[Eu2L4]·H2O,
and NEt4[NaEu2L4]·H2O and at slightly lower
temperature for Na2[Eu2L4]·3H2O (198 °C),
(NH4)2[Eu2L4]·4H2O (184 °C) and
(HNEt3)2[Eu2L4]·3H2O (192 °C). The total
weight loss upon heating of the samples till
600 °C equals 52–65 %.
CONCLUSIONS. The new binuclear tetra
kis-complexes of YIII and EuIII with tetramethyl
N,N′-(2,2,3,3,4,4-hexafluoro-1,5-dioxopenta
ne-1,5-diyl)bis(phosphoramidate) and diffe
rent cations have been successfully obtained
and characterized. The variation of the cations
has allowed obtaining compounds with differ-
ent solubility, i.e., soluble in water or in organic
solvents. It was found that complexes contain
different amounts of moisture depending on
the cation and the temperature of decomposi-
tion varies in the range near 155–190 °C. The
highest thermal stability among YIII compounds
was observed for the complexes Cs2[Y2L4]·H2O
and (NMe4)2[Y2L4]·H2O. The luminescence
studies of the obtained compounds allowed us
to conclude the lowest symmetry of EuIII ion
coordination environment for Сs2[Eu2L4]·H2O
and (NH4)2[Eu2L4]·4H2O, which results in the
highest values of red/orange ratio and low-
est values of radiative luminesce decay time.
The highest EuIII intrinsic quantum yield (90
and 83%, respectively) has been observed for
Cs2[Eu2L4]·H2O and (NMe4)2[Eu2L4]·H2O,
which can be partially explained by the absence
of moisture in these complexes. The rather high
intensity of transition 5D0→ 7F4 observed for
(NMe4)2[Eu2L4]·H2O and NEt4[NaEu2L4]·H2O
is an interesting feature, which needs further
investigations.
ACKNOWLEDGMENTS. This work
was supported by the Ministry of
Education and Science of Ukraine
(grants no. 22BF037-04, and В/218
(0123U100990)).
33https://ucj.org.ua
Nataliia Kariaka, Viktor Trush, Igor Fesych, Olena Gnatyuk, Ivan Gnatyuk, Galyna Dovbeshko, Volodymyr Amirkhanov UCJ № 11 / Vol. 91
ВПЛИВ КАТІОНІВ НА ТЕРМІЧНУ СТІЙКІСТЬ ТА
ЛЮМІНЕСЦЕНТНІ ВЛАСТИВОСТІ БІЯДЕРНИХ
КОМПЛЕКСІВ РІДКОЗЕМЕЛЬНИХ ЕЛЕМЕНТІВ
ІЗ БІС-КАРБАЦИЛАМІДОФОСФАТАМИ
Наталія Каряка1,*, Віктор Труш1,
Ігор Фесич1, Олена Гнатюк2, Іван Гнатюк2,
Галина Довбешко2, Володимир Амірханов1
1Хімічний факультет Київського нацiо-
нального унiверситету iм. Тараса Шевченка,
вул. Гетьмана Павла Скоропадського, 12,
Київ 01033, Україна;
2 Відділ фізики біологічних систем, Інститут
фізики Національної академії наук України,
проспект Науки, 46, Київ, Україна
e-mail: natka04@i.ua
Було одержано серію комплексних спо-
лук ітрію (ІІІ) та європію (ІІІ) з біс-карба
циламідофосфатом тетраметил-N,N′-(2,2,
3,3,4,4-гексафлуоро-1,5-діоксопентан-1,5-
диіл)біс(фосфорамідатом) та різними ка
тіонами з метою вивчення впливу природи
катіона на термічні та спектральні власти-
вості комплексних сполук. Було показано,
що природа катіона значно впливає на такі
властивості комплексів, як розчинність,
термічна стійкість та люмінесцентні харак-
теристики. Комплекси європію (ІІІ) демон-
струють сенсибілізовану лігандами f-f лю-
мінесценцію. Інтенсивність люмінесценції,
розщеплення та співвідношення інтенсив-
ностей смуг у спектрах, а також час життя
люмінесценції і власний квантовий вихід
для досліджених сполук суттєво залежали
від природи катіона. Червоно/помаранчеве
співвідношення для синтезованих комп-
лексів європію (ІІІ) варіюється від 2.6 до
7.6, час життя люмінесценції – від 0.76 до
2.74 мс, а власний квантовий вихід – від 24
до 90 %. Температура розкладання комп-
лексів залежно від природи катіона варію-
ється в діапазоні 155–190 °C.
Ключові слова: рідкоземельні елементи,
біс-карбациламідофосфат, координаційні
сполуки, люмінесценція, термогравімет
ричний аналіз.
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Стаття надійшла 25.08.2025.
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| record_format | ojs |
| resource_txt_mv | ucjorgua/21/faa5407504210af7f881bf47f961e621.pdf |
| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-7562026-07-22T08:23:56Z CATION EFFECT ON THERMAL STABILITY AND LUMINESCENT PROPERTIES OF BINUCLEAR RARE EARTH ANIONIC COMPLEXES WITH BISCARBACYLAMIDOPHOSPHATE Kariaka, Nataliia Trush, Viktor Amirkhanov, Volodymyr Fesych, Igor Gnatyuk, Olena Gnatyuk, Ivan Dovbeshko, Galyna rare earth element, bis-carbacylamidophosphate, coordination compounds, luminescence, thermal gravimetric analysis. A series of new binuclear anionic coordination compounds of yttrium (III) and europium&nbsp;(III) with bis-carbacylamidophosphate ligand tetramethyl N,N′-(2,2,3,3,4,4-hexafluoro-1,5-dioxopentane-1,5-diyl)bis(phosphoramidate) and six different cations has been obtained with an aim to study the cation influence on the thermal and spectral properties of the complexes. The synthesis of coordination compounds was carried out using standard techniques based on the exchange reaction between lanthanide nitrates and the sodium or triethylammonium salt of the ligand in non-aqueous solutions. The complexes’ composition was established by means of elemental and thermal gravimetric analyses as well as 1H NMR spectroscopy. The chelating type of metal binding with participation of both chelating cores of the bis-carbacylamidophosphate was confirmed by IR spectroscopy. It was shown that the cation nature greatly influences the properties of complexes, such as solubility, thermal stability, and luminescence characteristics, as well as determines the degree of the complexes’ hydration. The europium (III) complexes exhibit f-f emission, which is sensitized by the ligands. The luminescence intensity, bands splitting, and bands intensity ratios, as well as luminescence decay time and intrinsic quantum yield, were found to be strongly dependent on the cation in the complexes under study. The red/orange ratio for the europium&nbsp;(III) complexes varies from 2.6 to 7.6, the luminescence decay time varies from 0.76 to 2.74 ms, and the intrinsic quantum yield varies from 24 to 90&nbsp;%. The temperature of decomposition varies in the range near 155–190 °C, depending on the cation. The manuscript contributes to the studies of influence of outer sphere interactions on the luminescence of lanthanides’ complexes, which is important for design of luminescent compounds with suitable for practical application properties. V.I.Vernadsky Institute of General and Inorganic Chemistry 2025-12-25 Article Article Inorganic Chemistry Неорганическая химия Неорганічна хімія application/pdf https://ucj.org.ua/index.php/journal/article/view/756 10.33609/2708-129X.91.11.2025.22-34 Ukrainian Chemistry Journal; Vol. 91 No. 11 (2025): Ukrainian Chemistry Journal; 22-34 Украинский химический журнал; ##issue.vol## 91 ##issue.no## 11 (2025): Ukrainian Chemistry Journal; 22-34 Український хімічний журнал; Том 91 № 11 (2025): Ukrainian Chemistry Journal; 22-34 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/756/391 Copyright (c) 2025 Nataliia Kariaka, Viktor Trush, Volodymyr Amirkhanov, Igor Fesych, Olena Gnatyuk, Ivan Gnatyuk, Galyna Dovbeshko https://creativecommons.org/licenses/by-nc/4.0 |
| spellingShingle | Kariaka, Nataliia Trush, Viktor Amirkhanov, Volodymyr Fesych, Igor Gnatyuk, Olena Gnatyuk, Ivan Dovbeshko, Galyna CATION EFFECT ON THERMAL STABILITY AND LUMINESCENT PROPERTIES OF BINUCLEAR RARE EARTH ANIONIC COMPLEXES WITH BISCARBACYLAMIDOPHOSPHATE |
| title | CATION EFFECT ON THERMAL STABILITY AND LUMINESCENT PROPERTIES OF BINUCLEAR RARE EARTH ANIONIC COMPLEXES WITH BISCARBACYLAMIDOPHOSPHATE |
| title_full | CATION EFFECT ON THERMAL STABILITY AND LUMINESCENT PROPERTIES OF BINUCLEAR RARE EARTH ANIONIC COMPLEXES WITH BISCARBACYLAMIDOPHOSPHATE |
| title_fullStr | CATION EFFECT ON THERMAL STABILITY AND LUMINESCENT PROPERTIES OF BINUCLEAR RARE EARTH ANIONIC COMPLEXES WITH BISCARBACYLAMIDOPHOSPHATE |
| title_full_unstemmed | CATION EFFECT ON THERMAL STABILITY AND LUMINESCENT PROPERTIES OF BINUCLEAR RARE EARTH ANIONIC COMPLEXES WITH BISCARBACYLAMIDOPHOSPHATE |
| title_short | CATION EFFECT ON THERMAL STABILITY AND LUMINESCENT PROPERTIES OF BINUCLEAR RARE EARTH ANIONIC COMPLEXES WITH BISCARBACYLAMIDOPHOSPHATE |
| title_sort | cation effect on thermal stability and luminescent properties of binuclear rare earth anionic complexes with biscarbacylamidophosphate |
| topic_facet | rare earth element bis-carbacylamidophosphate coordination compounds luminescence thermal gravimetric analysis. |
| url | https://ucj.org.ua/index.php/journal/article/view/756 |
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