HOMO- AND HETERONUCLEAR Yb(III) AND Lu(III) COMPLEXES WITH CALIX[4]ARENE MODIFIED WITH PORPHYRIN SUBSTITUENTS.
In this work we describe the approaches for the synthesis of lanthanide-containing homo- and heteronuclear complexes using 5,11,17,23-tetra-tert-butyl-25,27-dihydroxy-26,28-bis[(N-meso-(p-aminophenyl)-meso-triphenylporphyrincarbonyl)methoxy]-calix[4]arene (1). Such spatially preorganizedcalix[4]are...
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| Дата: | 2023 |
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| Автори: | , , , , , |
| Формат: | Стаття |
| Мова: | Англійська |
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V.I.Vernadsky Institute of General and Inorganic Chemistry
2023
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Репозитарії
Ukrainian Chemistry Journal| _version_ | 1871465983284084736 |
|---|---|
| author | Rusakova, Natalia Malinka, Olena Korovin, Oleksandr Smola, Serhii Snurnikova, Olga Rusakova, Mariia |
| author_facet | Rusakova, Natalia Malinka, Olena Korovin, Oleksandr Smola, Serhii Snurnikova, Olga Rusakova, Mariia |
| author_institution_txt_mv | [
{
"author": "Natalia Rusakova",
"institution": "A.V. Bogatsky Physico-chemical Institute National Academy of Sciences of Ukraine"
},
{
"author": "Olena Malinka",
"institution": "Odessa National Academy of Food Technology"
},
{
"author": "Oleksandr Korovin",
"institution": "A.V. Bogatsky Physico-chemical Institute National Academy of Sciences of Ukraine"
},
{
"author": "Serhii Smola",
"institution": "A.V. Bogatsky Physico-chemical Institute National Academy of Sciences of Ukraine"
},
{
"author": "Olga Snurnikova",
"institution": "A.V. Bogatsky Physico-Chemical Institute of the NAS of Ukraine"
},
{
"author": "Mariia Rusakova",
"institution": "I.I. Mechnikov Odessa National University"
}
] |
| author_sort | Rusakova, Natalia |
| baseUrl_str | https://ucj.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-22T08:23:52Z |
| description | In this work we describe the approaches for the synthesis of lanthanide-containing homo- and heteronuclear complexes using 5,11,17,23-tetra-tert-butyl-25,27-dihydroxy-26,28-bis[(N-meso-(p-aminophenyl)-meso-triphenylporphyrincarbonyl)methoxy]-calix[4]arene (1). Such spatially preorganizedcalix[4]arene macrocycle facilitates lanthanide cation coordination, impacting the structure and analytical signal of porphyrin substituents. The study employs two synthesis strategies resulting in mononuclear and homobinuclear complexes, influenced by steric effects and changes in hydrogen bonding. The complexes exhibit changes in fluorescence spectra due to intramolecular dimerization and hydrogen bonding during complex formation. Mononuclear complexes (Ln-1) are synthesized under mild conditions, while homobinuclear complexes (Ln2-1) require high-boiling solvents and specific reaction conditions, detailed synthesis procedures are described. The structural changes during complex formation were analyzed with the use of NMR analysis. The absorption spectra of lanthanide complexes demonstrate shifts in maxima, reflecting coordination changes, with notable variations between mononuclear and homobinuclear complexes. Additionally, heteronuclear compounds with copper(II), zinc(II), and palladium(II) exhibit distinctive absorption patterns, emphasizing the role of d-metal ions. Luminescence studies reveal the sensitization of 4f-luminescence by both calix[4]arene and porphyrin fragments. The use of deuterated solvents enhances 4f-luminescence intensity, highlighting solvent effects. Furthermore, 4f-luminescence characteristics were investigated in both solid and solution states for heterometallic compounds, emphasizing differences between copper-containing and zinc/palladium-containing complexes. The results offer valuable insights into the design, synthesis, and spectral properties of these complexes, showcasing their potential applications in various fields, and the findings contribute to the understanding of lanthanide-porphyrin systems and their coordination behavior. |
| doi_str_mv | 10.33609/2708-129X.89.09.2023.52-63 |
| first_indexed | 2025-09-24T17:43:53Z |
| format | Article |
| fulltext |
52 ISSN 2708-129X. Укр. хім. журн., 2023
UDC: 546.482:546.793:547.44(043.3) doi: 10.33609/2708-129X.89.09.2023.52-63
HOMO- AND HETERONUCLEAR Yb(III) AND Lu(III) COMPLEXES WITH
CALIX[4]ARENE MODIFIED WITH PORPHYRIN SUBSTITUENTS.
N.V. Rusakova1*, O.V. Snurnikova1, S.S. Smola1,
O.Yu. Korovin1, E.V. Malinka2, M.Yu. Rusakova3
1O.V. Bogatsky Physico-Chemical Institute of the National Academy of Sciences of Ukraine;
86 Lustdorfska road, 65080 Odesa, Ukraine
2Odessa National University of Technology,
112 Kanatna Street, 65039 Odesa, Ukraine;
3I.I. Mechnikov Odesa National University;
2 Dvoryanskaya Street, 65082 Odesa, Ukraine
*е-mail: natavrusakova@gmail.com
In this work we describe the approaches for the synthesis of lanthanide-containing homo- and
heteronuclear complexes using 5,11,17,23-tetra-tert-butyl-25,27-dihydroxy-26,28-bis[(N-meso-
(p-aminophenyl)-meso-triphenylporphyrincarbonyl)methoxy]-calix[4]arene (1). Such spatially
preorganized calix[4]arene macrocycle facilitates lanthanide cation coordination, impacting the
structure and analytical signal of porphyrin substituents. The study employs two synthesis stra
tegies resulting in mononuclear and homobinuclear complexes, influenced by steric effects and
changes in hydrogen bonding. The complexes exhibit changes in fluorescence spectra due to in-
tramolecular dimerization and hydrogen bonding during complex formation. Mononuclear com-
plexes (Ln-1) are synthesized under mild conditions, while homobinuclear complexes (Ln2-1)
require high-boiling solvents and specific reaction conditions, detailed synthesis procedures are
described. The structural changes during complex formation were analyzed with the use of NMR
analysis. The absorption spectra of lanthanide complexes demonstrate shifts in maxima, reflect-
ing coordination changes, with notable variations between mononuclear and homobinuclear
complexes. Additionally, heteronuclear compounds with copper(II), zinc(II), and palladium(II)
exhibit distinctive absorption patterns, emphasizing the role of d-metal ions. Luminescence stu
dies reveal the sensitization of 4f-luminescence by both calix[4]arene and porphyrin fragments.
The use of deuterated solvents enhances 4f-luminescence intensity, highlighting solvent effects.
Furthermore, 4f-luminescence characteristics were investigated in both solid and solution states
for heterometallic compounds, emphasizing differences between copper-containing and zinc/pal-
ladium-containing complexes. The results offer valuable insights into the design, synthesis, and
spectral properties of these complexes, showcasing their potential applications in various fields,
and the findings contribute to the understanding of lanthanide-porphyrin systems and their co-
ordination behavior.
Key words: lanthanide, complexes, calix[4]arene, porphyrin, synthesis, luminescence.
53https://ucj.org.ua
N.V. Rusakova, O.V. Snurnikova, S.S. Smola, O.Yu. Korovin, E.V. Malinka, M.Yu. Rusakova UCJ № 09 / Vol. 89
INTRODUCTION. One of the most im-
portant incentives for research in the field of
lanthanide chemistry is their ability to form
luminescent compounds with various organic
chromophore ligands. The luminescent pro
perties of such compounds depend on the na-
ture of the f-metal chromophore and ligand,
the environment, and other factors. 4f-lu-
minescence in the near infrared (IR) range
is highly demanded in medicine (biomarker
technology) for a number of important rea-
sons: the complete absence of absorption and
luminescence overlap of biological objects in
certain wavelength regions of this range [1, 2].
The IR range is safe for humans compared
to the UV / visible range; IR photons scatter
much less than UV/visible light.
Infrared research is also being stimulated
by the defense sector's demand for all military
night vision equipment: binoculars, drones,
armored vehicles, infrared goggles, etc. Lan-
thanide compounds are now widely used for
security purposes, in fiber optic telecommuni-
cations networks.
Heteronuclear lanthanide-containing com-
plexes have recently attracted increasing atten-
tion not only due to their optical, but also mag-
netic and catalytic properties. In most works
devoted to such complexes, as a rule, acyclic
ligands containing chromophore fragments
were studied [3−5].
Functionalization of macrocyclic ligands by
chelating fragments is one of the most promi
sing directions in the design of heteronuclear
lanthanide complexes. At the same time, such
classes of compounds as calix[4]arenes and
porphyrins, due to the presence of extended
π-electron system, can be considered as con-
venient molecular platforms for creating he
teronuclear complexes that luminesce in the
visible (calix[4]arenes) and near-IR region
(porphyrins).
Calix[4]arenes are used as molecular scaf-
folds for constructing three-dimensional re-
ceptors in combination with porphyrin frag-
ments via covalent bonds [6, 7]. Functiona
lization of phenolic hydroxyl groups in por-
phyrin-calix[4]arenes conjugates leads to a
multiple increase in their receptor ability [8] as
well as makes it possible to successfully apply a
wide range of spectral methods to study inter-
molecular interactions.
Tetrapyrroles are one of the optimal com-
pounds for obtaining objects emitting in the IR
range (macrocycles themselves are character-
ized by intense absorption in the UV and visible
regions of the spectrum). Low-energy donor
triplet T-levels provide efficient intramolecular
energy transfer to resonant levels of lanthanide
ions emitting in the IR range, among which
Nd(III), Er(III), Yb(III) have the most inten-
sive signal [9]. The synthesis and study of com-
plex compounds with tetrapyrroles having se-
veral donor centers are of interest in connec-
tion with the possibility of their use as primary
molecular blocks for constructing more com-
plex polynuclear systems with a given struc-
ture and predictable properties. The presence
of metal centers of different nature in such
complexes makes it possible to control the pos-
sibility of effective luminescence of both the li-
gand itself and the lanthanide ion. In this case,
the choice of a strategy for the synthesis of such
compounds is of particular importance.
The purpose of this work is to develop ap-
proaches to the synthesis of new lanthanide-con-
taining homo- and heteronuclear complexes
based on 5,11,17,23-tetra-tert-butyl-25,27-di
hydroxy-26,28-bis[(N-meso-(p-aminophenyl)-
meso-triphenylporphyrincarbonyl)methoxy]-
54 ISSN 2708-129X. Укр. хім. журн., 2023
HOMO- AND HETERONUCLEAR Yb(III) AND Lu(III) COMPLEXES WITH CALIX[4]ARENE
MODIFIED WITH PORPHYRIN SUBSTITUENTS.INORGANIC CHEMISTRY
calix[4]arene (1) and establishing the influence
of the structure of the obtained complexes on
their spectral characteristics.
EXPERIMENT AND RESULTS DISCUS-
SION. Synthesis of 5,11,17,23-tetra-tert-butyl-
25,27-dihydroxy-26,28-bis[(N-meso-(p-ami-
nophenyl)-meso-triphenylporphyrincarbonyl)-
methoxy]calix[4]arene (1) was carried out with
the use carboxymethoxycalix[4]arene(2) and
p-monoamino-meso-tetraphenylporphyrin (3)
as starting reagents according to [10]. The dif-
ference of the proposed technique is the use of
low temperature (-10−(-15)ºС) to exclude the
formation of by-products, which lead to the in-
crease of the yield of the ligand up to 75−80%.
5,11,17,23-tetra-tert-butyl-25,27-dihyd-
roxy-26,28-bis[(N-meso-(p-aminophenyl)-
meso-triphenylporphyrincarbonyl)methoxy]
calix[4]arene, ESI-MS: 1988 (11%) [М+2],
670 (82%), 628 (100%). NMR 1H: (300 MHz,
CDCl3): 2.81 (s, 4Н, NHpyr.), 1.18 (s, 18Н,
(СН3)3С), 1.31 (s, 18 Н, (СН3)3С), 3.69 (d, 4Н,
ArCH2Ar), 4.48 (d, 4Н, ArCH2Ar), 4.94 (s,
4Н, OCH2СО), 7.15 (s, 4Н, ArH), 7.22 (s, 4Н,
ArН), 7.65−7.76 (m, 20 Н, СНporf.), 8.12−8.18
(m, 10Н, СНporf.), 8.27 (d, 8Н, СНporf.), 8.78
(s, 8Н, ArНporf.), 8.83 (s, 2Н, 2ОН), 8.88 (d,
4Н, СНporf), 9.17 (d, 4Н, СНporf), 11.11 (s, 2Н,
NHCO).
The main idea behind the design of calix[4]
arene-porphyrin systems is that a spatially pre-
organized calix[4]arene macrocycle accepts a
lanthanide cation consequently changing the
structure and the analytical signal of porphy-
rin substituents. The interaction of the orbi
tals of the porphyrin rings (intramolecular di-
merization) and the intramolecular hydrogen
bonds between the amide groups keep these
substituents close to each other, whereas, dur-
ing complex formation along the lower rim of
the calixarene, the distance between the por-
phyrin fragments increases. These changes are
observed in the fluorescence spectra.
Depending on the synthesis strategy with
calix[4]arene-diporphyrin (1), two types of
complexes were obtained. The first type, a
mononuclear complex Ln-1 was synthesized
using lanthanide hexachlorides (LnCl3×6H2O),
with the participation of donor groups of the
lower rim of calixarene (Fig. 1a, Ln = Yb(III),
Lu(III)). The second type, a homobinuclear
complex Ln2-1 was synthesized by the interac-
tion of lanthanide porphyrinates Ln-3 with di-
carboxymethoxy-calix[4]arene (2) − (Fig. 1b).
In contrast to the previously described me
thods [11], the complexation reaction with
porphyrin-calix[4]arenes was carried out in
the presence of equimolar amounts of triethyl-
amine. Higher temperature conditions and an
increase in reaction time are probably caused
by the steric effects of bulky substituents, as
well as changes in the system of hydrogen
bonds between them. The yield of complexes
is 60−65%.
Lanthanide chloride (0.15 mmol) LnCl3×
6H2O was dissolved under heating in 15 ml
of acetonitrile and boiled in the presence
of triethyl orthoformate (TEOF, 0.5 ml) for
30 min. Then an equimolar amount of ligand 1
(0.15 mmol) was added. The reaction mixture
was stirred until the ligand was completely dis-
solved, and then triethylamine (0.1 ml) was
added and boiled for 4.5−5 hours. After the
end of the synthesis, the solvent was removed.
The obtained solid product was dissolved in
chloroform (15−20 ml) and washed with wa-
ter (3×20 ml). The organic fraction was evapo
rated, the complex was dried at 110−120°C
for 3.5−4 hours. The yield of complexes is
70−72%.
55https://ucj.org.ua
N.V. Rusakova, O.V. Snurnikova, S.S. Smola, O.Yu. Korovin, E.V. Malinka, M.Yu. Rusakova UCJ № 09 / Vol. 89
Fig. 1 − Scheme of synthesis of mono- (a) and binuclear (b) complexes based on calix[4]arene-dipor-
phyrin.
3
Depending on the synthesis strategy with calix[4]arene-diporphyrin (1), two types of
complexes were obtained. The first type, a mononuclear complex Ln-1 was synthesized using
lanthanide hexachlorides (LnCl3×6H2O), with the participation of donor groups of the lower rim
of calixarene (Fig. 1a, Ln = Yb(III),Lu(III)). The second type, a homobinuclear complex Ln2-1
was synthesized by the interaction of lanthanide porphyrinates Ln-3 with dicarboxymethoxy-
calix[4]arene (2) − (Fig. 1b). In contrast to the previously described methods [11], the
complexation reaction with porphyrin-calix[4]arenes was carried out in the presence of
equimolar amounts of triethylamine. Higher temperature conditions and an increase in reaction
time are probably caused by the steric effects of bulky substituents, as well as changes in the
system of hydrogen bonds between them. The yield of complexes is 60−65%.
Fig. 1 − Scheme of synthesis of mono- (a) and binuclear (b) complexes based on calix[4]arene-
diporphyrin.
Lanthanide chloride (0.15 mmol) LnCl3×6H2O was dissolved under heating in 15 ml of
acetonitrile and boiled in the presence of triethylorthoformate (TEOF, 0.5 ml) for 30 min. Then
an equimolar amount of ligand 1 (0.15 mmol) was added. The reaction mixture was stirred until
the ligand was completely dissolved, and then triethylamine (0.1 ml) was added and boiled for
4.5−5 hours. After the end of the synthesis, the solvent was removed. The obtained solid product
was dissolved in chloroform (15−20 ml) and washed with water (3×20 ml). The organic fraction
was evaporated, the complex was dried at 110−120°C for 3.5−4 hours. The yield of complexes is
70−72%.
Yb-1, [Yb(1)(CH3CN)Cl], Elemental analysis for C138H119N11ClO6Yb: Сalculated %: C,
74.1, H, 5.4, Ln, 7.7; Cl, 1.6; Found, %: C, 74.2, H, 5.7, Ln, 7.9; Cl, 1.4. MS (MALDI), m/z:
2235 [(M+H)+].
Lu-1, [Yb(1)(CH3CN)Cl], Elemental analysis for C138H119N11ClO6Lu: Сalculated %: C,
74.1, H, 5.4, Ln, 7.8; Cl, 1.6; Found, %: C, 73.9, H, 5.3, Ln, 8.0; Cl, 1.5. MS (MALDI), m/z:
2237 [(M+H)+].
Synthesis of Ln2-1 homobinuclear complexes was carried out from the corresponding Ln-
3 lanthanide porphyrinates [9]. A sample (0.17 mmol) of 2 was dissolved in 10 ml of methylene
Yb-1, [Yb(1)(CH3CN)Cl], Elemental ana
lysis for C138H119N11ClO6Yb: Сalculated %: C,
74.1, H, 5.4, Ln, 7.7; Cl, 1.6; Found, %: C, 74.2,
H, 5.7, Ln, 7.9; Cl, 1.4. MS (MALDI), m/z: 2235
[(M+H)+].
Lu-1, [Yb(1)(CH3CN)Cl], Elemental ana
lysis for C138H119N11ClO6Lu: Сalculated %: C,
74.1, H, 5.4, Ln, 7.8; Cl, 1.6; Found, %: C, 73.9,
H, 5.3, Ln, 8.0; Cl, 1.5. MS (MALDI), m/z: 2237
[(M+H)+].
Synthesis of Ln2-1 homobinuclear com-
plexes was carried out from the corresponding
Ln-3 lanthanide porphyrinates [9]. A sam-
ple (0.17 mmol) of 2 was dissolved in 10 ml
of methylene chloride, cooled to 0−(-3)ºС,
and dicyclohexylcarbodiimide (6.82 mmol)
was added. The resulting mixture was stirred
while cooling for 10−15 minutes, then the
required amount of lanthanide porphyrinate
Ln-3 (0.34 mmol) was added, and stirring was
continued for more than three hours. The re-
action progress was monitored by thin-layer
chromatography in chloroform-hexane-ace-
tonitrile (10:10:1). To remove cyclohexylurea,
the reaction mixture was kept at a tempera-
ture of -10–(-15)ºС for 10−12 hours, the re-
sulting precipitate was filtered off. The mo
ther liquor was evaporated and the dry resi-
due was dissolved in a minimal amount of a
mixture of chloroform-hexane-acetonitrile
(10:10:1). The resulting solution was passed
through a column packed with silica gel
using the above mentioned mixture as eluent.
Yield 50−56%.
56 ISSN 2708-129X. Укр. хім. журн., 2023
HOMO- AND HETERONUCLEAR Yb(III) AND Lu(III) COMPLEXES WITH CALIX[4]ARENE
MODIFIED WITH PORPHYRIN SUBSTITUENTS.INORGANIC CHEMISTRY
Yb2-1, [Yb2(1)(CH3CN)2Cl2], Elemental
analysis for C140H120N12Cl2O6Yb2: Сalculated,
%: C, 67.7, H, 4.9, Ln, 13.9; Cl, 2.9; Found, %:
C, 67.6, H, 5.1, Ln, 14.1; Cl, 2.7. MS (MALDI),
m/z: 2483 [(M+H)+].
Lu2-1, [Lu2(1)(CH3CN)2Cl2], Elemental
analysis for C140H120N12Cl2O6Lu2: Calculated,
%: C, 67.6, H, 4.9, Ln, 14.1; Cl, 2.9; Found,% :
C, 67.5, H, 4.7, Ln, 14.3; Cl, 3.1. MS (MALDI),
m/z: 2485 [(M+H)+].
Elemental analysis data of the homonuclear
compounds were confirmed by 1Н NMR spec-
tra of complexes with diamagnetic lutetium ion
and make it possible to identify some structural
changes that occur during complex formation.
The disappearance of the signals of the protons
of the phenolic groups of Lu-1 is a consequence
of their replacement by a lanthanide ion, and the
shift of the signals of the protons of the O-CH2-
CO groups of the complex to the low field (∆δ =
0.37 ppm) indicates the participation of oxygen
atoms of ether groups in the formation metal
ion coordination site. The signals from protons
of methylene bridges at 3.40 and 3.75 ppm for
Lu-1, (3.69 and 4.48 ppm for 1) with the values
of the difference between them (∆δ = 0.35 and
0.79 ppm, respectively), indicates a decrease in
the distortion of the calix[4]arene macrocycle
in the complex compared to the ligand. As for
the complex Lu2-1, in which the lanthanide ion
is coordinated by the pyrrole nitrogen atoms,
in the NMR spectrum there are no significant
changes in the bands of the calix[4]arene com-
ponent compared to the ligand. At the same
time, the signals of the NH protons of the pyrrole
fragments disappear, which indicates their sub-
stitution during complex formation, and the
signals of the protons located in the β-positions
of the porphyrins shift to the low field, which is
a consequence of a redistribution of the elect
ron density in the porphyrinate fragments.
Heteronuclear compounds were synthesi
zed with the use of mononuclear complexes of
copper (II), zinc (II) and palladium (II)with va-
cant donor groups. The choice of d-metals was
determined both by the specifics of their comp
lexation with the porphyrin macrocycle and by
the spectral features of the metal ions. Selec-
tive introduction of the lanthanide ion into the
lower rim of the calix[4]arene or into the ca
vity of the porphyrinate substituent was reali
zed due to significant differences in the condi-
tions of complex formation. The formation of
complexes of Ln(III) with calix[4]arenes takes
place under relatively mild conditions, and the
preparation of lanthanide-porphyrins requires
the use of high-boiling solvents [9, 12, 13].
The synthesis was carried out according
to the scheme presented in Fig. 2. The reac-
tion mixture was boiled for 5−6 hours and
left overnight at room temperature. The com-
plex was precipitated with ethanol (50 ml), the
precipitate was filtered, washed with ethanol
(3×50 ml). They were dried at room tempe
rature for a day in a vacuum desiccator. The
yields of target products were 48−54%.
Yb-Cu2-1, [YbCu2(1)(CH3CN)Cl]. Elemen-
tal analysis for C138H115N11ClO6YbCu2: Calcu-
lated, %: С, 70.3; H, 4.9; Yb, 7.3; Cu, 5.4; Cl, 1.5;
Found,%: C, 70.5; H, 5.1;Yb, 7.4; Cu, 5.5; Cl,
1.3. MS (МАLDI), m/z: 2357 [(M+Н)+].
Lu-Cu2-1, [LuCu2(1)(CH3CN)Cl]. Elemen-
tal analysis for C138H115N11ClO6LuCu2: Calcu-
lated, %: С, 70.2; H, 4.9; Lu, 7.4; Cu, 5.4; Cl, 1.5;
Found,% : C, 70.0; H, 5.1;Lu, 7.6; Cu, 5.2; Cl,
1.6. MS (МАLDI), m/z: 2358 [(M+Н)+].
Yb-Zn2-1, [YbZn2(1)(CH3CN)Cl]. Elemen-
tal analysis for C136H112N10ClO6YbZn2: Calcu-
lated, %: С, 70.2; H, 4.9; Yb, 7.3; Zn, 5.5; Cl,
1.5; Found, %: C, 70.3; H, 5.1; Yb, 7.5; Zn, 5.6;
Cl, 1.7. MS (МАLDI), m/z: 2359 [(M+Н)+].
57https://ucj.org.ua
N.V. Rusakova, O.V. Snurnikova, S.S. Smola, O.Yu. Korovin, E.V. Malinka, M.Yu. Rusakova UCJ № 09 / Vol. 89
Fig. 2 − Scheme of synthesis of heteronuclear complexes.
M = Cu(II), Zn(II), Pd(II); Ln = Yb(III), Lu(III)
5
Fig. 2 − Scheme of synthesis of heteronuclear complexes. M = Cu(II), Zn(II), Pd(II); Ln = Yb(III),
Lu(III)
Yb-Cu2-1, [YbCu2(1)(CH3CN)Cl]. Elemental analysis for C138H115N11ClO6YbCu2:
Calculated, %: С, 70.3; H, 4.9; Yb, 7.3; Cu, 5.4; Cl, 1.5; Found,%: C, 70.5; H, 5.1;Yb, 7.4; Cu,
5.5; Cl, 1.3. MS (МАLDI), m/z: 2357 [(M+Н)+].
Lu-Cu2-1, [LuCu2(1)(CH3CN)Cl]. Elemental analysis for C138H115N11ClO6LuCu2:
Calculated, %: С, 70.2; H, 4.9; Lu, 7.4; Cu, 5.4; Cl, 1.5; Found,% : C, 70.0; H, 5.1;Lu, 7.6; Cu,
5.2; Cl, 1.6. MS (МАLDI), m/z: 2358 [(M+Н)+].
Yb-Zn2-1, [YbZn2(1)(CH3CN)Cl]. Elemental analysis for C136H112N10ClO6YbZn2:
Calculated, %: С, 70.2; H, 4.9; Yb, 7.3; Zn, 5.5; Cl, 1.5; Found, %: C, 70.3; H, 5.1; Yb, 7.5; Zn,
5.6; Cl, 1.7. MS (МАLDI), m/z: 2359 [(M+Н)+].
Lu-Zn2-1, [LuZn2(1)(CH3CN)Cl]. Elemental analysis for C136H112N10ClO6LuZn2:
calculated, %: С, 70.1; H, 4.9; Lu, 7.4; Zn, 5.5; Cl, 1.5; Found, %: C, 70.3; H, 5.0; Lu, 7.5; Zn,
5.7; Cl, 1.7. MS (МАLDI), m/z: 2360 [(M+Н)+]. NMR 1H (CDCl3), ppm: 1.18 (s, 18H,
(СН3)3С), 1.32 (s, 18H, (СН3)3С), 3.49 (d, 4H, ArCН2Ar), 4.20 (d, 4H, ArCН2Ar), 4.92 (s, 4H,
OCH2СО), 7.15 (s, 4H, ArH), 7.23 (s, 4Н, ArH), 7.51−7.70 (m, 20Н, СНporph.), 8.12−8.18 (m,
10Н, СНporph.), 8.27 (d, 8Н, СНporph.), 8.70 (s, 8Н, СНporph.), 8.85−8.88 (m, 4Н, СНporph.), 8.93 (d,
2Н, NHCO), 9.27 (d, 4Н, СНporph.)
Yb-Pd2-1, [LuPd2(1)(CH3CN)Cl]. Elemental analysis for C138H115N11ClO6YbPd2:
Calculated, %: С, 67.8; H, 4.7; Yb, 7.1; Pd, 8.7; Cl, 1.5; Found, %: C, 67.7; H, 4.7; Yb, 7.1; Pd,
8.9; Cl, 1.6. MS (МАLDI), m/z: 2443 [(M+Н)+].
Lu-Pd2-1, [LuPd2(1)(CH3CN)Cl]. Elemental analysis for C138H115N11ClO6LuPd2:
Calculated, %: С, 67.8; H, 4.7; Lu, 7.1; Pd, 8.7; Cl, 1.5; Found, %: C, 67.7; H, 4.9; Lu, 7.3; Pd,
8.9; Cl, 1.6. MS (МАLDI), m/z: 2444 [(M+Н)+].
The formation of lanthanide complexes with 1 leads to changes in the shape, intensity, and
position of the absorption spectra maxima (Table 1). When the Lu(III) ion is coordinated at the
lower rim of the calix[4]arene component of 1, the absorption spectra of the Lu-1 complex
change significantly, both in comparison with the ligand and the lutetium-containing complex of
the initial calixarene Lu-2. In the UV region for the Lu-1 complex, a broadened but not split
band with a maximum at 280 nm and a second band at 312 nm are detected, which confirms the
coordination of the lanthanide ion by phenolic groups. In this case, a bathochromic shift (5 nm)
of the first band and a hypsochromic (8 nm) shift of the second band relative to the spectrum of
the dicarboxycalix[4]arene complex are observed.
Porphyrin-originated bands maxima and intensity in the spectrum of Lu-1 (410−650 nm
region) practically do not change compared to the ligand, which indicates a slight change in the
position of the porphyrin substituents relative to each other in the complex compared to the free
ligand. It should be noted that the absorption spectra of complexes with ytterbium and lutetium
Lu-Zn2-1, [LuZn2(1)(CH3CN)Cl]. Elemen-
tal analysis for C136H112N10ClO6LuZn2: calcula
ted, %: С, 70.1; H, 4.9; Lu, 7.4; Zn, 5.5; Cl, 1.5;
Found, %: C, 70.3; H, 5.0; Lu, 7.5; Zn, 5.7; Cl,
1.7. MS (МАLDI), m/z: 2360 [(M+Н)+]. NMR
1H (CDCl3), ppm: 1.18 (s, 18H, (СН3)3С), 1.32
(s, 18H, (СН3)3С), 3.49 (d, 4H, ArCН2Ar), 4.20
(d, 4H, ArCН2Ar), 4.92 (s, 4H, OCH2СО), 7.15
(s, 4H, ArH), 7.23 (s, 4Н, ArH), 7.51−7.70
(m, 20Н, СНporph.), 8.12−8.18 (m, 10Н,
СНporph.), 8.27 (d, 8Н, СНporph.), 8.70 (s, 8Н,
СНporph.), 8.85−8.88 (m, 4Н, СНporph.), 8.93 (d,
2Н, NHCO), 9.27 (d, 4Н, СНporph.)
Yb-Pd2-1, [LuPd2(1)(CH3CN)Cl]. Elemen-
tal analysis for C138H115N11ClO6YbPd2: Calcu-
lated, %: С, 67.8; H, 4.7; Yb, 7.1; Pd, 8.7; Cl, 1.5;
Found, %: C, 67.7; H, 4.7; Yb, 7.1; Pd, 8.9; Cl,
1.6. MS (МАLDI), m/z: 2443 [(M+Н)+].
Lu-Pd2-1, [LuPd2(1)(CH3CN)Cl]. Elemen-
tal analysis for C138H115N11ClO6LuPd2: Calcu-
lated, %: С, 67.8; H, 4.7; Lu, 7.1; Pd, 8.7; Cl, 1.5;
Found, %: C, 67.7; H, 4.9; Lu, 7.3; Pd, 8.9; Cl,
1.6. MS (МАLDI), m/z: 2444 [(M+Н)+].
The formation of lanthanide complexes
with 1 leads to changes in the shape, intensity,
and position of the absorption spectra maxima
(Table 1). When the Lu(III) ion is coordinated
at the lower rim of the calix[4]arene compo-
nent of 1, the absorption spectra of the Lu-1
complex change significantly, both in compar-
ison with the ligand and the lutetium-contain-
ing complex of the initial calixarene Lu-2. In
the UV region for the Lu-1 complex, a broade
ned but not split band with a maximum at
280 nm and a second band at 312 nm are de-
tected, which confirms the coordination of the
lanthanide ion by phenolic groups. In this case,
a bathochromic shift (5 nm) of the first band
and a hypsochromic (8 nm) shift of the second
band relative to the spectrum of the dicarboxy-
calix[4]arene complex are observed.
Porphyrin-originated bands maxima and
intensity in the spectrum of Lu-1 (410−650 nm
region) practically do not change compared to
the ligand, which indicates a slight change in
the position of the porphyrin substituents rel-
ative to each other in the complex compared
to the free ligand. It should be noted that the
58 ISSN 2708-129X. Укр. хім. журн., 2023
HOMO- AND HETERONUCLEAR Yb(III) AND Lu(III) COMPLEXES WITH CALIX[4]ARENE
MODIFIED WITH PORPHYRIN SUBSTITUENTS.INORGANIC CHEMISTRY
absorption spectra of complexes with ytter-
bium and lutetium ions coincide, which indi-
cates their identical structure.
In the absorption spectrum of the Lu2-1
complex some characteristic changes during
the formation of metal porphyrinates were
observed such as a bathochromic shift of the
Soret band (Δλ = 7 nm) compared to 1 as well
as the presence of only two bands in the visible
region instead of four in 1. The absorption of
the calix[4]arene component, in comparison
with the ligand, does not undergo changes in
complexes of this type.
4f-Luminescence excitation spectra of
Yb(III) complexes appear to be similar to the
absorption spectra of the corresponding com-
pounds. The observed similarity indicates an
intramolecular excitation energy transfer from
the organic part of the complex molecule to
the resonance levels of Yb(III)ions. Howe
ver, in these objects it was interesting to trace
changes not only in the 4f-luminescent charac-
teristics of ytterbium-containing compounds,
but also in the fluorescence and phosphores-
cence spectra of complexes with diamagnetic
lutetium ions.
Table1.
Spectral-luminescent characteristics of homo- and heteronuclear complexes of Lu(III)
(С=1·10-5M, DMF).
Compound λmax, nm / (lgε) λfl, nm ES, cm-1 λphos,nm ET, cm-1
1 274 (3.8), 410/417 (4,2/4.8), 515 (3.6), 550 (3.3),
590 (3.1), 644 (2.9)
650, 718 15 390 845 11830
Lu-1 280(3.4), 312 (2.5), 418 (5.1),516 (4.2), 552 (3.8),
591 (3.5)648 (3.4)
652
710
15 500 845 11 800
Lu2-1 278 (3.8), 425 (4.9), 557 (3.5), 595 (3.1) 648
715
15 400 852 11 700
Lu-Cu2-1 279 (3.6), 312 (2.6), 416 (5.28), 541(4.23),
576 (3.53)
610 16 390 820 12 200
Lu-Zn2-1 280 (3.3), 314 (2.5), 423 (5.24), 560 (4.26),
602 (3.90)
602
656
16 600 780 12 800
Lu-Pd2-1 280 (3.3), 312 (2.6), 415 (5.53), 517 (4.75),
563 (sh)
562, 605 17 800 685 14 600
Lu-2 273 (3.6), 276 (3.5), 320 (2.6) 406 24 600 420 23 800
Lu-3 425 (4.8), 557 (3.3), 597 (3.0) 624
682
16 000 858 11 700
It should be noted that the ligand-centered
luminescence from the calix[4]arene compo-
nent is not observed in the spectrum of Lu-1
complex. At the same time, fluorescence bands
with maxima at 652 and 710 nm and low-tem-
perature phosphorescence bands with a maxi
mum at 845 nm, characteristic for the por-
phyrin macrocycle, were recorded. This fact is
probably associated with the additional energy
transfer from the triplet levels of the calix[4]
arene component to the corresponding levels
of porphyrinate substituents.
59https://ucj.org.ua
N.V. Rusakova, O.V. Snurnikova, S.S. Smola, O.Yu. Korovin, E.V. Malinka, M.Yu. Rusakova UCJ № 09 / Vol. 89
Fig. 3 − 4f-Luminescence spectra of Yb2-1 (1),
Yb-3 (2), Yb-1(3) and Yb-2 (4) (СYb = 1×10-5M,
DMF, 278К).
The 4f-luminescence of the mononuclear
complex Yb-1 is 1.3 times more intense than
that of a similar complex with calixarene. The
maximum of the 4f-emission varies from 976
to 985 nm. When the complex is excited in
Soret band (417−425 nm), a 4f-luminescent
signal is detected, the intensity of which is very
low.
Insignificant changes in the energies of
singlet and triplet levels compared to 1 are
revealed in the fluorescence and phosphores-
cence spectra of the binuclear complex Lu2-1
(Table 1). However, it should be noted that the
energies of the the excited singlet and triplet
levels differ from the original “block” Lu-3.
The values of the energy of the triplet levels
of calix[4]arene (~23800 cm-1) and porphyrin
(~11700 cm-1) are higher than the emitting
level of ytterbium Yb(III) (2F5/2, 10300 cm-1),
which makes intramolecular energy transfer
possible from the macrocyclic components of
the complex to the lanthanide ion. In the IR
region, due to the 4f-luminescence of Yb(III)
ions, the energy transfer occurs in both mono
nuclear and binuclear complexes (Table 2).
When excited in Soret band, they lead to lu-
minescence of Yb2-1 almost twice as high as
that of the original “block” Yb-3 under simi-
lar conditions. Moreover, 4f-luminescence of
the binuclear complexYb2-1 is observed upon
320 nm excitation, which is the band of the ca-
lix[4]arene “block”, and its intensity is almost
the same as the signal excited in Soret band.
Thus, it can be assumed that in this complex
4f-luminescence is sensitized not only by por-
phyrin, but also by calix[4]arene fragments.
Table 2.
4f-Luminescent parameters of the homo-
nuclear Yb(III) complexes (С =1·10-5 M, DMF).
Complex λmax, nm φ
Yb-1 985, 1008, 1036 0.0032
Yb2-1 978, 1007, 1026 0.0047
Yb-2 982, 1003, 1027 0.0028
Yb-3 976, 1005, 1024 0.0042
In order to minimize the influence of OH-
and CH-vibrations of solvent molecules, a
series of solutions with different contents of
deuterated solvent were studied. It was shown
that with increasing of the concentration of
DMSO-d6 and DMF-d6, the luminescence in-
tensity continuously grows up: more smooth-
ly for the Yb-1 complex (Fig. 4, a), while for
Yb2-1 a sharp increase in intensity is observed
at DMSO-d6 concentrations above 60 vol.%
(Fig. 4, b).The use of deuterated solvents
leads to an increase in the intensity of ytter-
bium 4f-luminescence by 5.5 and 2.3 times in
DMSO-d6 or by 3.6 and 2.0 times in DMF-d6
for Yb2-1 and Yb-1, respectively.
7
Fig. 3 − 4f-Luminescence spectra of Yb2-1 (1), Yb-3 (2), Yb-1(3) иYb-2 (4) (СYb = 110-5M, DMF,
278К).
The 4f-luminescence of the mononuclear complex Yb-1 is 1.3 times more intense than that
of a similar complex with calixarene. The maximum of the 4f-emission varies from 976 to 985
nm. When the complex is excited in Soret band (417−425 nm), a 4f-luminescent signal is
detected, the intensity of which is very low.
Insignificant changes in the energies of singlet and triplet levels compared to 1 are
revealed in the fluorescence and phosphorescence spectra of the binuclear complex Lu2-1 (Table
1). However, it should be noted that the energies of the the excited singlet and triplet levels differ
from the original “block” Lu-3. The values of the energy of the triplet levels of calix[4]arene
(~23800 cm-1) and porphyrin (~11700 cm-1) are higher than the emitting level of ytterbium
Yb(III) (2F5/2, 10300 cm-1), which makes intramolecular energy transfer possible from the
macrocyclic components of the complex to the lanthanide ion. In the IR region, due to the 4f-
luminescence of Yb(III) ions, the energy transfer occurs in both mononuclear and binuclear
complexes (Table2). When excited in Soret band, they lead to luminescence of Yb2-1 almost
twice as high as that of the original “block” Yb-3 under similar conditions. Moreover, 4f-
luminescence of the binuclear complexYb2-1 is observed upon 320 nm excitation, which is the
band of the calix[4]arene “block”, and its intensity is almost the same as the signal excited in
Soret band. Thus, it can be assumed that in this complex 4f-luminescence is sensitized not only
by porphyrin, but also by calix[4]arene fragments.
Table 2.
4f-Luminescent parameters of the homonuclear Yb(III) complexes
(С =1·10-5 M, DMF).
Complex
λmax, nm
φ
Yb-1 985, 1008, 1036 0.0032
Yb2-1 978, 1007, 1026 0.0047
Yb-2 982, 1003, 1027 0.0028
Yb-3 976, 1005, 1024 0.0042
In order to minimize the influence of OH- and CH-vibrations of solvent molecules, a series
of solutions with different contents of deuterated solvent were studied. It was shown that with
increasing of the concentration of DMSO-d6 and DMF-d6, the luminescence intensity
60 ISSN 2708-129X. Укр. хім. журн., 2023
HOMO- AND HETERONUCLEAR Yb(III) AND Lu(III) COMPLEXES WITH CALIX[4]ARENE
MODIFIED WITH PORPHYRIN SUBSTITUENTS.INORGANIC CHEMISTRY
Fig. 4 − Plot of the intensity of 4f-luminescence of the complexes Yb-1 (a) and Yb2-1(b) vs the content
of deuterated solvents.
The formation of heteronuclear complexes
with lanthanides and d-elements coordinat-
ed in porphyrin fragments was monitored by
changes in the characteristic bands in the ab-
sorption spectrum. The parameters of the ab-
sorption spectrum (Table 1) of heteronuclear
complexes strongly depends on the nature of
the d-metal ion, which is caused by the forma-
tion of molecular orbitals from the coplanar
ligand chromophore and a metal ion.
The absorption spectra of f-d-heteronuclear
complexes and the spectra of corresponding
d-porphyrinates are very similar. The intensi-
ty of the Soret band increases, when d-metal
ions are coordinated (Table 1). This fact indi-
cates that the singlet levels in the molecule are
highly populated and, as a consequence, more
efficient molecular fluorescence and phospho-
rescence, as well as sensitized luminescence of
lanthanide ions, are possible.
In the molecular fluorescence spectra of f-d
complexes, bands were found in the region of
550–610 nm and 600–660 nm, corresponding
to the 0–0 and 0–1 transitions. Due to the low
fluorescence intensity for copper (II) porphy-
rinates, only the first transition was detected.
The energy values of the triplet levels, as fol-
lows from the phosphorescence spectra, de-
crease from Lu-Cu2-1 to Lu-Pd2-1.
4f-Luminescent properties have been studi
ed for heterometallic compounds both in solid
state and in solutions. For Yb(III)-Cu(II) com-
plexes, it was not possible to detect 4f-lumines-
cence in solution. Its absence is explained by
the fact that the intersystem crossing conver-
sion T1→S0 in copper (II) porphyrinate has a
very high probability (about 1012 s-1), and the
probability of transitions T1→2F5/2 for Yb(III)
is in the range of 108−1010 s-1 [14]. Thus, the
process of luminescence sensitization becomes
non-competitive: its probability is 2−4 orders
of magnitude lower than the probability of the
intercombination transition T1→S0.
In contrast to the copper-containing comp
lex, in heteronuclear compounds of zinc and
palladium it was possible to detect 4f-lumines-
cence of Yb(III) in 975−985 nm region. In he
teronuclear complexes with zinc, an increase
8
continuously grows up: more smoothly for the Yb-1 complex (Fig. 4, a), while for Yb2-1a sharp
increase in intensity is observed at DMSO-d6 concentrations above 60 vol.% (Fig. 4, b).The use
of deuterated solvents leads to an increase in the intensity of ytterbium 4f luminescence by 5.5
and 2.3 times in DMSO-d6 or by 3.6 and 2.0 times in DMF-d6for Yb2-1 and Yb-1, respectively.
Fig. 4 − Plot of the intensity of 4f luminescence of the complexes Yb-1 (a) and Yb2-1(b) vs the
content of deuterated solvents.
The formation of heteronuclear complexes with lanthanides and d-elements coordinated in
porphyrin fragments was monitored by changes in the characteristic bands in the absorption
spectrum. The parameters of the absorption spectrum (Table 1) of heteronuclear complexes
strongly depends on the nature of the d-metal ion, which is caused by the formation of molecular
orbitals from the coplanar ligand chromophore and a metal ion.
The absorption spectra of f-d-heteronuclear complexes and the spectra of corresponding d-
porphyrinates are very similar. The intensity of the Soret band increases, when d-metal ions are
coordinated (Table 1). This fact indicates that the singlet levels in the molecule are highly
populated and, as a consequence, more efficient molecular fluorescence and phosphorescence, as
well as sensitized luminescence of lanthanide ions, are possible.
In the molecular fluorescence spectra of f-d complexes, bands were found in the region of
550–610 nm and 600–660 nm, corresponding to the 0–0 and 0–1 transitions. Due to the low
fluorescence intensity for copper (II) porphyrinates, only the first transition was detected. The
energy values of the triplet levels, as follows from the phosphorescence spectra, decrease from
Lu-Cu2-1 to Lu-Pd2-1.
4f-Luminescent properties have been studied for heterometallic compounds both in solid
state and in solutions. For Yb(III)-Cu(II) complexes, it was not possible to detect 4f-
luminescence in solution. Its absence is explained by the fact that the intersystem crossing
conversion T1→S0 in copper (II) porphyrinate has a very high probability (about 1012 s-1), and
the probability of transitions T1→2F5/2 for Yb(III) is in the range of 108−1010 s-1 [14]. Thus, the
process of luminescence sensitization becomes non-competitive: its probability is 2−4 orders of
magnitude lower than the probability of the intercombination transition T1→S0.
In contrast to the copper-containing complex, in heteronuclear compounds of zinc and
palladium it was possible to detect 4f-luminescence of Yb(III) in 975−985 nm region. In
heteronuclear complexes with zinc, an increase in 4f-luminescence of ytterbium is observed
compared to mononuclear by 1.8 times, both in the solid sample and in solution (φ4f = 0.0058),
for palladium complexes the increase is slightly less by 1.4 times (φ4f = 0.0045), which can be
explained by the competition of two processes T1→S0 (≈104 s-1) and T1→2F7/2 (≈108 - 1010 s-1).
CONCLUSIONS. Calix[4]arenes covalently modified with porphyrin fragments are
convenientpolytopic molecular platforms for the preparation and study of homo- and
heteronuclear f-d-complexes.In mononuclear complexesLn-1, the lanthanide ion coordinates
8
continuously grows up: more smoothly for the Yb-1 complex (Fig. 4, a), while for Yb2-1a sharp
increase in intensity is observed at DMSO-d6 concentrations above 60 vol.% (Fig. 4, b).The use
of deuterated solvents leads to an increase in the intensity of ytterbium 4f luminescence by 5.5
and 2.3 times in DMSO-d6 or by 3.6 and 2.0 times in DMF-d6for Yb2-1 and Yb-1, respectively.
Fig. 4 − Plot of the intensity of 4f luminescence of the complexes Yb-1 (a) and Yb2-1(b) vs the
content of deuterated solvents.
The formation of heteronuclear complexes with lanthanides and d-elements coordinated in
porphyrin fragments was monitored by changes in the characteristic bands in the absorption
spectrum. The parameters of the absorption spectrum (Table 1) of heteronuclear complexes
strongly depends on the nature of the d-metal ion, which is caused by the formation of molecular
orbitals from the coplanar ligand chromophore and a metal ion.
The absorption spectra of f-d-heteronuclear complexes and the spectra of corresponding d-
porphyrinates are very similar. The intensity of the Soret band increases, when d-metal ions are
coordinated (Table 1). This fact indicates that the singlet levels in the molecule are highly
populated and, as a consequence, more efficient molecular fluorescence and phosphorescence, as
well as sensitized luminescence of lanthanide ions, are possible.
In the molecular fluorescence spectra of f-d complexes, bands were found in the region of
550–610 nm and 600–660 nm, corresponding to the 0–0 and 0–1 transitions. Due to the low
fluorescence intensity for copper (II) porphyrinates, only the first transition was detected. The
energy values of the triplet levels, as follows from the phosphorescence spectra, decrease from
Lu-Cu2-1 to Lu-Pd2-1.
4f-Luminescent properties have been studied for heterometallic compounds both in solid
state and in solutions. For Yb(III)-Cu(II) complexes, it was not possible to detect 4f-
luminescence in solution. Its absence is explained by the fact that the intersystem crossing
conversion T1→S0 in copper (II) porphyrinate has a very high probability (about 1012 s-1), and
the probability of transitions T1→2F5/2 for Yb(III) is in the range of 108−1010 s-1 [14]. Thus, the
process of luminescence sensitization becomes non-competitive: its probability is 2−4 orders of
magnitude lower than the probability of the intercombination transition T1→S0.
In contrast to the copper-containing complex, in heteronuclear compounds of zinc and
palladium it was possible to detect 4f-luminescence of Yb(III) in 975−985 nm region. In
heteronuclear complexes with zinc, an increase in 4f-luminescence of ytterbium is observed
compared to mononuclear by 1.8 times, both in the solid sample and in solution (φ4f = 0.0058),
for palladium complexes the increase is slightly less by 1.4 times (φ4f = 0.0045), which can be
explained by the competition of two processes T1→S0 (≈104 s-1) and T1→2F7/2 (≈108 - 1010 s-1).
CONCLUSIONS. Calix[4]arenes covalently modified with porphyrin fragments are
convenientpolytopic molecular platforms for the preparation and study of homo- and
heteronuclear f-d-complexes.In mononuclear complexesLn-1, the lanthanide ion coordinates
61https://ucj.org.ua
N.V. Rusakova, O.V. Snurnikova, S.S. Smola, O.Yu. Korovin, E.V. Malinka, M.Yu. Rusakova UCJ № 09 / Vol. 89
in 4f-luminescence of ytterbium is observed
compared to mononuclear by 1.8 times, both in
the solid sample and in solution (φ4f = 0.0058),
for palladium complexes the increase is slight-
ly less by 1.4 times (φ4f = 0.0045), which can be
explained by the competition of two processes
T1→S0 (≈104 s-1) and T1→2F7/2 (≈108 - 1010 s-1).
CONCLUSIONS. Calix[4]arenes covalently
modified with porphyrin fragments are con-
venient polytopic molecular platforms for the
preparation and study of homo- and heteronu-
clear f-d-complexes. In mononuclear complex-
es Ln-1, the lanthanide ion coordinates four
oxygen atoms of the lower rim of calixarene
and two oxygen atoms of the carbonyl groups
of the substituents to form two five-mem-
bered metallocycles. In binuclear complexes
Ln2-1 lanthanide ions are coordinated along
the macro ring of porphyrin fragments and
are located on the periphery of the molecule.
The coordination polyhedron of lanthanide
ion in heteronuclear f-d complexes Ln-M2-1
is formed by oxygen atoms: two from the phe-
nolic groups of the lower rim of calix[4]arene
and four from carboxymethoxy groups. The
d-metal ions (Zn(II), Cu(II), Pd(II)) are co-
ordinated along the periphery of the complex
molecule in the porphyrinate rings. It has been
shown that the coordination of the lanthanide
ion along the lower rim of calix[4]arene has
virtually no effect on porphyrin fluorescence,
but sensitization of 4f luminescence occurs
both with the participation of the calix[4]arene
matrix and porphyrin fragments. It has been
established that in heteronuclear complexes
based on calix[4]arene-diporphyrin, the deter-
mining factor in the efficiency of 4f-lumines-
cence sensitization is the nature of the d-metal.
The maximum 4f-luminescence characteristics
were found for Ln(III)–Zn(II) complexes.
AKNOWLEDGEMENT. The work was
carried out with the financial support
of the National Academy of Sciences of
Ukraine within the state budget topic «New
near-infrared luminescent materials based
on modified tetrapyrrole and complex oxide
compounds of d- and f-elements: synthesis,
design, properties». The state registration
number of the work is 0122U000415.
ГОМО- ТА ГЕТЕРОЯДЕРНІ КОМПЛЕКСИ
Yb(III) ТА Lu(III) З КАЛІКС[4]АРЕНОМ,
МОДИФІКОВАНИМ ПОРФІРИНОВИМИ
ЗАМІСНИКАМИ
Н. В. Русакова, О. В. Снурнікова,
С. С. Смола, О. Ю. Коровін,
О. В. Малінка, М. Ю. Русакова
1Фізико-хімічний інститут ім. О. В. Богат-
ського НАН України,
Люстдорфська дорога, 86, Одеса 65080,
Україна;
2Одеський національний технологічний уні-
верситет,
вул. Канатна, 112, Одеса 65039, Україна;
3Одеський національний університет
ім. І. І. Мечникова,
вул. Дворянська, 2, Одеса 65082, Україна
*е-mail: natavrusakova@gmail.com
У цій роботі описано підходи до синте-
зу лантанідвмісних гомо- та гетероядерних
комплексів із використанням 5,11,17,23-
тетра-трет-бутил-25,27-дигідрокси-26, 28-
біс[(N-мезо-(n-амінофеніл)-мезо-трифе
нілпорфіринкарбоніл)метокси]-калікс
[4]арену (1). Такий просторово заздалегідь
62 ISSN 2708-129X. Укр. хім. журн., 2023
HOMO- AND HETERONUCLEAR Yb(III) AND Lu(III) COMPLEXES WITH CALIX[4]ARENE
MODIFIED WITH PORPHYRIN SUBSTITUENTS.INORGANIC CHEMISTRY
організований калікс[4]ареновий макро-
цикл полегшує координацію катіонів лан-
танідів, впливаючи на структуру та аналі-
тичний сигнал порфіринових замісників. У
дослідженні використано дві стратегії син-
тезу, що призводять до одноядерних і го-
мобіядерних комплексів під впливом сте-
ричних ефектів і змін у водневих зв’язках.
У комплексах виявлено зміни в спектрах
флуоресценції внаслідок внутрішньомоле-
кулярної димеризації та водневих зв’язків
під час утворення комплексу. Моноядерні
комплекси (Ln-1) синтезовано в м'яких умо-
вах, тоді як гомоядерні комплекси (Ln2-1)
вимагають висококиплячих розчинників і
специфічних умов реакції. Процедури син-
тезу детально описано. Структурні зміни
під час комплексоутворення аналізували за
допомогою ЯМР-спектрів. Спектри погли-
нання комплексів лантанідів демонструють
зміщення максимумів, що відображають
зміни координації з помітними варіаціями
між моноядерними та гомобінуклеарни-
ми комплексами. Крім цього, гетероядерні
сполуки з міддю (II), цинком (II) і паладі-
єм (II) демонструють характерні моделі по-
глинання, що підкреслює роль іонів d-ме-
талів. Дослідження люмінесценції вияв-
ляють сенсибілізацію 4f-люмінесценції як
калікс[4]ареновими, так і порфіриновими
фрагментами. Використання дейтерованих
розчинників посилює інтенсивність 4f-лю-
мінесценції, що вказує на вплив розчинни-
ка. Крім цього, досліджено характеристики
4f-люмінесценції як у твердому стані, так і
в розчині для гетерометалевих сполук, та
виявлено відмінності між комплексами,
що містять мідь, і комплексами, що містять
цинк/паладій. Результати дають достатньо
повне уявлення про дизайн, синтез і спект
ральні властивості цих комплексів, демон-
струючи їхнє потенційне застосування в
різних галузях, а результати сприяють ро-
зумінню лантанід-порфіринових систем та
їхніх координаційних властивостей.
Ключові слова: лантаніди, комплекси,
калікс[4]арен, порфірин, синтез, люмінес-
ценція.
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Стаття надійшла 10. 09. 2023.
|
| id | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-588 |
| institution | Ukrainian Chemistry Journal |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-07-23T01:10:42Z |
| publishDate | 2023 |
| publisher | V.I.Vernadsky Institute of General and Inorganic Chemistry |
| record_format | ojs |
| resource_txt_mv | ucjorgua/40/900cf8415a0422b873030d6e2d202e40.pdf |
| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-5882026-07-22T08:23:52Z HOMO- AND HETERONUCLEAR Yb(III) AND Lu(III) COMPLEXES WITH CALIX[4]ARENE MODIFIED WITH PORPHYRIN SUBSTITUENTS. Rusakova, Natalia Malinka, Olena Korovin, Oleksandr Smola, Serhii Snurnikova, Olga Rusakova, Mariia lanthanide, complexes, calix[4]arene, porphyrin, synthesis, luminescence. In this work we describe the approaches for the synthesis of lanthanide-containing homo- and heteronuclear complexes using 5,11,17,23-tetra-tert-butyl-25,27-dihydroxy-26,28-bis[(N-meso-(p-aminophenyl)-meso-triphenylporphyrincarbonyl)methoxy]-calix[4]arene (1). Such spatially preorganizedcalix[4]arene macrocycle facilitates lanthanide cation coordination, impacting the structure and analytical signal of porphyrin substituents. The study employs two synthesis strategies resulting in mononuclear and homobinuclear complexes, influenced by steric effects and changes in hydrogen bonding. The complexes exhibit changes in fluorescence spectra due to intramolecular dimerization and hydrogen bonding during complex formation. Mononuclear complexes (Ln-1) are synthesized under mild conditions, while homobinuclear complexes (Ln2-1) require high-boiling solvents and specific reaction conditions, detailed synthesis procedures are described. The structural changes during complex formation were analyzed with the use of NMR analysis. The absorption spectra of lanthanide complexes demonstrate shifts in maxima, reflecting coordination changes, with notable variations between mononuclear and homobinuclear complexes. Additionally, heteronuclear compounds with copper(II), zinc(II), and palladium(II) exhibit distinctive absorption patterns, emphasizing the role of d-metal ions. Luminescence studies reveal the sensitization of 4f-luminescence by both calix[4]arene and porphyrin fragments. The use of deuterated solvents enhances 4f-luminescence intensity, highlighting solvent effects. Furthermore, 4f-luminescence characteristics were investigated in both solid and solution states for heterometallic compounds, emphasizing differences between copper-containing and zinc/palladium-containing complexes. The results offer valuable insights into the design, synthesis, and spectral properties of these complexes, showcasing their potential applications in various fields, and the findings contribute to the understanding of lanthanide-porphyrin systems and their coordination behavior. V.I.Vernadsky Institute of General and Inorganic Chemistry 2023-10-25 Article Article Inorganic Chemistry Неорганическая химия Неорганічна хімія application/pdf https://ucj.org.ua/index.php/journal/article/view/588 10.33609/2708-129X.89.09.2023.52-63 Ukrainian Chemistry Journal; Vol. 89 No. 9 (2023): Ukrainian Chemistry Journal; 52-63 Украинский химический журнал; ##issue.vol## 89 ##issue.no## 9 (2023): Ukrainian Chemistry Journal; 52-63 Український хімічний журнал; Том 89 № 9 (2023): Український хімічний журнал; 52-63 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/588/300 Copyright (c) 2023 Natalia Rusakova, Olena Malinka, Oleksandr Korovin, Serhii Smola, Olga Snurnikova, Mariia Rusakova https://creativecommons.org/licenses/by-nc/4.0 |
| spellingShingle | Rusakova, Natalia Malinka, Olena Korovin, Oleksandr Smola, Serhii Snurnikova, Olga Rusakova, Mariia HOMO- AND HETERONUCLEAR Yb(III) AND Lu(III) COMPLEXES WITH CALIX[4]ARENE MODIFIED WITH PORPHYRIN SUBSTITUENTS. |
| title | HOMO- AND HETERONUCLEAR Yb(III) AND Lu(III) COMPLEXES WITH CALIX[4]ARENE MODIFIED WITH PORPHYRIN SUBSTITUENTS. |
| title_full | HOMO- AND HETERONUCLEAR Yb(III) AND Lu(III) COMPLEXES WITH CALIX[4]ARENE MODIFIED WITH PORPHYRIN SUBSTITUENTS. |
| title_fullStr | HOMO- AND HETERONUCLEAR Yb(III) AND Lu(III) COMPLEXES WITH CALIX[4]ARENE MODIFIED WITH PORPHYRIN SUBSTITUENTS. |
| title_full_unstemmed | HOMO- AND HETERONUCLEAR Yb(III) AND Lu(III) COMPLEXES WITH CALIX[4]ARENE MODIFIED WITH PORPHYRIN SUBSTITUENTS. |
| title_short | HOMO- AND HETERONUCLEAR Yb(III) AND Lu(III) COMPLEXES WITH CALIX[4]ARENE MODIFIED WITH PORPHYRIN SUBSTITUENTS. |
| title_sort | homo- and heteronuclear yb(iii) and lu(iii) complexes with calix[4]arene modified with porphyrin substituents. |
| topic_facet | lanthanide complexes calix[4]arene porphyrin synthesis luminescence. |
| url | https://ucj.org.ua/index.php/journal/article/view/588 |
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