ОСОБЛИВОСТІ СТРУКТУРИ ТА СПЕКТРАЛЬНО-ЛЮМІНЕСЦЕНТНИХ ВЛАСТИВОСТЕЙ КАРБОКСИМЕТОКСИЗАМІЩЕНИХ КАЛІКС[4]АРЕНІВ ТА ЇХ КОМПЛЕКСІВ З ЛАНТАНІДАМИ
Spectral-luminescent properties of a variety of carboxymethoxy-substituted p-tert-butyl-calix[4]arenes and their complexes with lanthanides (Nd, Er, Yb) that exhibit the 4f-luminescence in the IR-spectrum region have been investigated. The effect of substitution of hydrogen phenolic atoms by carboxy...
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| author | Smola, Serhii Rusakova, Nataliia Snurnikova, Olga Alekseeva, Elena Kirichenko, Tatyana |
| author_facet | Smola, Serhii Rusakova, Nataliia Snurnikova, Olga Alekseeva, Elena Kirichenko, Tatyana |
| author_institution_txt_mv | [
{
"author": "Serhii Smola",
"institution": ".V. Bogatsky Physico-chemical Institute, National Academy of Sciences of Ukraine, 86, Lustdorfskaya Doroga, 65080, Odessa"
},
{
"author": "Nataliia Rusakova",
"institution": "A.V. Bogatsky Physico-chemical Institute, National Academy of Sciences of Ukraine, 86, Lustdorfskaya Doroga, 65080, Odessa"
},
{
"author": "Olga Snurnikova",
"institution": "A.V. Bogatsky Physico-chemical Institute, National Academy of Sciences of Ukraine, 86, Lustdorfskaya Doroga, 65080, Odessa"
},
{
"author": "Elena Alekseeva",
"institution": "A.V. Bogatsky Physico-chemical Institute, National Academy of Sciences of Ukraine, 86, Lustdorfskaya Doroga, 65080, Odessa"
},
{
"author": "Tatyana Kirichenko",
"institution": "A.V. Bogatsky Physico-chemical Institute, National Academy of Sciences of Ukraine, 86, Lustdorfskaya Doroga, 65080, Odessa"
}
] |
| author_sort | Smola, Serhii |
| baseUrl_str | https://ucj.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-22T08:23:42Z |
| description | Spectral-luminescent properties of a variety of carboxymethoxy-substituted p-tert-butyl-calix[4]arenes and their complexes with lanthanides (Nd, Er, Yb) that exhibit the 4f-luminescence in the IR-spectrum region have been investigated. The effect of substitution of hydrogen phenolic atoms by carboxymethoxy groups on the stability and spectral-luminescent characteristics of both the ligands and lanthanide complexes was analyzed. Thus, based on the combination of the results obtained by means of elemental analysis, mass spectrometry, IR and 1H NMR spectroscopy, and taking into account the data of pH-metric titration, spectrophotometric and luminescence measurements, it can be concluded that lanthanide ions form neutral complexes of 1:1 ratio with L1H4 - L4H4. This is explained by the presence of mobile hydrogen atoms of phenol and/or carboxyl groups in the molecules of these ligands. An increase in the number of donor substituents leads to changes in the number of solvent molecules in the series L3H4 < L1H4 < L2H4 < L4H4 from 0.8 to 2.4 for neodymium complexes, from 1.2 to 2.2 - for ytterbium complexes. Both the quantum yield and lifetime of the 4f-luminescence of the neodymium and ytterbium complexes and also the luminescence intensity of the erbium-containing compounds change in the same order. |
| doi_str_mv | 10.33609/0041-6045.86.3.2020.9-18 |
| first_indexed | 2025-09-24T17:43:24Z |
| format | Article |
| fulltext |
Неорганічна хімія
ISSN 0041-6045. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 3 9
UDC 547.639:541.49:546.650:535.37 doi: 10.33609/0041-6045.86.3.2020.9-18
S. S. Smola, O. V. Snurnikova, E. A. Alekseeva, T. I. Kirichenko, N. V. Rusakova*
PECULIARITIES OF STRUCTURE AND SPECTRAL-LUMINESCENT
PROPERTIES OF CARBOXYMETHOXY-SUBSTITUTED CALIX[4]ARENES AND
THEIR COMPLEXES WITH LANTHANIDES
A. V. Bogatsky Physico-Chemical Institute, National Academy of Sciences of Ukraine; 86
Lyustdorfskaya doroga, Odessa, 65080, Ukraine
*е-mail: natavrusakova@gmail.com
Spectral- luminescent properties of a variety of carboxymethoxy-substituted p-tert-butyl-
calix[4]arenes and their complexes with lanthanides (Nd, Er, Yb) that exhibit the 4f-
luminescence in the IR-spectrum region have been investigated. The effect of substitu-
tion of hydrogen phenolic atoms by carboxymethoxy groups on the stability and spec-
tral- luminescent characteristics of both the ligands and lanthanide complexes was ana-
lyzed.
K e y w o r d s: calix[4]arenes, lanthanide-containing complexes, NIR-luminescence.
INTRODUCTION. Having a spatially-
organized cavity and specific physicochemi-
cal properties, calix[4]arenes are com-
pounds, which are increasingly used in
guest-host chemistry [1]. The structure of the
spatially organized calix[4]arene molecules
delineates a hydrophilic (rims) and a hydro-
phobic (cavity) fragments, and the size and
spatial proximity of the functional groups
impart a number of significant features to
their chemical behavior. The most accessible
method for modifying the lower rim is the
replacement of the hydrogen atom of the
phenol groups, for example, with different
numbers of alkylcarboxyl substituents. It is
known that the introduction of four carboxyl
fragments along the lower rim of the calix
[4] arene promotes the formation of more
stable lanthanide-containing complexes in
comparison with p-tert-butylcalix[4]arene
[TBC] [2]. However, until now, the study of
the effect of sequential introduction of
alkylcarboxyl substituents and, consequent-
ly, the structure of symmetrically and
asymmetrically substituted calix[4]arenes on
the physicochemical, in particular, spectral-
luminescent properties of ligands and com-
plexes with lanthanides has not been con-
ducted.
The aim of this work was to establish the
relationship between the structure of
the series of carboxymethoxy-containing
calix[4]arenes (L1Н4L4Н4) and acid-base,
complex-forming, spectral-luminescent
properties of ligands themselves, as well as
their lanthanide-containing complexes.
© S. S. Smola, O. V. Snurnikova, E. A. Alekseeva, T. I. Kirichenko, N. V. Rusakova, 2020
S. S. Smola, O. V. Snurnikova, E. A. Alekseeva, T. I. Kirichenko, N. V. Rusakova
10 ISSN 0041-6045. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 3
The analysis of symmetric (L2Н4, L4Н4) and
asymmetric (L1Н4, L3Н4) ligands was made
and the number of solvent molecules located
in the inner coordination sphere of the com-
plexes was calculated.
Fig.1. Structure of carboxymethoxy-containing
calix[4]arenes L1Н4-L4Н4
EXPERIMENT AND DISCUSSION OF
THE RESULTS. Ligands L1Н4-L4Н4 and the
corresponding lanthanide-containing com-
plexes were synthesized according to the
methods described in [2, 3]. Complexes
were isolated in solid state and identified by
means of elemental analysis, mass spec-
trometry, IR, 1H NMR spectroscopy (Table
S1-S2).
pH-Potentiometric titration was carried
out on an ionomer EV-74. The glass elec-
trode SL-43-07 (calibrated with standard
buffer solutions) and silver chloride refer-
ence electrode were used.
Absorption spectra in the UV and visible
regions were recorded on a Specord M-40
UV / VIS spectrophotometer in quartz cu-
vettes 1-10 mm thick, and in the IR region
(4000-400 cm-1) on a Shimadzu FT-IR
8400S spectrophotometer (in KBr pellets
and in CHCl3).
Fluorescence excitation end emission
spectra, as well as phosphorescence and 4f-
luminescence were recorded on a Fluorolog
FL 3-22 spectrophotometer (Horiba Jobin
Yvon, Xe-450 W ozone-free lamp) equipped
with a photomultiplier R928P (Hamamatsu,
Japan) for the visible spectrum region and a
liquid nitrogen cooled InGaAs photoresistor
(DSS-IGA020L, Electro-Optical Systems,
Inc.) for the NIR area.
Values of the singlet (ES) and triplet lev-
els (ET) of the derivatives of calyx[4]arenes
and lutetium-containing complexes were
determined by known procedure [4] at 77K
using phosphorescence spectra obtained with
different time delays after the excitation
pulse.
Fig.2. The equilibrium diagrams of protonated
ligand forms in water-methanol solutions as a
function of pH at 298 K and μ= 0.15 M: а -
L1H4; b - L3H4
Speculiarities of structure and spectral-luminescent properties…
ISSN 0041-6045. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 3 11
T a b l e 1
Acid-base dissociation constants of p-tert-
butyl-calix[4]arenes
Compound pK1 pK2 pK3 pK4
L1H4 7.8 9.4 10.3 >11
L2H4 4.3 6.8 9.6 >11
L3H4 4.9 5.8 7.6 9.9
L4H4 3.9 5.6 7.3 8.5
TBC [7] 9.2 11.5 >14 -
The integral fluorescence intensity (Ifl)
was measured based on the area under the
band contour. The values of the relative
quantum yield of 4f-luminescence (φ) of
lanthanide ions (measurement error ± 20%)
in the complexes were calculated by the
methods described in [5, 6].
It is known that one of the characteristic
features of calix[4]arenes is the ability to
form intramolecular hydrogen bonds, which
significantly affect conformational, acid-
base, spectral, and complexing properties
[7]. The consecutive replacement of OH
groups leads to disruption of these bonds,
therefore, affects all the above properties,
and primarily the dissociation constants of
the test compounds (Table 1).
The values of the first dissociation con-
stant of L1H4 and p-tert-butyl-calix[4]arene
(TBC) were fairly close, while pK1 value for
L2H4 is lower than for L1H4 by 3.5. This fact
confirms, according to [7], the formation of
a cycle of hydrogen bonds involving the
COOH group in the case of L1H4, and a sig-
nificant weakening of them upon transition
to L2H4. The higher pK1 value in the case of
L3H4 compared to L2H4 indicates the greater
contribution in hydrogen bond formation for
L3H4. Close values of pK2 and pK3 for lig-
ands L3H4 and L4H4 indicate the stabilization
of the anions H3L- and H2L2- due to the for-
mation of hydrogen bonds by carboxyl
groups. The main forms of L1H4, L2H4 in the
alkaline region are [H2L2-], [HL3-], [L4-], and
the ligands L3H4, L4H4 – [HL3-], [L4-]. The
shape of the distribution of ligands L1H4 and
L3H4 shown in Fig. 2 allows one to consider
carboxymethoxy-calix[4]arenes as tetra-
basic acids, in which, when complexing, the
protons of both carboxyl and phenol groups
can be replaced by a lanthanide ion. The re-
sults of potentiometric titration point to the
weakening of intramolecular hydrogen
bonds in the series L1H4 > L3H4 > L2H4 >
L4H4, which is confirmed by the results of
1H NMR and IR spectroscopy.
In 1H NMR spectra of symmetric ligand
(TBC, L2H4, L4H4) solutions, proton signals
of methylene bridges of the calix[4]arene
macrocycle appear as two doublets (3.25-
3.55 and 4.15-4.55 ppm) with an intensity of
4H for each, and ligands (L1Н4 and L3Н4) -
in the form of two pairs of doublets with a
small difference in the values of chemical
shifts (3.25-3.75 ppm and 4.10-4.25 ppm)
with an intensity of 2H for each. It is this
type of spectra that is characteristic for
“cone” conformation [7]. The broadened
singlets from protons of OH groups in weak
fields (9.00-10.35 ppm) indicate their partic-
ipation in the formation of hydrogen bonds.
It should be noted that the δOH value for the
studied ligands changes in such way: TBC
(10.34 ppm) > L1H4 (9.47 ppm) > L3H4 (9.30
ppm) > L2H4 (9.00 ppm).
In 1H NMR spectra of complexes with
diamagnetic lutetium ion there are no proton
signals of the carboxyl and hydroxyl groups,
S. S. Smola, O. V. Snurnikova, E. A. Alekseeva, T. I. Kirichenko, N. V. Rusakova
12 ISSN 0041-6045. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 3
which indicates their replacement by a lan-
thanide ion and confirms the IR spectrosco-
py data. The observed decrease in the num-
ber of proton signals of tert-butyl substitu-
ents in the spectra of LuL1H and LuL3H
complexes indicates, according to [8], the
"alignment" of the complex structure com-
pared to the corresponding asymmetrically
substituted ligands. The formation of com-
plexes based on symmetrical ligands L2H4
and L4H4 does not introduce changes in the
number and intensity of the proton signals of
these groups, i.e. the symmetry of the coor-
dination center during complexation is pre-
served. Significant shifts in the signals of
protons of aromatic nuclei (Δδ = +0.12±0.22
ppm) and CH2CO-groups (Δδ = +0.08±0.14
ppm) in comparison with ligands L1Н4 -
L3Н4 confirm participation of oxygen atoms
of ester fragments in coordination of metal
in these complexes.
The presence of intense wide bands of
stretching vibrations of the OH group in the
3100-3400 cm-1 region in IR spectra of L1H4
- L4H4 also indicates the presence of
intramolecular hydrogen bonds. Replace-
ment of phenol groups with carboxymethoxy
ones leads to a shift in the frequency of the
bands to the long-wavelength region (L1H4
(3170 cm-1) < L2H4 (3320 cm-1) < L3H4
(3375 cm-1)) as compared to TBC (3130 cm-
1). These changes in IR spectra, similar to
the 1H NMR spectra [8, 9], indicate a signif-
icant weakening of intramolecular hydrogen
bonds with an increase in the number of
carboxymethoxy groups.
A significant decrease in the intensities
of the stretching vibration bands of OH
groups in IR spectra of lanthanide-
containing complexes in the region of 3150-
3350 cm-1, the disappearance of bands in the
region v (C=O) = 1740-1750 cm-1, as well as
the absorption bands of OH and COOH de-
formation vibrations in the fingerprints re-
gion (730-780, 800-830, 880-910, 1180-
1250 cm-1) indicate that all the correspond-
ing substituents are connected with the lan-
thanide ion. This is also confirmed by the
appearance of bands in the region of 1595-
1600 cm-1 and 1440-1470 cm-1, related to
νas(C-O) and νs(C-O), respectively. It should
be noted that, in contrast to LnL4H, a short-
wavelength shift (20-50 cm-1) of the v(-
CH2-OAr) oscillations in the 1030-1050 cm-1
region is observed for LnL1Н - LnL3Н com-
plexes, confirming the participation of ether
oxygen atoms in the complexing of the
metal.
Fig. 3. Absorption and fluorescence spectra of
solutions in dioxane at 298 K: а – L1Н4, λexc=
308 nm; b – L2Н4, λexc= 312 nm; c - L3Н4, λexc=
310 nm; d – L4Н4, λexc= 309 nm
Speculiarities of structure and spectral-luminescent properties…
ISSN 0041-6045. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 3 13
T a b l e 2.
Data of the absorption, fluorescence and phosphorescence spectra of calix[4]arenes L1Н4–L4Н4
Ligand Solvent λI, λII nm
(lg ε)
λfl,
нм τfl, ns ES, sm-1 λphos,
nm
τphos,
ms ET,sm-1
L1Н4
DO 274
(3.88)
283
(3.92) 402 9.2±0.2 24900 420 210±8 23800
DMF 280
(3.95)
286
(sh.) 410 9.6±0.2 24400 429 234±8 23300
L2Н4
DO 268
(3.89)
280
(3.93) 395 6.4±0.4 25300 406 208±4 24600
DMF 288
(3.94)
296
(sh.) 411 4.2±0.2
15.3±0.5 24300 422 291±4 23700
L3Н4
DO 264
(3.57)
270
(3.50) 399 15.4±0.7 25100 412 259±15 24300
DMF 278
(sh.)
285
(3.70) 405 3.4±0.3
13.5±0.8 24700 436 138±9 22900
L4Н4
DO 260
(3.75)
267
(3.78) 392 5.7±0.4 25500 424 140±5 23600
DMF 278
(3.67)
280
(sh.) 409 4.8±0.5
18±2 24450 439 280±5 22800
The absorption spectra of the free lig-
ands in dioxane at room temperature are
characterized by wide bands split into two
components with maxima at 260-274 nm
and 270-283 nm (lgε = 3.50-3.95), which
correspond to π→π* -transitions of aromatic
fragments (Fig. 3 and Table 1).
It should be noted that as the number of
substituents increases, hypsochromic shifts
in the absorption band maxima are observed,
observed, although the molar extinction co-
efficients and the intensity ratio of the bands
remain constant. In comparison with TBC
(λI = 280, λII = 288 nm), the introduction of
one carboxyl group practically does not af-
fect the position and intensity of the absorp-
tion bands. When the number of carbox-
yl (di-, tri- and tetra- substituted ligands)
is increased, a hypsochromic shift of the ab-
sorption band maxima from 3-6 to 14-16 nm
is observed and the absorption intensity de-
creases by 10-12%. These changes, accord-
ing to [8], in the absorption spectra in a se-
ries of carboxy derivatives of the ca-
lix[4]arene are explained by structural
changes in the chain of intramolecular hy-
drogen bonds that form substitutes of the
lower rim. A significant difference should be
noted in the absorption spectra in the
dimethylformamide (DMF) and dioxane
(DO) media, which indicates the interaction
of ligands with the molecules of the basic
solvent - dimethylformamide. Along with
the absorption spectra, the fluorescence /
phosphorescence spectra of the ligands also
undergo significant changes.
S. S. Smola, O. V. Snurnikova, E. A. Alekseeva, T. I. Kirichenko, N. V. Rusakova
14 ISSN 0041-6045. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 3
T a b l e 3.
Spectroscopic properties of Lu(III) complexes with L1H4 – L4H4 (С=1×10-4 M, dioxane)
Complex λI, λII, λIII, nm (lg ε) λfl,
nm τfl, ns ES,sm-1 λphos,
nm
τphos,
ms ET,sm-1
LuL1H 283
(3.74)
290
(3.71)
307
(2.85) 404 6.6±0.3 24750 424 259±9 23600
LuL2H 273
(3.58)
276
(3.59)
320
(2.62) 406 6.0±0.2 24600 420 133±8 23800
LuL3H 278
(3.20)
284
(3.18)
312
(2.36) 409 8.9±0.1 24450 452 344±5 22100
LuL4H 277
(3.90)
288
(sh.) - 411
9.8±0.2 24300 445 144±5 22400
Solutions of carboxyalkyl[4]arenes in
dioxane show fluorescence in the form of a
broad band in the 390-415 nm region
(24100-25640 cm-1, λexc = 300-320 nm),
which corresponds to the transition from the
lower excited 1ππ * to the ground level.
When a time delay (10-20 μs) and cooling to
77 K were used, the phosphorescence of the
ligands was detected, the maximum band of
which was batochromically shifted by 15-30
nm relative to the fluorescence (Table 2).
The fluorescence spectra of solutions of all
ligands in DMF, in comparison with solu-
tions in dioxane, are batochromically shifted
by 6-17 nm, and phosphorescence - by 9-24
nm, respectively. The values of the singlet S1
and triplet T1 energy levels, as well as the
energy gaps between them, do not undergo
significant changes, although for L3H4 ΔE
increases by 960 cm-1. Biexponential fitting
of the fluorescence decay curves of L2H4 -
L4H4 in DMF also confirms complexation
with solvent molecules. The largest values of
τ in comparison with the rest of the series are
observed for solutions of L3H4 in dioxane.
The absorption spectra of lanthanide (III)
complexes (Er, Yb, Nd, Lu) with identical
ligands coincide, indicating that the method
of coordination of the lanthanide ion in this
row remains the same. The formation of all
lanthanide complexes with L1H4-L4H4 leads
to a bathochromic shift of the maxima of the
absorption, fluorescence, and phosphores-
cence spectra as compared with the ligands
(Table 3). The appearance of a broad band in
the region of 307-320 nm (lg ε = 2.85-2.36)
in the absorption spectra of L1H4-L3H4 com-
plexes, according to [10], indicates the par-
ticipation of phenol OH-groups in complex
formation. The stability constants of the cor-
responding complexes were calculated in
anhydrous methanol: (2×10-4 M): 8.7 ± 1.6
(LuL1H), 10.3±1.5 (LuL2H), 14.3±0.8
(LuL3H), 18.4±1.4 (LuL4H). As can be seen
from the data presented, a significant in-
crease in the stability constants is observed
with an increase in the number of
carboxymethoxy groups along the lower rim
of the ligands.
In all LnL1H - LnL4H compounds, 4f-
luminescence of Nd3+, Er3+ and Yb3+ ions is
realized in the infrared region of the spec-
Speculiarities of structure and spectral-luminescent properties…
ISSN 0041-6045. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 3 15
T a b l e 4
4f-Luminescent properties of Ln(III) complexes with L1H4 – L4H4 (С=1×10-4 M, methanol)
Complex λ., nm φ×103 τ (СН3ОН),
mcs
τ (СD3ОD),
mcs
q
YbL1H 982; 1004; 1052 3.7 0.62 45.2 1.4
YbL2H 982; 1007; 1050 3.2 0.55 38.4 1.6
YbL3H 978; 1002; 1026 4.0 0.71 52.3 1.2
YbL4H 976: 1024; 1051 2.2 0.41 30.1 2.2
NdL1H 895; 1067; 1075 0.23 0.07 0.42 1.2
NdL3H 895; 1065; 1076 0.18 0.05 0.32 1.8
NdL3H 895; 1065; 1075 0.29 0.09 0.54 0.8
NdL4H 889; 1069; 1073 0.15 0.04 0.30 2.4
Ilum., a.u.
ErL1H 1530 7.8
ErL2H 1530 5.4
ErL3H 1530 9.7
ErL4H 1530 3.6
trum. It is known [11] that the efficiency of
4f-luminescence in lanthanide complexes is
in definite dependence on the energy of the
ligand singlet and triplet levels (Table 3). It
was found that the triplet levels of L1H4 –
L4H4 are higher than the radiating levels of
the lanthanide ions, in particular, Er3+ (4I13/2,
6500 cm-1), Yb3+ (2F5/2, 10300 cm-1) and
Nd3+ (4F3/2, 11460 cm-1), which make possi-
ble an intramolecular energy transfer from
the organic part of the complex to the lan-
thanide ion. The lowest energy (22100 cm-1)
and the maximum lifetime of the triplet level
(344 ms) were registered for the LuL3H
complex. For mono- and di-derivatives, the
energy of the triplet levels is practically the
same, while the lifetime of the latter is half
that of the complex with mono-acid.
The 4f-luminescence of Er3+ ions with a
maximum at 1530 nm (6540 cm-1) corre-
sponding to the 4I13/2 → 4I15/2 transition was
observed for the first time in complexes with
carboxymethoxy derivatives of ca-
lix[4]arenes (Fig. 4). The tendency of the
change in the luminescence intensity in
complexes with erbium is analogous to
changes in the values of the quantum yield
of 4f-luminescence in neodymium and ytter-
bium complexes: ErL3H > ErL1H > ErL2H >
ErL4H.
It was determined that the molecular
fluorescence of carboxymethoxyca-
lix[4]arenes in complexes with Nd3+ is prac-
tically quenched in comparison with luteti-
um-containing complexes, and the 4f-
luminescence characteristic of neodymium
in the near IR region (850-1100 nm) is ob-
served upon excitation into the ligand ab-
sorption band, which indicates the energy
transfer from the organic chromophore to the
S. S. Smola, O. V. Snurnikova, E. A. Alekseeva, T. I. Kirichenko, N. V. Rusakova
16 ISSN 0041-6045. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 3
Fig.4. 4f-Luminescence spectra of Yb(III) com-
plexes (a) with L3H4 (1), L1H4 (2), L2H4 (3),
L4H4 (4); Er(III) complexes (b) with L3H4 (1),
L4H4 (2) (C=1×10-3 M, МеОН, 298 K)
radiating lanthanide ion. Neodymium spectra
with ligands L1H4 - L4H4 are characterized
by bands with a maximum in the range of
889-895 nm (11173 - 11250 cm-1, 4F3/2 →
4I9/2 transition), 1065 - 1069 nm (9350-9400
cm-1) and 1073 - 1076 nm (9250 - 9300 cm-
1), which correspond to the split transition
4F3/2 → 4I11/2. The relative quantum yields
and lifetime of the 4f-luminescence of the
complexes in methanol at room temperature
are (0.15-0.29)×10-3 and 0.04-0.09 μs (Table
4). The decay curves of the Nd3+ ion lumi-
nescence in the studied complexes fit to a
single exponential decay law, which indi-
cates the equivalence of the radiating
centers.
The positions of the maxima and the
structure of the 4f-luminescence spectra of
the ytterbium-containing complexes are due
to the 2F5/2 → 2F7/2 (975-986 nm) transition
and practically coincide for all compounds.
At 77 K, the positions of the maxima in the-
se spectra are shifted (by 20-30 cm-1) to the
long-wavelength region, and the spectra
themselves are split into three components.
Such a splitting is a consequence of the low
symmetry of the coordination polyhedron of
these complexes. The splitting of the 2F7/2
level is 677, 659, 478, 731 cm-1 in complex-
es with L1H4 - L4H4, respectively, that allows
us to conclude that the influence of the lig-
and field of L1H4 and L2H4 is the closest to
the Yb3+ ion. It should be noted that the
quantum yield of 4f-luminescence in ytterbi-
um complexes is higher than that for neo-
dymium compounds. Obviously, the deter-
mining effect in this case is caused by the
vibrations of OH and CH groups of mole-
cules surrounding the lanthanide ion, leading
to non-radiative energy losses (Table 4).
The number of methanol molecules
(q(CH3OH), Table 4) in the inner coordina-
tion sphere of Nd3 + and Yb3+ ions in com-
plexes with L1H4 - L4H4 was determined
based on the lifetime of 4f-luminescence in
CH3OH and CD3OD according to [12]. The
largest number of solvent molecules is char-
acterized by complexes of Nd3+ and Yb3+
with tetra- derivative: 2.2 and 2.4, respec-
tively. In complexes with mono- and di-
derivatives, the coordination sphere of lan-
thanide ions contains practically the same
number of methanol molecules (1.2-1.8),
which indirectly confirms the similarity of
coordination nodes of the corresponding
complexes. As for complexes with a tri-
substituted calix[4]arene, the number of
CH3OH molecules in them is the smallest,
which explains the highest values of the
quantum yields in a series of these com-
pounds.
Authors are grateful to the National
Academy of Sciences of Ukraine for the fi-
nancial support of this work.
CONCLUSIONS. Thus, based on the
combination of the results obtained by
Speculiarities of structure and spectral-luminescent properties…
ISSN 0041-6045. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 3 17
means of elemental analysis, mass spec-
trometry, IR and 1H NMR spectroscopy, and
taking into account the data of pH-metric
titration, spectrophotometric and lumines-
cence measurements, it can be concluded
that lanthanide ions form neutral complexes
of 1:1 ratio with L1H4 - L4H4. This is ex-
plained by the presence of mobile hydrogen
atoms of phenol and/or carboxyl groups in
the molecules of these ligands. An increase
in the number of donor substituents leads to
changes in the number of solvent molecules
in the series L3H4 < L1H4 < L2H4 < L4H4
from 0.8 to 2.4 for neodymium complexes,
from 1.2 to 2.2 - for ytterbium complexes.
Both the quantum yield and lifetime of the
4f-luminescence of the neodymium and yt-
terbium complexes and also the lumines-
cence intensity of the erbium-containing
compounds change in the same order.
ОСОБЛИВОСТІ СТРУКТУРИ ТА СПЕК-
ТРАЛЬНО-ЛЮМІНЕСЦЕНТНИХ ВЛАСТИ-
ВОСТЕЙ КАРБОКСИМЕТОКСИЗАМІ-
ЩЕНИХ КАЛІКС[4]АРЕНІВ ТА ЇХ
КОМПЛЕКСІВ З ЛАНТАНІДАМИ
С.С. Смола, О.В. Снурнікова, О.О.
Алексеєва, T.I. Kіріченко, Н.В. Русакова*
Фізико-хімічний інститут ім. О.В. Богатсь-
кого НАН України, Люстдорфська дорога,
86, Одеса, 65080, Україна
*е-mail: natavrusakova@gmail.com
Досліджено спектрально-люмінесцентні
властивості різних карбоксиметоксизаміще-
них п-трет-бутил-калікс[4]аренів та їх
комплексів з лантанідами (Nd, Er, Yb), які
виявляють 4f-люмінесценцію в ІЧ-області
спектра. Проаналізовано вплив заміщення
фенольних атомів водню карбоксиметоксиг-
рупами на стабільність та спектрально-
люмінесцентні характеристики як лігандів,
так і лантанідних комплексів.
К л ю ч о в і с л о в а: калікс[4]арени,
лантанідвмісні комплекси, люмінесценція у
ближній ІЧ-області
ОСОБЕННОСТИ СТРУКТУРЫ И
СПЕКТРАЛЬНО-ЛЮМИНЕСЦЕНТНЫХ
СВОЙСТВ КАРБОКСИМЕТОКСИ ЗАМЕ-
ЩЕННЫХ КАЛИКС[4]АРЕНОВ И ИХ
КОМПЛЕКСОВ С ЛАНТАНИДАМИ
С.С. Смола, О.В. Снурникова, Е.А. Алексева,
T.И. Kириченко, Н.В. Русакова *
Физико-химический институт им. А.В. Бо-
гатского НАН Украины, Люстдорфская до-
рога, 86, Одесса, 65080, Украина
*е-mail: natavrusakova@gmail.com
Исследованы спектрально-люминесцентные
свойства различных карбоксиметоксизаме-
щенных п-трет-бутил-каликс[4]аренов и их
комплексов с лантанидами (Nd, Er, Yb), ко-
торые проявляют 4f-люминесценцию в ИК-
области спектра. Проанализировано влияние
замещения фенольных атомов водорода кар-
боксиметоксигруппами на стабильность и
спектрально-люминесцентные характеристи-
ки как лигандов, так и лантанидных ком-
плексов.
К л ю ч е в ы е с л о в а: каликс [4] арены,
лантанидные комплексы, люминесценция в
ближней ИК-области
REFERENCES
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mailto:%20natavrusakova@gmail.com
mailto:%20natavrusakova@gmail.com
S. S. Smola, O. V. Snurnikova, E. A. Alekseeva, T. I. Kirichenko, N. V. Rusakova
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Надійшла 16.03.2020
http://www.sciencedirect.com/science/article/pii/S0022231397001130
http://www.sciencedirect.com/science/article/pii/S0022231397001130
http://www.sciencedirect.com/science/article/pii/S0022231397001130
http://www.journal.csj.jp/doi/abs/10.1246/bcsj.63.3480
http://www.journal.csj.jp/doi/abs/10.1246/bcsj.63.3480
http://www.sciencedirect.com/science/article/pii/S0022231396001263
http://www.sciencedirect.com/science/article/pii/S0022231396001263
http://www.sciencedirect.com/science/article/pii/S0022231396001263
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| id | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-132 |
| institution | Ukrainian Chemistry Journal |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-07-23T01:01:54Z |
| publishDate | 2020 |
| publisher | V.I.Vernadsky Institute of General and Inorganic Chemistry |
| record_format | ojs |
| resource_txt_mv | ucjorgua/61/7155eb581af3d41090ab39e05f8f9261.pdf |
| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-1322026-07-22T08:23:42Z PECULIARITIES OF STRUCTURE AND SPECTRAL-LUMINESCENT PROPERTIES OF CARBOXYMETHOXY-SUBSTITUTED CALIX[4]ARENES AND THEIR COMPLEXES WITH LANTHANIDES ОСОБЕННОСТИ СТРУКТУРЫ И СПЕКТРАЛЬНО-ЛЮМИНЕСЦЕНТНЫХ СВОЙСТВ КАРБОКСИМЕТОКСИЗАМЕЩЕННЫХ КАЛИКС[4]АРЕНОВ И ИХ КОМПЛЕКСОВ С ЛАНТАНИДАМИ ОСОБЛИВОСТІ СТРУКТУРИ ТА СПЕКТРАЛЬНО-ЛЮМІНЕСЦЕНТНИХ ВЛАСТИВОСТЕЙ КАРБОКСИМЕТОКСИЗАМІЩЕНИХ КАЛІКС[4]АРЕНІВ ТА ЇХ КОМПЛЕКСІВ З ЛАНТАНІДАМИ Smola, Serhii Rusakova, Nataliia Snurnikova, Olga Alekseeva, Elena Kirichenko, Tatyana calix[4]arenes, lanthanide-containing complexes, NIR-luminescence Spectral-luminescent properties of a variety of carboxymethoxy-substituted p-tert-butyl-calix[4]arenes and their complexes with lanthanides (Nd, Er, Yb) that exhibit the 4f-luminescence in the IR-spectrum region have been investigated. The effect of substitution of hydrogen phenolic atoms by carboxymethoxy groups on the stability and spectral-luminescent characteristics of both the ligands and lanthanide complexes was analyzed. Thus, based on the combination of the results obtained by means of elemental analysis, mass spectrometry, IR and 1H NMR spectroscopy, and taking into account the data of pH-metric titration, spectrophotometric and luminescence measurements, it can be concluded that lanthanide ions form neutral complexes of 1:1 ratio with L1H4 - L4H4. This is explained by the presence of mobile hydrogen atoms of phenol and/or carboxyl groups in the molecules of these ligands. An increase in the number of donor substituents leads to changes in the number of solvent molecules in the series L3H4 &lt; L1H4 &lt; L2H4 &lt; L4H4 from 0.8 to 2.4 for neodymium complexes, from 1.2 to 2.2 - for ytterbium complexes. Both the quantum yield and lifetime of the 4f-luminescence of the neodymium and ytterbium complexes and also the luminescence intensity of the erbium-containing compounds change in the same order. V.I.Vernadsky Institute of General and Inorganic Chemistry 2020-04-07 Article Article Inorganic Chemistry Неорганическая химия Неорганічна хімія application/pdf https://ucj.org.ua/index.php/journal/article/view/132 10.33609/0041-6045.86.3.2020.9-18 Ukrainian Chemistry Journal; Vol. 86 No. 3 (2020): Ukrainian Chemistry Journal; 9-18 Украинский химический журнал; ##issue.vol## 86 ##issue.no## 3 (2020): Украинский химический журнал; 9-18 Український хімічний журнал; Том 86 № 3 (2020): Український хімічний журнал; 9-18 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/132/84 Copyright (c) 2020 Serhii Smola, Nataliia Rusakova, Olga Snurnikova, Elena Alekseeva, Tatyana Kirichenko https://creativecommons.org/licenses/by-nc/4.0 |
| spellingShingle | Smola, Serhii Rusakova, Nataliia Snurnikova, Olga Alekseeva, Elena Kirichenko, Tatyana ОСОБЛИВОСТІ СТРУКТУРИ ТА СПЕКТРАЛЬНО-ЛЮМІНЕСЦЕНТНИХ ВЛАСТИВОСТЕЙ КАРБОКСИМЕТОКСИЗАМІЩЕНИХ КАЛІКС[4]АРЕНІВ ТА ЇХ КОМПЛЕКСІВ З ЛАНТАНІДАМИ |
| title | ОСОБЛИВОСТІ СТРУКТУРИ ТА СПЕКТРАЛЬНО-ЛЮМІНЕСЦЕНТНИХ ВЛАСТИВОСТЕЙ КАРБОКСИМЕТОКСИЗАМІЩЕНИХ КАЛІКС[4]АРЕНІВ ТА ЇХ КОМПЛЕКСІВ З ЛАНТАНІДАМИ |
| title_alt | PECULIARITIES OF STRUCTURE AND SPECTRAL-LUMINESCENT PROPERTIES OF CARBOXYMETHOXY-SUBSTITUTED CALIX[4]ARENES AND THEIR COMPLEXES WITH LANTHANIDES ОСОБЕННОСТИ СТРУКТУРЫ И СПЕКТРАЛЬНО-ЛЮМИНЕСЦЕНТНЫХ СВОЙСТВ КАРБОКСИМЕТОКСИЗАМЕЩЕННЫХ КАЛИКС[4]АРЕНОВ И ИХ КОМПЛЕКСОВ С ЛАНТАНИДАМИ |
| title_full | ОСОБЛИВОСТІ СТРУКТУРИ ТА СПЕКТРАЛЬНО-ЛЮМІНЕСЦЕНТНИХ ВЛАСТИВОСТЕЙ КАРБОКСИМЕТОКСИЗАМІЩЕНИХ КАЛІКС[4]АРЕНІВ ТА ЇХ КОМПЛЕКСІВ З ЛАНТАНІДАМИ |
| title_fullStr | ОСОБЛИВОСТІ СТРУКТУРИ ТА СПЕКТРАЛЬНО-ЛЮМІНЕСЦЕНТНИХ ВЛАСТИВОСТЕЙ КАРБОКСИМЕТОКСИЗАМІЩЕНИХ КАЛІКС[4]АРЕНІВ ТА ЇХ КОМПЛЕКСІВ З ЛАНТАНІДАМИ |
| title_full_unstemmed | ОСОБЛИВОСТІ СТРУКТУРИ ТА СПЕКТРАЛЬНО-ЛЮМІНЕСЦЕНТНИХ ВЛАСТИВОСТЕЙ КАРБОКСИМЕТОКСИЗАМІЩЕНИХ КАЛІКС[4]АРЕНІВ ТА ЇХ КОМПЛЕКСІВ З ЛАНТАНІДАМИ |
| title_short | ОСОБЛИВОСТІ СТРУКТУРИ ТА СПЕКТРАЛЬНО-ЛЮМІНЕСЦЕНТНИХ ВЛАСТИВОСТЕЙ КАРБОКСИМЕТОКСИЗАМІЩЕНИХ КАЛІКС[4]АРЕНІВ ТА ЇХ КОМПЛЕКСІВ З ЛАНТАНІДАМИ |
| title_sort | особливості структури та спектрально-люмінесцентних властивостей карбоксиметоксизаміщених калікс[4]аренів та їх комплексів з лантанідами |
| topic_facet | calix[4]arenes lanthanide-containing complexes NIR-luminescence |
| url | https://ucj.org.ua/index.php/journal/article/view/132 |
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