КАЛІКС[4]АРЕНИ, МОДИФІКОВАНІ ПО НИЖНЬОМУ ОБОДУ ФРАГМЕНТАМИ ЕДТА (ДТПА), ТА ЇХ Ln(III) КОМПЛЕКСИ (Ln = Yb, Lu): СИНТЕЗ ТА ЛЮМІНЕСЦЕНТНІ ВЛАСТИВОСТІ У БЛИЖНІЙ ІЧ ОБЛАСТІ
Derivatives of p-tert-butylcalix[4]arene substituted on the lower rim with fragments of aminopolycarboxylic acids (EDTA, DTPA) were obtained. Mono and binuclear complexes with lanthanide (III) ions were synthesized using these compounds. The effect of the number and type of aminopolycarboxylic acid...
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| author | Smola, Serhii Fadieiev, Yevhen Rusakova, Mariia Snurnikova, Olga Alyeksyeyeva, Olena Rusakova, Nataliya |
| author_facet | Smola, Serhii Fadieiev, Yevhen Rusakova, Mariia Snurnikova, Olga Alyeksyeyeva, Olena Rusakova, Nataliya |
| author_institution_txt_mv | [
{
"author": "Serhii Smola",
"institution": "A.V. Bogatsky Physico-Chemical Institute of the NAS of Ukraine"
},
{
"author": "Yevhen Fadieiev",
"institution": "A.V. Bogatsky Physico-Chemical Institute of the NAS of Ukraine"
},
{
"author": "Mariia Rusakova",
"institution": "I.I. Mechnikov Odessa National University"
},
{
"author": "Olga Snurnikova",
"institution": "A.V. Bogatsky Physico-Chemical Institute of the NAS of Ukraine"
},
{
"author": "Olena Alyeksyeyeva",
"institution": "A.V. Bogatsky Physico-Chemical Institute of the NAS of Ukraine"
},
{
"author": "Nataliya Rusakova",
"institution": "A.V. Bogatsky Physico-Chemical Institute of the NAS of Ukraine"
}
] |
| author_sort | Smola, Serhii |
| baseUrl_str | https://ucj.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-22T08:23:43Z |
| description | Derivatives of p-tert-butylcalix[4]arene substituted on the lower rim with fragments of aminopolycarboxylic acids (EDTA, DTPA) were obtained. Mono and binuclear complexes with lanthanide (III) ions were synthesized using these compounds. The effect of the number and type of aminopolycarboxylic acid fragments on the luminescence of ligands and complexes was studied. The influence of the distance between the emitting ion and the calixarene macrocycle on the intensity of 4f-luminescence was analyzed. |
| doi_str_mv | 10.33609/2708-129X.86.5.2020.13-23 |
| first_indexed | 2025-09-24T17:43:25Z |
| format | Article |
| fulltext |
Неорганічна хімія
ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 5 13
UDC 547.639:541.49:546.650:535.37 doi: 10.33609/2708-129X.86.5.2020.13-23
S.S. Smola1, Ye.N. Fadieiev1, M.Yu. Rusakova2, O.V. Snurnikova1, O.A. Alyeksyeyeva
1, N.V. Rusakova1*
Lower rim-modified calix[4]arenes with fragments of EDTA (DTPA) and their Ln(III)
complexes (Ln = Yb, Lu): synthesis and NIR-luminescent properties
1 A. V. Bogatsky Physico-Chemical Institute, National Academy of Sciences of Ukraine; 86
Lyustdorfskaya doroga, Odessa, 65080, Ukraine
2I.I. Mechnikov Odessa National University; 2 Dvoryanskaya str., Odessa, 65082, Ukraine
*е-mail: natavrusakova@gmail.com
Derivatives of p-tert-butylcalix[4]arene substituted on the lower rim with fragments of
aminopolycarboxylic acids (EDTA, DTPA) were obtained. Mono and binuclear com-
plexes with lanthanide (III) ions were synthesized using these compounds. The effect of
the number and type of aminopolycarboxylic acid fragments on the luminescence of lig-
ands and complexes was studied. The influence of the distance between the emitting ion
and the calixarene macrocycle on the intensity of 4f- luminescence was analyzed.
K e y w o r d s: calix[4]arenes, EDTA, DTPA, lanthanides, luminescence.
INTRODUCTION. Coordination com-
pounds of lanthanides with calix[n]arenes
are of great interest as the building blocks
for supramolecular ensembles, such as calix-
porphyrin ionic associates, calix-crown
ethers, complex compounds with neutral
molecules, systems for the selective recogni-
tion of components of biologically active
substances (amino acids, ribonucleic acids)
[1]. The possibility of the functionalization
of lower and upper rims with various sub-
stituents determines the prospects for the use
of lanthanide-calix[n]arenes in many fields
of material science (luminescent coatings,
materials for lasers, fiber-optic transmission
lines), medicine (contrast agents), analytical
and bioanalytical chemistry (various lumi-
nescent sensors and markers), in the for-
mation of enzyme-like systems and mem-
branes [2].
The introduction of nitrogen-containing
groups at the lower rim of calixarene
through the modification of amido and ami-
no groups allows one to obtain a series of
nitrogen-containing receptors with different
binding ability to metal cations [3]. Among
widely used chelating agents amino-
polycarboxylic (APC) acids are the conven-
ient compounds in terms of high stability of
their metal complexes. Therefore, the study
of the properties of such compounds is rele-
vant and promising.
© S.S. Smola, Ye.N. Fadieiev, M.Yu. Rusakova, O.V. Snurnikova, O.A. Alyeksyeyeva,
N.V. Rusakova, 2020
S.S. Smola, Ye.N. Fadieiev, M.Yu. Rusakova, O.V. Snurnikova, O.A. Alyeksyeyeva, N.V. Rusakova
14 ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 5
EXPERIMENT AND DISCUSSION OF
THE RESULTS. All reagents and solvents in
spectroscopic studies purchased from com-
mercial suppliers had the analytical grade
and used without further purification. The
compounds L1H3, L2H2 and L7H5 were syn-
thesized according to methods described ear-
lier [4, 5]. Synthesis of mononuclear com-
plexes L1H3 and L2H2 with lanthanide ions
was described previously (Fig. 1) [6]. Mon-
onuclear (for L3H6, L4H7 and L7H5) and
homobinuclear (for L5H8 and L6H10) com-
plexes with ytterbium (III) and lutetium (III)
were obtained with the use of calix[4]arenes
containing aminopolycarboxylic acid frag-
ments, which chelate the lanthanide ion.
All ligands and complexes were ob-
tained in solid state and characterized by
means of elemental analysis, mass spec-
trometry (MALDI), thin-layer chromatog-
raphy (TLC), and NMR spectroscopy. The
lanthanide content in the complexes was de-
termined with the use of the complexometric
method with an arsenazo I indicator. Mass
spectra of the compounds by the MALDI
method were recorded on a Varian Autoflex
II spectrometer. 1 H NMR spectra were ob-
tained on a Bruker Avance-300 spectrometer
(300 MHz) in DMSO-d6 solutions with an
internal TMS standard at 25°C. IR spectra
were recorded on a Shimadzu FT-IR 8400S
spectrophotometer in KBr pellets.
Absorption spectra in the UV and visi-
ble regions were recorded using Specord
M40 UV/VIS spectrophotometer. The lumi-
nescence excitation and emission spectra
were recorded on a Fluorolog FL 3-22
spectrofluorimeter, Horiba JobinYvon (Xe
lamp 450 W), equipped for measurements
both at room temperature and at 77 K (PMT
R928P for the visible region and InGaAs
photo-resistance cooled for 77 K for the IR
region).
Modification of p-tert-calix[4]arene.
The general approach for the modification of
a calix[4]arene molecule with EDTA or
DTPA fragments was in the acylation of the
appropriate dianhydride with aminoethoxy
groups located at the lower rim of p-tert-
butylcalix[4]arene. The reaction was held in
DMF at 80°С in presence of triethylamine
(Fig. 1). Compounds L3H6 and L4H7 were
obtained from monoaminoethoxy ca-
lix[4]arene L1H3. The synthesis of the
diaminoethoxy derivative (L2H2), with two
amino and anhydride fragments in the
macrocycle molecule at the opposite ends,
suggests the possibility of the formation of
several reaction products. Using one equiva-
lent of DTPA dianhydride, according to [5],
the compound L7H5 was obtained, in which
the chelating fragment acts as a bridge con-
necting two opposite phenolic rings of the
macrocycle. With the gradual addition of the
nucleophilic agent (L2H2) dropwise to the
solution of APC dianhydride taken in a 6-
fold excess, it was possible to add two acid
fragments to the calix[4]arene matrix (com-
pounds L5H8 and L6H10).
L3H6: Yield: 83%. Mp>320°C. Calc. fo
rC56H75N3O11, %: С 69.61, Н 7.82; found,
%: С 69.48, Н 7.51. MS (MALDI): 965
(М+). IR (KBr), ν, cm-1: 3346 (NH, OH),
2961 (C-H), 2868 (C-H), 1758 (C=O), 1483
(С-С). NMR1H (DMSO-d6), δ, ppm.: 1.11 s
(9Н, t-Bu), 1.14 s (18Н, t-Bu), 1.16 s (9Н, t-
Bu), 2.72-2.90 m (4H, N-(CН2)2-N), 3.05 s
(6H, N-CH2-CO), 3.34 s (2H, N-CH2-CO),
3.39 d (4Н, Ar-CН2-Ar), 4.06 d (2Н, Ar-
CН2-Ar), 4.27 d (2Н, Ar-CН2-Ar), 6.88 d
Lower rim-modified calix[4]arenes with fragments of EDTA (DTPA)…
ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 5 15
Fig. 1. Scheme of the lower rim modification of
calix[4]arenes with APC fragments
(2Н, Ar-H), 7.02 s (2Н, Ar-H), 7.05 d
(2Н,Ar-H), 7.18 s (2Н, Ar-H), 11.88 s (3H,
COOH).
L4H7: Yield: 81%. Mp>320°C. Calc.
for C60H82N4O13, %: С 67.52, Н 7.74, found,
%: С 67.22, Н 7.95.MS (MALDI): 1066
(М+). IR (KBr), ν, cm-1: 3348 (NH+OH),
2964 (C-H), 2868 (C-H), 1760 (C=O), 1483
(С-С). NMR1H (DMSO-d6), δ, ppm: 1.12 s
(9Н, t-Bu), 1.14 s (18Н, t-Bu), 1.16 s (9Н, t-
Bu), 2.72-2.90 m (8H, N-(CН2)2-N), 3.07 s
(8H, N-CH2-CO), 3.34 s (2H, N-CH2-CO),
3.39 d (4Н, Ar-CН2-Ar), 4.06 d (2Н, Ar-
CН2-Ar), 4.27 d (2Н, Ar-CН2-Ar), 6.87 d
(2Н, Ar-H), 7.00 s (2Н, Ar-H), 7.04 d (2Н,
Ar-H), 7.14 s (2Н, Ar-H), 11.88 s (4H,
COOH).
L5H8: Yield: 74%. Mp>320°C. Calc.
for C56H75N3O11, %: С 69.61, Н 7.82; found,
%: С 69.48, Н 7.51. MS (MALDI): 1282
(М+). IR (KBr), ν, cm-1: 3364 (NH, OH),
2961 (C-H), 2866 (C-H), 1754 (C=O), 1476
(С-С). NMR1H (DMSO-d6), δ, ppm: 1.10 s
(18Н, t-Bu), 1.24 s (18Н, t-Bu), 2.72-2.90 m
(8H, N-(CН2)2-N), 3.06 s(12H, N-CH2-CO ),
3.35 s (4H, N-CH2-CO), 3.43 d (4H, Ar-
CН2-Ar), 4.40 d (4H, Ar-CН2-Ar), 6.92 s
(4Н, Ar-H), 7.05 s (4Н, Ar-H), 11.68 s (6H,
COOH).
L6H10: Yield: 75%. Mp>320°C. Calc.
for C56H75N3O11, %: С 69.61, Н 7.82; found,
%: С 69.48, Н 7.51. MS (MALDI): 1484
(М+). IR (KBr), ν, cm-1: 3367 (NH, OH),
2962 (C-H), 2867 (C-H), 1756 (C=O), 1476
(С-С).NMR1H (DMSO-d6), δ, ppm: 1.10 s
(18Н, t-Bu), 1.24 s (18Н, t-Bu), 2.72-2.90 m
(16H, N-(CН2)2-N), 3.07 s (16H, N-CH2-CO
), 3.35 s (4H, N-CH2-CO), 3.40 d (4H, Ar-
CН2-Ar), 4.41 d (4H, Ar-CН2-Ar), 6.93 s
(4Н, Ar-H), 7.05 s (4Н, Ar-H), 11.68 s (8H,
COOH).
L7H5: Yield: 72%. Mp>320°C. Calc.
for C62H85N5O12, %: С 68.17, Н 7.84, found,
%: С 68.54, Н 7.32.MS (MALDI): 1091
(М+). IR (KBr), ν, cm-1: 3365 (NH, OH),
2961 (C-H), 2866 (C-H), 1755 (C=O), 1476
(С-С).NMR1H (DMSO-d6), δ, ppm: 0.99 s
(18Н, t-Bu), 1.03 s (18Н, t-Bu), 2.33 t (4H,
N-(CН2)2-N), 2.79 t (4H, N-(CН2)2-N), 3.05
s (6H, N-CH2-CO), 3.32 s (4H, N-CH2-CO),
3.43 d (4H, Ar-CН2-Ar), 4.40 d (4H, Ar-
CН2-Ar), 6.92 s (4H, Ar-H), 7.04 s (4H, Ar-
H), 11.88 s (3H, COOH).
S.S. Smola, Ye.N. Fadieiev, M.Yu. Rusakova, O.V. Snurnikova, O.A. Alyeksyeyeva, N.V. Rusakova
16 ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 5
To identify the obtained compounds by
mass spectrometry, the MALDI method was
used, since the FAB method did not give un-
ambiguous results. This is probably due to
the high affinity of APC fragments to the
polar matrix (m-nitrobenzyl alcohol), which
leads to increased fragmentation of mole-
cules. Peaks of molecular ions were recorded
in MALDI mass spectra recorded under
conditions of determination of negative ions.
In addition to them, peaks were observed in
the spectrum, indicating fragmentation, in
which the hydroxy groups of APC fragments
were sequentially separated.
In PMR spectra of modified ca-
lix[4]arenes, insignificant changes in the po-
sition of the signals of protons of tert-butyl
groups, protons of methylene bridges of the
calixarene macrocycle and phenolic rings are
observed in comparison with the spectra of
aminoethoxy derivatives, which indicates the
cone conformation of the macrocycle mole-
cules [6]. In the 2.4–3.5 ppm region, a series
of signals appear relative to the protons of
methylene groups of aminopolycarboxylate.
Signals of protons of carboxy groups appear
at δ = 11.9 ppm. Instead of two proton sig-
nals of amino and hydroxy groups, which
are observed in the spectrum of the initial
amino derivatives, a wide singlet appears at
δ = 7.9 ppm, which is associated with the
participation of amide protons in the for-
mation of a hydrogen bond with phenolic
protons.
The assignment of bands in the IR
spectra of free ligands was carried out in ac-
cordance with published data for substituted
calix [4] arenes.The IR spectra of the ob-
tained compounds contain vibrational ab-
sorption bands from groups of both the
macrocyclic platform and the APC fragment.
In the 3200–3600 cm -1 region a broad band
with maxima at 3346–3373 cm –1 is ob-
served, which is likely due to the overlap of
vibration bands of OH bonds of the lower
rim of the calix[4]arene and unassociated
NH bonds of the amide group. In the region
of 2850–3000 cm–1, a group of bands is ob-
served, which was assigned to a superposi-
tion of stretching and deformation vibrations
of CH-bonds from both calix[4]arene and
acid fragments. The IR spectra of the L3H6-
L7H5 compounds are characterized by the
presence of an intense band in the region of
1754–1760 cm–1, which remains almost at
the sameposition when the number and type
of acid fragments change. This band was as-
signed to the stretching vibrations of car-
boxyl groups. As for the bands in the region
of 1470–1490 cm–1, they can be attributed to
the deformation vibrations of the CH2-
groups superimposed on the frequency of
asymmetric vibrations of the carboxyl group.
In addition, in the range of 1440–1460 cm–1,
there is a band of skeletal vibrations of the
aromatic component of the macrocycle,
which also complicates the interpretation of
IR spectra.
Synthesis of Yb(III) and Lu(III) com-
plexes. The synthesis of lanthanide-
containing complexes based on modified ca-
lix[4]arenes was carried out by the interac-
tion of the ligand with lanthanide chlorides
hexahydrates at the rate of 0.9 mol of LnCl3
for each APC fragment. Significantly greater
stability constants of rare earth
aminopolycarboxylates (logK = 15 – 19)
compared with complexes in which the ion
is coordinated by phenolic oxygen atoms
(logK = 3 – 8) suggests that the calixarene
Lower rim-modified calix[4]arenes with fragments of EDTA (DTPA)…
ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 5 17
T a b l e 1
Data of elemental analysis and mass spectrometric measurements of lanthanides complexes
with calix[4]arenes
Complex
m/z
(MALDI),
(%)
(calculated / found), %
C H Ln
YbL3(DMF)2 1135[М+] 58.1/58.3 6.8/6.5 13.5/13.7
YbL4(DMF) 1236[М+] 57.7/57.8 6.6/6.3 13.2/12.9
Yb2L5(DMF)4 1622[М+] 50.2/50.4 6.1/6.2 18.1/18.4
Yb2L6(DMF)2 1824[М+] 49.9/49.5 5.9/5.6 17.6/17.4
YbL7(DMF) 1261[М+] 58.5/58.2 6.7/6.5 13.0/13.2
LuL3(DMF)2 1137[М+] 60.0/60.2 6.8/6.6 13.6/13.3
LuL4(DMF) 1238[М+] 58.2/58.6 6.4/6.1 14.1/14.4
Lu2L5(DMF)4 1626[М+] 50.1/50.4 6.1/6.3 18.2/18.0
Lu2L6(DMF)2 1828[М+] 49.9/49.7 5.9/5.7 17.7/17.4
LuL7(DMF) 1263[М+] 58.4/58.2 6.7/6.5 13.1/13.2
fragment is not involved in coordination.
The data of elemental analysis and mass
spectrometric measurements of complexes
of lanthanides with calix[4]arenes are given
in Table 1. In the MALDI mass spectra
mono- and binuclear complexes of ca-
lix[4]arene derivatives, peaks of the corre-
sponding molecular ions are observed.
LuL3H3: IR (KBr), ν, cm-1: 3328 (NH,
OH), 2961 (C-H), 2868 (C-H), 1654 (C=O),
1479 (С-С). NMR1H (DMSO-d6), δ,
ppm:1.12 s (9Н, t-Bu), 1.15 s (18Н, t-Bu),
1.17 s (9Н, t-Bu), 2.95-3.13 t (4H, N-
(CН2)2-N), 3.26-3.54 m (8H, N-CH2-CO),
3.36 d (4Н, Ar-CН2-Ar), 4.02 d (2Н, Ar-
CН2-Ar), 4.28 d (2Н, Ar-CН2-Ar), 6.90 d
(2Н, Ar-H), 7.04 s (2Н, Ar-H), 7.09 d (2Н,
Ar-H), 7.15 s (2Н, Ar-H).
LuL4H4: IR (KBr), ν, cm-1: 3346 (NH,
OH), 2961 (C-H), 2868 (C-H), 1653 (C=O),
1482 (С-С). NMR1H (DMSO-d6), δ,
ppm:1.10 s (9Н, t-Bu), 1.14 s (18Н, t-Bu),
1.17 s (9Н, t-Bu), 2.95-3.13 m (8H, N-
(CН2)2-N), 3.22-3.45 m (10H, N-CH2-CO),
3.42 d (4Н, Ar-CН2-Ar), 4.09 d (2Н, Ar-
CН2-Ar), 4.29 d (2Н, Ar-CН2-Ar),6.88 d
(2Н, Ar-H), 7.01 s (2Н, Ar-H), 7.05 d (2Н,
Ar-H), 7.16 s (2Н, Ar-H), 11.88 s (1H,
COOH).
Lu2L5H2: IR (KBr), ν, cm-1: 3343
(NH, OH), 2963 (C-H), 2867 (C-H), 1649
(C=O), 1478 (С-С). NMR1H (DMSO-d6), δ,
ppm: 1.08 s (18Н, t-Bu), 1.21 s (18Н, t-Bu),
2.93-3.09 m (8H, N-(CН2)2-N), 3.24-3.54 m
(16H, N-CH2-CO), 3.43 d (4H, Ar-CН2-Ar),
4.40 d (4H, Ar-CН2-Ar), 6.92 s (4Н, Ar-H),
7.05 s (4Н, Ar-H).
Lu2L6H4: IR (KBr), ν, cm-1: 3336
(NH, OH), 2961 (C-H), 2866 (C-H), 1652
(C=O), 1476 (С-С). NMR1H (DMSO-d6), δ,
S.S. Smola, Ye.N. Fadieiev, M.Yu. Rusakova, O.V. Snurnikova, O.A. Alyeksyeyeva, N.V. Rusakova
18 ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 5
ppm: 1.08 s (18Н, t-Bu), 1.22 s (18Н, t-Bu),
2.94-3.11 m (16H, N-(CН2)2-N), 3.24-3.54
m (20H, N-CH2-CO), 3.48 d (4H, Ar-CН2-
Ar), 4.35 d (4H, Ar-CН2-Ar), 6.93 s (4Н,
Ar-H), 7.03 s (4Н,Ar-H), 11.68 s (2H,
COOH).
LuL7H2: IR (KBr), ν, cm-1: 3340 (NH,
OH), 2962 (C-H), 2868 (C-H), 1648 (C=O),
1479 (С-С). NMR1H (DMSO-d6), δ,
ppm:1.00 s (18Н, t-Bu), 1.03 s (18Н, t-Bu),
2.95-3.13 m (8H, N-(CН2)2-N), 3.22-3.45 m
(10H, N-CH2-CO), 3.46 d (4H, Ar-CН2-Ar),
4.44 d (4H, Ar-CН2-Ar), 6.91 s (4H, Ar-H),
7.05 s(4H, Ar-H).
NMR spectra of Lu(III) complexes
were compared with the data obtained for
free ligands. A shift of the proton signals of
methylene groups from APC fragments to
the low field region by 0.20–0.25 ppm was
found. At the same time, the signals of the
phenyl, tert-butyl and methylene protons
remains practically unchanged, which is
probably due to the absence of the coordina-
tion of calix[4]arene phenolic fragments by
Lu(III) ion. In the spectra of the complexes
LuL3H3, Lu2L5H2, and LuL7H2, the signals
of the protons of the carboxyl groups disap-
pear, and for LuL4H4 and Lu2L6H4 the signal
intensity decreases by 4 times indicating the
coordination of Lu(III) ions by the chelating
APC fragment.
In all IR spectra of the complexes, the
conservation of the broadened intense band
is observed at 3200-3600 cm-1. In this area,
vibrational bands of both amide NH-bonds
and phenolic hydroxy groups are superim-
posed, as well as the remaining hydroxy
groups of APC fragments, which compli-
cates their analysis. However, the absence of
a significant shift in the maximum of this
band may indicate the preservation of the
hydrogen bond system and the absence of
ionization of phenolic hydroxy groups. It
was not possible to define the bands corre-
sponding to the symmetric vibrations of the
carboxy groups, which is probably due to the
overlap of a large number of calyx[4]arene
macrocycle bands in this region (1350 –
1450 cm-1). The coordination of the lantha-
nide ion is confirmed because of the appear-
ance of ν(Ln-О) bands at 455-460 cm-1.
According to the results of physico-
chemical methods, it can be assumed that the
coordination polyhedron of lanthanide in
synthesized complexes is formed due to ter-
tiary nitrogen atoms and oxygen atoms of
APC fragments. Solvent molecules (DMF)
also are present in the coordination sphere,
which is typical for lanthanide
aminopolycarboxylates [7] (Fig. 2). The lan-
thanide ions is not coordinated by the donor
atoms of the lower rime phenolic groups,
probably, because of the steric factors and
the length of linkers linking calix[4]arenes to
an acid fragment. This was previously
proved for the mononuclear complex L7H5
with europium (III) [5]. Figure 2 shows the
structure of the homonuclear complexes
LnL3H3, Ln2L5H2 and LnL7H2, where Ln =
Yb(III), Lu(III).
Fig. 2. Structure of lanthanide-containing
complexes of calix[4]arenes
Lower rim-modified calix[4]arenes with fragments of EDTA (DTPA)…
ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 5 19
T a b l e 2
Spectral and luminescent properties of ligands and their complexes with lutetium (III) (С =
1×10-4 M; DMF)
Compound Absorption
λ, nm, (lgε)
Molecular fluorescence
λfl, nm λph, nm ЕS,cm-1 ЕT,cm-1
L3H6 278 (4.01)
286 (4.03) 418 444 23920 22520
L4H7 279 (4.04)
286 (4.06) 416 440 24040 22730
L5H8
282 (4.03)
290 (4.02) 423 449 23640 22270
L6H10
283 (4.04)
290 (4.03) 421 443 23750 22570
L7H5 280 (4.04)
288 (4.03) 420 455 23810 21980
LuL3H3 274 (3.94)
281 (3.95) 432 468 23150 21370
LuL4H4 276 (3.96)
284 (3.97) 430 465 23250 21500
Lu2L5H2 275 (3.95)
283 (3.96) 434 470 23040 21270
Lu2L6H4 276 (3.97)
283 (3.99) 433 467 23090 21410
LuL7H2 278 (3.96)
285 (3.93) 437 474 22880 21100
Spectral-luminescent properties. The
absorption spectra of the compounds L3H6 -
L7H5 contain two characteristic bands of
calixarenes in the region of 270–290 nm (ε =
7000–10000). An increase of intensity and a
bathochromic shift of 3-12 nm are observed
comparing to the spectra of the initial
aminoethoxy derivatives L1H3 and L2H2. It is
known that ionization of phenolic hydroxy
groups, upon their dissociation or complex
formation, leads to the appearance of bands
in the absorption spectra in the range 300–
320 nm. The absence of these bands in the
spectra of the complexes confirms that the
hydroxy groups of calix[4]arene do not par-
ticipate in the coordination of lanthanide
ions (Table 2).
Fluorescence is observed in the region
of 410–420 nm for all solutions of ca-
lix[4]arenes at 295 K (Fig. 3a). Moreover, in
comparison with the initial aminoethoxy de-
rivatives, a bathochromic shift of these
bands is observed (by 700–1000 cm-1). The
phosphorescence spectra determining the
lower triplet state of the ligand were record-
ed when the samples were cooled to 77 K.
The phosphorescence spectra of ligands also
undergo significant changes: a bathochromic
S.S. Smola, Ye.N. Fadieiev, M.Yu. Rusakova, O.V. Snurnikova, O.A. Alyeksyeyeva, N.V. Rusakova
20 ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 5
Fig. 3. Spectra of molecular fluorescence (a),
phosphorescence (b) Lu2L6H4 and 4f-
luminescence Yb2L6H4 (c) (С=10-3M; DMF).
shift of 1000-1700 cm-1 is observed. It is as-
sociated with a decrease in the energy of tri-
plet levels (ET1 = 21980-22730 cm-1) (Fig.
3b) (Table 2). Positions of singlet levels in
complexes decrease by 500-1500 cm-1 and
triplet levels by 600-1000 cm-1. The intensity
of the bands remains virtually unchanged as
compared to ligands.
The data in Table 2 indicate that since
the triplet levels are higher than the reso-
nance level of the Yb(III) ion (10200-10300
cm-1), 4f-luminescence is possible for all
compounds through the intramolecular ener-
gy transfer mechanism. When all the Yb(III)
complexes are excited at the absorption
maxima, a band in the region of 975–985 nm
is observed in the luminescence spectra (Fig.
3), which corresponds to the transition from
the excited 2F5/2 level of the lanthanide ion to
the ground level 2F7/2. Due to the excitation
energy transfer to ytterbium ion, the molecu-
lar fluorescence of the complexes is signifi-
cantly quenched in comparison with ligands
(more than 80%). It was found that the quan-
tum yields of 4f-luminescence of ytterbium
complexes with L3H6 and L4H7 are lower
than for compounds with the initial
aminoethoxy derivatives (Table 3).
T a b l e 3
Spectral-luminescent characteristics of
Yb(III)-calix[4]arenes complexes
Complex λmax, nm φ×103
YbL1* 981 1.9
YbL2(Cl)* 982 1.6
YbL3H3 981 1.1
YbL4H4 981 1.3
YbL5H3 981 2.3
Yb2L6H2 981 2.4
Yb2L7H4 982 2.1
Two main factors that influence the 4f-
luminescence intensity of complexes of
modified calix[4]arenes as compared to
complexes of the initial aminoethoxy deriva-
tives should be taken into account. First, the
coordination of the ion with the APC frag-
ment leaves a minimum space for solvent
molecules (which have luminescence
quenching effect) in the internal coordina-
tion sphere of the complex. Secondly, the
emitting ion is removed from the calixarene
photoantenna, which affects the decrease in
luminescence intensity.
As a result of structural optimization
Lower rim-modified calix[4]arenes with fragments of EDTA (DTPA)…
ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 5 21
by means of the molecular mechanics meth-
od (HyperChem 8.0.6 program), it was
shown that Yb(III) ion is 4 times (about
8.6Å) more distant from phenolic oxygen
atoms in comparison with the complexes of
the initial L1H3 and L2H2. The largest quan-
tum yield among mononuclear complexes
was found for the complex with L7H5, in
which this distance decreases to 5.9Å.
In binuclear complexes Yb2L5H2 and
Yb2L6H4, in spite of the removal of emitting
ions from the calix[4]arene, the intensity of
4f-luminescence increases by 1.7-2 times in
comparison with mononuclear complexes.
Since molecular fluorescence is completely
quenched in both mononuclear and binuclear
complexes, an increase of intensity and
quantum yield of Yb-centered emission is
the evidence of the more efficient excitation
energy transfer due to a decrease in non-
radiative losses.
Less intense signal in the case of both
mono- and binuclear EDTA-substituted
complexes are likely due to the fact that the
ytterbium ion coordinated by the EDTA
fragment forms donor-acceptor bonds with
only six donor atoms. Thus, the coordination
sphere of the lanthanide ion is less saturated,
and extra-coordination of larger number of
solvent molecules is possible. Latter leads to
an additional possibility of dissipating the
excitation energy. The estimated number of
donor atoms (for DTPA-derivatives) provid-
ed by one acid fragment is 8, which is typi-
cal for diethylenetriaminepentaacetates of
lanthanides [7].
It was also found that Lu(III) complex-
es reveal biological activity. The antibacteri-
al activity of the L4H7 derivative and its lute-
tium complex were studied against various
species of Gram positive, such as Staphylo-
coccus aureus, as well as Escherichia coli
(Gram negative) bacteria. L4H7 was charac-
terized by a rather high level of antibacterial
action on S. aureus cells, practically without
affecting the Gram negative microorganism
development, while its lutetium complex had
an inhibitory effect on both species of test
microorganisms.
Authors are grateful to the National
Academy of Sciences of Ukraine for the fi-
nancial support of this work.
CONCLUSIONS. Calix[4]arenes sub-
stituted at the lower rim with fragments of
aminopolycarboxylic acids (EDTA, DTPA)
were synthesized. Mono and binuclear com-
plexes with lanthanide (III) ions were syn-
thesized using these compounds. All com-
pounds were characterized by means of var-
ious physico-chemical methods, and struc-
tures of complexes were proposed. 4f-
Luminescence of the lanthanide ion is real-
ized in the mononuclear complexes of ca-
lix[4]arenes, and when an additional ion is
introduced into the macrocycle, its intensity
is approximately doubled. The data obtained
allow us to conclude that the structure of
functionalized ligands significantly affects
the differences in the luminescent properties
of complexes based on them. In this case,
the effect of the structure of additional lig-
ands, their amount, and the method of com-
bining with the macrocycle is manifested.
This is confirmed by the fact that the com-
plexes of lanthanides with calix[4]arenes,
which are the basic compounds for the pro-
duction of APC-modified ligands (p-tert-
butylcalix[4]arenes, L1H3 and L2H2), have
approximately equal values of the quantum
yields of 4f-luminescence.
S.S. Smola, Ye.N. Fadieiev, M.Yu. Rusakova, O.V. Snurnikova, O.A. Alyeksyeyeva, N.V. Rusakova
22 ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 5
КАЛІКС[4]АРЕНИ, МОДИФІКОВАНІ ПО
НИЖНЬОМУ ОБОДУ ФРАГМЕНТАМИ
ЕДТА (ДТПА), ТА ЇХ Ln(III) КОМПЛЕКСИ
(Ln = Yb, Lu): СИНТЕЗ ТА ЛЮМІ-
НЕСЦЕНТНІ ВЛАСТИВОСТІ У БЛИЖНІЙ
ІЧ ОБЛАСТІ
С.С. Смола1, Є.М. Фадєєв1, М.Ю. Русакова2,
О.В. Снурнікова1, O.A. Алексеєва1, Н.В. Ру-
сакова1
1Фізико-хімічний інститут ім. О.В. Богат-
ського НАН України, Люстдорфська дорога,
86, Одеса, 65080, Україна
2Одеський національний університет ім. І.І.
Мечникова, Дворянська, 2, Одеса, 65082,
Україна
*е-mail: natavrusakova@gmail.com
Отримані похідні п-трет-бутілкалікс
[4]арену, заміщені по нижньоик ободу фраг-
ментами амінополікарбонових кислот
(ЕДТА, ДТПА). Моно та біядерні комплекси
з іонами лантанідів (III) були синтезовані за
допомогою цих сполук. Вивчено вплив
кількості та типу фрагментів амінополі-
карбонових кислот на люмінесценцію лі-
гандів та комплексів. Проаналізовано вплив
відстані між випромінюючим іоном і макро-
циклом каліксарену на інтенсивність 4f-
люмінесценції.
К л ю ч о в і с л о в а: калікс[4]арени, ЕДТА,
ДТПА, лантаніди, люмінесценція.
КАЛИКС[4]АРЕНЫ, МОДИФИЦИРОВАН-
НЫЕ ПО НИЖНЕМУ ОБОДУ ФРАГ-
МЕНТАМИ ЭДТА (ДТПА), И ИХ Ln(III)
КОМПЛЕКСЫ (Ln = Yb, Lu): СИНТЕЗ И
ЛЮМИНЕСЦЕНТНЫЕ СВОЙСТВА В
БЛИЖНЕЙ ИК ОБЛАСТИ
С.С. Смола1, Е.Н. Фадеев1, М.Ю. Русакова2,
О.В. Снурникова1, Е.A. Алексеева1, Н.В. Ру-
сакова1
1Физико-химический институт им. А.В. Бо-
гатского НАН Украины, Люстдорфская до-
рога, 86, Одесса, 65080, Украина
2Одесский национальный университет им.
И.И. Мечникова, Дворянская, 2, Одесса,
65082, Украина
*е-mail: natavrusakova@gmail.com
Получены производные п-трет-
бутилкаликс[4]арена, замещенные по ниж-
нему ободу фрагментами аминополикарбо-
новых кислот (ЭДТА, ДТПА). С помощью
этих соединений были синтезированы моно-
и биядерные комплексы с ионами лантани-
дов (III). Изучено влияние количества и типа
фрагментов аминополикарбоновых кислот на
люминесценцию лигандов и комплексов.
Проанализировано влияние расстояния меж-
ду излучающим ионом и макроциклом кали-
ксарена на интенсивность 4f-люминесцен-
ции.
К л ю ч е в ы е с л о в а: каликс[4]арены,
ЭДТА, ДТПА, лантаниды, люминесценция
REFERENCES
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Надійшла 12.05.2020
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| id | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-168 |
| institution | Ukrainian Chemistry Journal |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-07-23T01:02:20Z |
| publishDate | 2020 |
| publisher | V.I.Vernadsky Institute of General and Inorganic Chemistry |
| record_format | ojs |
| resource_txt_mv | ucjorgua/8b/e301c7a1eed308725a323153eef60a8b.pdf |
| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-1682026-07-22T08:23:43Z Lower rim-modified calix[4]arenes with fragments of EDTA (DTPA) and their Ln(III) complexes (Ln = Yb, Lu): synthesis and NIR-luminescent properties КАЛИКС[4]АРЕНЫ, МОДИФИЦИРОВАННЫЕ ПО НИЖНЕМУ ОБОДУ ФРАГМЕНТАМИ ЭДТА (ДТПА), И ИХ Ln(III) КОМПЛЕКСЫ (Ln = Yb, Lu): СИНТЕЗ И ЛЮМИНЕСЦЕНТНЫЕ СВОЙСТВА В БЛИЖНЕЙ ИК ОБЛАСТИ КАЛІКС[4]АРЕНИ, МОДИФІКОВАНІ ПО НИЖНЬОМУ ОБОДУ ФРАГМЕНТАМИ ЕДТА (ДТПА), ТА ЇХ Ln(III) КОМПЛЕКСИ (Ln = Yb, Lu): СИНТЕЗ ТА ЛЮМІНЕСЦЕНТНІ ВЛАСТИВОСТІ У БЛИЖНІЙ ІЧ ОБЛАСТІ Smola, Serhii Fadieiev, Yevhen Rusakova, Mariia Snurnikova, Olga Alyeksyeyeva, Olena Rusakova, Nataliya calix[4]arenes, EDTA, DTPA, lanthanides, luminescence. Derivatives of p-tert-butylcalix[4]arene substituted on the lower rim with fragments of aminopolycarboxylic acids (EDTA, DTPA) were obtained. Mono and binuclear complexes with lanthanide (III) ions were synthesized using these compounds. The effect of the number and type of aminopolycarboxylic acid fragments on the luminescence of ligands and complexes was studied. The influence of the distance between the emitting ion and the calixarene macrocycle on the intensity of 4f-luminescence was analyzed. V.I.Vernadsky Institute of General and Inorganic Chemistry 2020-07-15 Article Article Inorganic Chemistry Неорганическая химия Неорганічна хімія application/pdf https://ucj.org.ua/index.php/journal/article/view/168 10.33609/2708-129X.86.5.2020.13-23 Ukrainian Chemistry Journal; Vol. 86 No. 5 (2020): Ukrainian Chemistry Journal; 13-23 Украинский химический журнал; ##issue.vol## 86 ##issue.no## 5 (2020): Украинский химический журнал; 13-23 Український хімічний журнал; Том 86 № 5 (2020): Український хімічний журнал; 13-23 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/168/97 Copyright (c) 2020 Serhii Smola, Yevhen Fadieiev, Mariia Rusakova, Olga Snurnikova, Olena Alyeksyeyeva, Nataliya Rusakova https://creativecommons.org/licenses/by-nc/4.0 |
| spellingShingle | Smola, Serhii Fadieiev, Yevhen Rusakova, Mariia Snurnikova, Olga Alyeksyeyeva, Olena Rusakova, Nataliya КАЛІКС[4]АРЕНИ, МОДИФІКОВАНІ ПО НИЖНЬОМУ ОБОДУ ФРАГМЕНТАМИ ЕДТА (ДТПА), ТА ЇХ Ln(III) КОМПЛЕКСИ (Ln = Yb, Lu): СИНТЕЗ ТА ЛЮМІНЕСЦЕНТНІ ВЛАСТИВОСТІ У БЛИЖНІЙ ІЧ ОБЛАСТІ |
| title | КАЛІКС[4]АРЕНИ, МОДИФІКОВАНІ ПО НИЖНЬОМУ ОБОДУ ФРАГМЕНТАМИ ЕДТА (ДТПА), ТА ЇХ Ln(III) КОМПЛЕКСИ (Ln = Yb, Lu): СИНТЕЗ ТА ЛЮМІНЕСЦЕНТНІ ВЛАСТИВОСТІ У БЛИЖНІЙ ІЧ ОБЛАСТІ |
| title_alt | Lower rim-modified calix[4]arenes with fragments of EDTA (DTPA) and their Ln(III) complexes (Ln = Yb, Lu): synthesis and NIR-luminescent properties КАЛИКС[4]АРЕНЫ, МОДИФИЦИРОВАННЫЕ ПО НИЖНЕМУ ОБОДУ ФРАГМЕНТАМИ ЭДТА (ДТПА), И ИХ Ln(III) КОМПЛЕКСЫ (Ln = Yb, Lu): СИНТЕЗ И ЛЮМИНЕСЦЕНТНЫЕ СВОЙСТВА В БЛИЖНЕЙ ИК ОБЛАСТИ |
| title_full | КАЛІКС[4]АРЕНИ, МОДИФІКОВАНІ ПО НИЖНЬОМУ ОБОДУ ФРАГМЕНТАМИ ЕДТА (ДТПА), ТА ЇХ Ln(III) КОМПЛЕКСИ (Ln = Yb, Lu): СИНТЕЗ ТА ЛЮМІНЕСЦЕНТНІ ВЛАСТИВОСТІ У БЛИЖНІЙ ІЧ ОБЛАСТІ |
| title_fullStr | КАЛІКС[4]АРЕНИ, МОДИФІКОВАНІ ПО НИЖНЬОМУ ОБОДУ ФРАГМЕНТАМИ ЕДТА (ДТПА), ТА ЇХ Ln(III) КОМПЛЕКСИ (Ln = Yb, Lu): СИНТЕЗ ТА ЛЮМІНЕСЦЕНТНІ ВЛАСТИВОСТІ У БЛИЖНІЙ ІЧ ОБЛАСТІ |
| title_full_unstemmed | КАЛІКС[4]АРЕНИ, МОДИФІКОВАНІ ПО НИЖНЬОМУ ОБОДУ ФРАГМЕНТАМИ ЕДТА (ДТПА), ТА ЇХ Ln(III) КОМПЛЕКСИ (Ln = Yb, Lu): СИНТЕЗ ТА ЛЮМІНЕСЦЕНТНІ ВЛАСТИВОСТІ У БЛИЖНІЙ ІЧ ОБЛАСТІ |
| title_short | КАЛІКС[4]АРЕНИ, МОДИФІКОВАНІ ПО НИЖНЬОМУ ОБОДУ ФРАГМЕНТАМИ ЕДТА (ДТПА), ТА ЇХ Ln(III) КОМПЛЕКСИ (Ln = Yb, Lu): СИНТЕЗ ТА ЛЮМІНЕСЦЕНТНІ ВЛАСТИВОСТІ У БЛИЖНІЙ ІЧ ОБЛАСТІ |
| title_sort | калікс[4]арени, модифіковані по нижньому ободу фрагментами едта (дтпа), та їх ln(iii) комплекси (ln = yb, lu): синтез та люмінесцентні властивості у ближній іч області |
| topic_facet | calix[4]arenes EDTA DTPA lanthanides luminescence. |
| url | https://ucj.org.ua/index.php/journal/article/view/168 |
| work_keys_str_mv | AT smolaserhii lowerrimmodifiedcalix4areneswithfragmentsofedtadtpaandtheirlniiicomplexeslnyblusynthesisandnirluminescentproperties AT fadieievyevhen lowerrimmodifiedcalix4areneswithfragmentsofedtadtpaandtheirlniiicomplexeslnyblusynthesisandnirluminescentproperties AT rusakovamariia lowerrimmodifiedcalix4areneswithfragmentsofedtadtpaandtheirlniiicomplexeslnyblusynthesisandnirluminescentproperties AT snurnikovaolga lowerrimmodifiedcalix4areneswithfragmentsofedtadtpaandtheirlniiicomplexeslnyblusynthesisandnirluminescentproperties AT alyeksyeyevaolena lowerrimmodifiedcalix4areneswithfragmentsofedtadtpaandtheirlniiicomplexeslnyblusynthesisandnirluminescentproperties AT rusakovanataliya lowerrimmodifiedcalix4areneswithfragmentsofedtadtpaandtheirlniiicomplexeslnyblusynthesisandnirluminescentproperties AT smolaserhii kaliks4arenymodificirovannyeponižnemuobodufragmentamiédtadtpaiihlniiikompleksylnyblusintezilûminescentnyesvojstvavbližnejikoblasti AT fadieievyevhen kaliks4arenymodificirovannyeponižnemuobodufragmentamiédtadtpaiihlniiikompleksylnyblusintezilûminescentnyesvojstvavbližnejikoblasti AT rusakovamariia kaliks4arenymodificirovannyeponižnemuobodufragmentamiédtadtpaiihlniiikompleksylnyblusintezilûminescentnyesvojstvavbližnejikoblasti AT snurnikovaolga kaliks4arenymodificirovannyeponižnemuobodufragmentamiédtadtpaiihlniiikompleksylnyblusintezilûminescentnyesvojstvavbližnejikoblasti AT alyeksyeyevaolena kaliks4arenymodificirovannyeponižnemuobodufragmentamiédtadtpaiihlniiikompleksylnyblusintezilûminescentnyesvojstvavbližnejikoblasti AT rusakovanataliya kaliks4arenymodificirovannyeponižnemuobodufragmentamiédtadtpaiihlniiikompleksylnyblusintezilûminescentnyesvojstvavbližnejikoblasti AT smolaserhii kalíks4arenimodifíkovaníponižnʹomuobodufragmentamiedtadtpataíhlniiikompleksilnyblusinteztalûmínescentnívlastivostíubližníjíčoblastí AT fadieievyevhen kalíks4arenimodifíkovaníponižnʹomuobodufragmentamiedtadtpataíhlniiikompleksilnyblusinteztalûmínescentnívlastivostíubližníjíčoblastí AT rusakovamariia kalíks4arenimodifíkovaníponižnʹomuobodufragmentamiedtadtpataíhlniiikompleksilnyblusinteztalûmínescentnívlastivostíubližníjíčoblastí AT snurnikovaolga kalíks4arenimodifíkovaníponižnʹomuobodufragmentamiedtadtpataíhlniiikompleksilnyblusinteztalûmínescentnívlastivostíubližníjíčoblastí AT alyeksyeyevaolena kalíks4arenimodifíkovaníponižnʹomuobodufragmentamiedtadtpataíhlniiikompleksilnyblusinteztalûmínescentnívlastivostíubližníjíčoblastí AT rusakovanataliya kalíks4arenimodifíkovaníponižnʹomuobodufragmentamiedtadtpataíhlniiikompleksilnyblusinteztalûmínescentnívlastivostíubližníjíčoblastí |