Synthesis and Luminescent Properties of Eu3+, Gd3+, and Tb3+ Complexes with Quinoline-4-carboxylic Acids

Article abstract of DOI:10.1134/S1070363219120144

New complex compounds LnL₃·nH₂O (n = 5–10) have been synthesized on the basis of Eu³⁺, Gd³⁺, and Tb³⁺ salts and quinoline-4-carboxylic acid derivatives obtained via the Pfitzinger reaction. Compositio

Full text of DOI:10.1134/S1070363219120144

ISSN 1070-3632, Russian Journal of General Chemistry, 2019, Vol. 89, No. 12, pp. 2413–2419. © Pleiades Publishing, Ltd., 2019.
Russian Text © The Author(s), 2019, published in Zhurnal Obshchei Khimii, 2019, Vol. 89, No. 12, pp. 1901–1908.
Synthesis and Luminescent Properties of Eu3+, Gd3+, and Tb3+
Complexes with Quinoline-4-carboxylic Acids
I. A. Kotlovaa,*, F. A. Kolokolova, V. V. Dotsenkoa,b, N. A. Aksenovb, and I. V. Aksenovab
a Kuban State University, ul. Stavropol’skaya 149, Krasnodar, 350040 Russia
b North-Caucasus Federal University, Stavropol, Russia
*e-mail: kot-tlova@mail.ru
Received May 17, 2019; revised May 17, 2019; accepted May 25, 2019
Abstract—New complex compounds LnL3·nH2O (n = 5–10) have been synthesized on the basis of Eu3+, Gd3+,
and Tb3+ salts and quinoline-4-carboxylic acid derivatives obtained via the Pfitzinger reaction. Composition and
structure of the ligands and the resulting complex compounds have been confirmed by NMR and IR spectroscopy,
thermogravimetry, and complexometric titration. Europium complex with 1,2,3,4-tetrahydroacridine-9-carboxylic
acid has exhibited efficient luminescence.
Keywords: quinoline-4-carboxylic acid derivatives, Pfitzinger reaction, lanthanides, luminescent properties,
complexation
DOI: 10.1134/S1070363219120144
The demand to the development of novel polyfunc-
tional complexes exhibiting efficient luminescence (in
particular, lanthanides complexes with organic ligands
favoring efficient energy transfer to the emission level
of the ion and improving the luminescence efficiency)
has recently emerged [1–8]. Synthesis and photolumi-
nescent properties of lanthanides complexes with a series
of 8-oxyquinoline derivatives [9–13] as well as with
quinoline-2,3-dicarboxylic acid [14] have been reported.
However, the lanthanides complexes with substituted
quinoline-4-carboxylic acids have not been systemati-
cally studied.
Complexes of Eu3+, Gd3+, and Tb3+ with aromatic and
heterocyclic ligands have been recognized as compounds
exhibiting efficient luminescence. Extending the studies
of heteroatomic ligands containing carboxylic groups
[15] and luminescent lanthanides carboxylates [16–20],
we explored the possibility of targeted synthesis and
photoluminescent properties of Eu3+, Gd3+, and Tb3+
complexes with substituted quinoline-4-carboxylic acids.
Purity and structure of compounds 1‒3 were confirmed
by means of comprehensive spectroscopy studies: IR and
NMR (1H, 13C, and 15N including DEPTQ, 1Н–13С HSQC,
and 1Н–13С HMBC). 1H NMR spectra of acids 1‒3 con-
tained a signal at 13.99‒14.01 ppm, typical of the carbox-
ylic group.Asimilar typical signal of the carboxylic group
was found in the 13С DEPTQ NMR spectra of acids 1‒3
at 167.5‒168.7 ppm. 15N NMR spectrum of compound 1
contained a signal of the quinoline nitrogen at 312.0 ppm
which revealed the cross peaks with H3 (8.41 ppm) and
H8 (8.11 ppm) protons in the HMBC 1Н–15N spectrum.
The principal chemical shifts and heteronuclear correla-
tions for compounds 1 and 3 are shown in Scheme 2;
complete sets of the observed correlations are collected
in Tables 1 and 2.
Complexes of Eu3+, Gd3+, and Tb3+ with acids 1‒3
were synthesized from alcoholic solutions containing the
lanthanide(III) ligand and the ligand (HL) in the 1 : 3 ratio
(Scheme 3). The composition of the obtained complexes
corresponded to the LnL3·nH2O (n = 5–10) formula, their
yield being 41‒84%.
First, we synthesized 2-(4-methoxyphenyl)quino-
line-4-carboxylic 1 (quin-OCH3), 2-(4-bromophenyl)-
quinoline-4-carboxylic 2 (quin-Br), and 1,2,3,4-tetrahy-
droacridine-9-carboxylic 3 [quin(CH2)4] acids.Acids 1‒3
were synthesized (Scheme 1) via the Pfitzinger reaction
(cf. [21]) using a modified procedure [22].
Complexes 4‒12 were pale-yellow powders. Their
composition and structure were confirmed by means of
IR spectroscopy, and the metal content was determined
by complexometric titration. According to the obtained
data, the composition of compounds 4‒12 was as fol-
2413

2414
KOTLOVA et al.
Scheme 1.
COOH
R1
O
R1
(1) KOH, EtOH, 8 h
(2) HCl
R2
+
O
R2
N
N
O
H
1
2
R = H, R = 4-CH OC H (quin-OCH ) (1), 4-BrC H (quin-Br) (2);
3
1
6
2
4
3
6
4
R + R = (CH ) [quin(CH ) ] (3).
2 4
2 4
Scheme 2.
HO167.7
O
8.61
H
COOH13.98
ꢀ
H
7.63 7.67
H 8.41
H
125.4
137.5
118.7
128.7
127.3
8.26
123.1
H 7.11
130.2
155.5
128.7
114.4
H
N
312.0
N
130.3
160.9
3.84
129.6
ꢀ
7.80 7.83
H
8.11
CH3
CH3
55.4
H
O
O
148.4
114.4
7.11
H
1
H14.00
HO168.7
O
7.92
H
O
O
ꢀ
2.87 2.90
H
128.3
26.3
139.5
122.0
ꢀ
7.67 7.72
H
H
124.3
126.6
22.0
22.2
ꢀ
1.80 1.86
125.7
ꢀ
1.86 1.92
7.54 7.58H
N
H
N
ꢀ
129.2
33.3
H
ꢀ
H
ꢀ
3.02 3.05
145.5 159.0
7.67 7.72
3
lows: Gd(quin-OCH3)3·5H2O (4), Tb(quin-OCH3)3·7H2O
(5), Eu(quin-OCH3)3·5H2O (6), Gd(quin-Br)3·7H2O
(7), Tb(quin-Br)3·6H2O (8), Eu(quin-Br)3·7H2O (9),
Gd[quin(CH2)4]3·5H2O (10), Tb[quin(CH2)4]3·10H2O
(11), and Eu[quin(CH2)4]3·6H2O (12).
stretching C=O band of the protonated carboxylic group
at 1650‒1715 cm–1 was shifted to shorter wavelengths,
typical of the stretching of ionized carboxylic group
νas(COO‒) and νs(COO‒). Since the difference in the
frequency of the asymmetric and symmetric stretching
Δν in the complexes spectra did not exceed 220 cm–1, the
ligands in the complexes were ionized and exhibited bi-
dentate coordination with the lanthanide(III) ions via two
oxygen atoms of the deprotonated carboxylic group [23].
The complexes composition was determined by ther-
mogravimetry. In the case of the Eu[quin(CH2)4]3·6H2O
complex (12), two exothermic effects were observed at
20–226 and 227–331°С, corresponding to the elimination
of 4 outer-sphere water molecules and 2 inner-sphere
water molecules, respectively (Fig. 1). A strong exo-
thermic effect observed at 332–575°С corresponded to
thermal decomposition of the complex and sequential
elimination of three ligand molecules. The residual mass
corresponded to europium oxide.
To explore the possibility of the application of the
obtained complexes as luminophors, we recorded their
luminescence spectra. The efficient luminescence de-
manded the closeness of the energies of the triplet ligand
level and the emission level of the lanthanide ion, the
triplet level of the ligand should be higher in energy by
1800‒3500 cm–1 [24].
In contrast to IR spectra of compounds 1‒3, those
of the complexes did not contain the group of bands at
2800‒2400 cm–1 assignable to the carboxylic acid dimers,
which indirectly confirmed the complex formation. The
Triplet levels of acids 1‒3 were determined from the
phosphorescence spectra of their complexes with Gd3+.
The Т1 energy was considered equal to that of the long-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 12 2019

SYNTHESIS AND LUMINESCENT PROPERTIES OF Eu3+, Gd3+, AND Tb3+ COMPLEXES
2415
Table 1. Correlations observed in the HMBC 1Н–13С HSQC and 1Н–13С spectra of 2-(4-methoxyphenyl)quinoline-4-carboxylic
acid 1a
δС, ppm
δН, ppm
HSQC 1H–13C
55.4* (MeO)
HMBC 1H–13C
160.9 (С-OMe)
3.84 s (3H, MeO)
7.11 d (2H, H3, H5, 4-MeOC6H4, 3J = 8.7 Hz)
114.4* (C3, C5 4-MeOC6H4) 114.4* (C3, C5, 4-MeOC6H4),
160.9 (С‒OMe),
128.7* (C2, C6, 4-MeOC6H4), 130.3 (C1,
4-MeOC6H4)
7.63‒7.67 m (1H, H6)
7.80‒7.83 m (1H, H7)
8.11 d (1H, H8, 3J = 8.6 Hz)
127.4* (C6)
130.2 (C7)
129.6* (C8)
123.1 (C4а), 130.2* (C7)
125.4* (C5), 148.4 (C8a)
123.1 (C4а), 127.4* (C6)
8.26 d (2H, H2, H6, 4-СН3OC6H4, 3J = 8.7 Hz) 128.7* (C2, C6 4-СН3OC6H4) 114.4* (C3, C5, 4-MeOC6H4),
128.7* (C2, C6,4-СН3OC6H4), 155.5 (C2),
160.9 (C-OMe)
8.41 s (1H, H3)
118.7* (C3)
125.4* (C5)
123.1 (C4a), 130.3 (C1, 4-MeOC6H4),
137.5 (C4), 155.5 (C2), 167.7 (COOH)
8.61 d (1H, H5, J = 8.6 Hz)
123.1 (C4a), 130.2* (C7), 137.5 (C4а), 148.4
(C8a)
13.99 br. s (1H, COOH)
–
–
a Hereafter (asterisk) marks the signals in the opposite phases.
wave emission band in the spectra: 17241 (1), 17094 (2),
and 19920 (3) cm–1. The energy of the triplet level of acids
1‒3 was lower in comparison with the resonance level
of the Tb3+ ion (5D4 20500 cm–1), and efficient intramo-
lecular energy transfer to the Tb3+ was impossible; that
was confirmed by the experimental data.
17250 cm–1), and the luminescence was not observed for
complexes 6, 9 of Eu3+ with those ligands. The energy
of triplet level T1 of acid 3 was optimal for Eu3+ ion,
and the corresponding complex 12 exhibited efficient
luminescence. The luminescence spectrum of complex
12 {Eu(H2O)2[quin(CH2)4]3·4H2O} is shown in Fig. 2;
characteristic emission of the Eu3+ ion (5D0–7F1, 5D0–7F2,
5D0–7F3, 5D0–7F4) was to be seen. The luminescence ef-
The energy of triplet levels T1 of acids 1 and 2 was
lower than that of resonance level of Eu3+ ion (5D0
Scheme 3.
N
N
COOH
O
O
R2
R2
_
R1
_
Ln3+
LnCl3, 3KOH, (nꢁꢀ 3)H2O
R1
O
O
R1
˜ nH2O
ꢀ3KCl
_
N
R2
O
O
1–3
R1
R2
N
4–12
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 12 2019

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KOTLOVA et al.
Table 2. Correlations observed in the HSQC 1Н–13С and HMBC 1Н–13С spectra of 1,2,3,4-tetrahydroacridine-9-carboxylic acid 3
δС, ppm
δН, ppm
HSQC 1H–13C
22.0 (C2)
HMBC 1H–13C
1.80‒1.86 m (2Н, H2)
1.86‒1.92 m (2H, H3)
2.87‒2.90 m (2H, H1)
3.02‒3.05 m (2H, H4)
7.54‒7.58 m (1H, H6)
22.2 (C3), 26.3 (C1), 33.3 (C4), 125.7 (C9а)
22.2 (C3)
26.3 (C1)
33.3 (C4)
126.6* (C6)
22.0 (C2), 26.3 (C1), 33.3 (C4), 159.0 (С4а)
22.0 (C2), 22.2 (C3), 125.7 (C9а), 139.5 (С9), 159.0 (С4а)
22.0 (C2), 22.2 (C3), 125.7 (C9а), 145.5 (С10а), 159.0 (С4а)
124.3* (C7), 128.3* (C8), 129.2* (C5), 145.5 (С10а
122.0 (C8а), 124.3* (C7), 126.6* (C6), 128.3* (C8), 129.2*
(C5), 139.5 (С9), 145.5 (С10а
)
7.67‒7.72 m (2H, H5, H7 overlap) 124.3* (C7), 129.2* (C5)
)
7.92 d (1Н, Н8, 3J = 8.3 Hz)
128.3* (C8)
122.0 (C8а), 124.3* (C7), 126.6* (C6)
–
14.00 br. s (1H, COOH)
–
ficiency is generally determined by comparing its inte-
gral intensity with that of the corresponding lanthanide
benzoate [16–20]. In the considered case, the integral
intensity of the Eu(H2O)2[quin(CH2)4]3·4H2O complex
luminescence was 3.36 times stronger than that of euro-
pium benzoate.
In summary, we prepared the complexes of Eu3+,
Gd3+, and Tb3+ with 2-(4-methoxyphenyl)quinoline-
4-carboxylic, 2-(4-bromophenyl)quinoline-4-carboxylic,
and 1,2,3,4-tetrahydroacridine-9-carboxylic acids. It was
found that europium complex with 1,2,3,4-tetrahydroac-
ridine-9-carboxylic acid exhibited the luminescent prop-
erties 3.36 times stronger in comparison with europium
benzoate.
EXPERIMENTAL
NMR spectra (1Н, 13С DEPTQ, HSQC H–13C,
1
1
1
HMBC H–13C, and HMBC H–15N) were recorded
using a Bruker Avance III HD NanoBay spectrometer
(400 MHz) in DMSO-d6, operating at 400, 101, and 40.55
MHz (1Н, 13С, and 15N, respectively). TMS or residual
signals of the solvent were used as internal references; in
the case of the 15N spectrum, liquid nitromethane served
as external reference (380.23 ppm). IR spectra were
recorded using a Bruker Vertex 70 spectrometer (4000‒
350 cm–1, ATR with a diamond crystal). Excitation
and emission spectra were recorded using a Fluorat-
02-Pamorama instrument equipped with a fiber-optic at-
Ĺ
exo
ɷɤɡɨ
Ȝ, nm
T, °ɋ
Fig. 2. Luminescence spectrum of the Eu(H2O)2[quin(CH2)4]3·
4H2O complex (12).
Fig. 1. Thermogram of the Eu(H2O)2[quin(CH2)4]3·4H2O
complex (12). (1) TG, (2) DSC, (3) DTG.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 12 2019

SYNTHESIS AND LUMINESCENT PROPERTIES OF Eu3+, Gd3+, AND Tb3+ COMPLEXES
2417
tachment for solid samples. The spectra at liquid nitrogen
atmosphere (77 K) were recorded using a cryostat.
8.64 d (1Н, Н5, J = 8.6 Hz), 14.01 br. s (1H, COOH). 13С
NMR spectrum, δС, ppm: 119.0 (C3), 123.6 (CBr), 123.9
(C4а), 125.5 (C8), 128.1 (C6), 129.3 (C5), 129.7 (C2, С6,
4-BrC6H4), 130.5 (C7), 132.0 (C3, С5, 4-BrC6H4), 136.9
(C4), 137.9 (C1, 4-BrC6H4), 148.2 (C8а), 154.7 (C2), 167.5
(COOH). 15N NMR spectrum: δN 311.7 ppm. Found, %:
С 58.54; H 3.13; N 4.28. C16H10BrNO2. Calculated, %:
С 58.56; H 3.07; N 4.27.
Purity of the obtained compounds was monitored by
TLC on Sorbfil-A plates (eluent: acetone–hexane 1 : 1,
the spots were visualized with iodine vapors and UV
light.). Thermogravimetric analysis was performed using
a NETSCH STA 409 PC/PG instrument at heating from
25 to 750°С (air atmosphere, 10 deg/min). Elemental
analysis (C, H, N) was performed using a Vario MICRO
cube instrument. The metals content was determined via
titration of a weakly acidic solutions with 0.05 M. EDTA
solution in the presence of 0.1% alcoholic solution of
Xylene Orange.
1,2,3,4-Tetrahydroacridine-9-carboxylic acid (3).
Yield5.02g(65%).IRspectrum,ν,cm–1:1595(С=С,C=N),
1
1653 (C=O). Н NMR spectrum, δ, ppm: 1.80‒1.86 m
(2Н, H2), 1.86‒1.92 m (2H, H3), 2.87‒2.90 m (2H, H1),
3.02‒3.05 m (2H, H4), 7.54‒7.58 m (1H, H6), 7.67‒7.72 m
(2H, H5, H7, signals overlap), 7.92 d (1Н, Н8, 3J = 8.3 Hz),
14.00 br. s (1H, COOH). 13С DEPTQ NMR spectrum,
δС, ppm: 22.0 (C2), 22.2 (C3), 26.3 (C1), 33.3 (C4), 122.0
(C8а), 124.3* (C7), 125.7 (C9а), 126.6* (C6), 128.3* (C8),
129.2* (C5), 139.5 (С9), 145.5 (С10а), 159.0 (С4а), 168.7
(COOH). Found, %: С 74.02; H 5.80; N 6.18. C14H13NO2.
Calculated, %: С 73.99; H 5.77; N 6.16.
Acids 1‒3 were prepared via a procedure adopted from
Ref. [22]. 0.034 mol of the corresponding ketone and
30 mL of 33% aqueous solution of potassium hydroxide
(d = 1.32 g/cm3, 0.23 mol) was added to a suspension
of 5.0 g (0.034 mol) of isatin in 30 mL of 96% ethanol.
The mixture was refluxed during 8 h, cooled down, and
acidified with HCl to рН = 2. After 24 h, the precipitate
was filtered off and washed with cold EtOH. The obtained
substance was refluxed during 10 min in an alkaline al-
coholic solution with activated carbon; the solution was
filtered through a paper filter, cooled, acidified with HCl
to рН = 2, and kept in a fridge overnight. The formed
precipitate was filtered off, washed with EtOH, and dried.
Complexes 4‒12. 10 mL of an alcoholic solution of
potassium hydroxide was added to 10 mL of an alcoholic
solution of 3 mmol of acid 1‒3. 10 mmol of an alcoholic
solution of 1 mmol of TbCl3, Gd(NO3)3, or EuCl3 was
added dropwise at stirring to the obtained solution. The
precipitate was filtered off, washed with cold alcohol,
and dried in air.
2-(4-Methoxyphenyl)quinoline-4-carboxylic acid
(1). Yield 5.03 g (53%). IR spectrum, ν, cm–1: 1599 (С=С,
C=N), 1651 (C=O). 1Н NMR spectrum, δ, ppm: 3.84 s
(3H, 4-СН3OC6H4), 7.11 d (2H, H3, H5, 4-СН3OC6H4,
3J = 8.7 Hz), 7.63‒7.67 m (1H, H6), 7.80‒7.83 m (1H,
Gd(quin-OCH3)3·5H2O (4). Yield 0.5084 g (47%).
IR spectrum, ν, cm–1: 1609 [νas(COO‒)], 1397 [νs(COO‒)].
Found, %: С 56.48; H 4.63; Gd 14.51; N 3.84.
GdC51H49N3O14. Calculated, %: С 56.45; H 4.55; Gd
14.49; N 3.87.
3
H7), 8.11 d (1H, H8, J = 8.6 Hz), 8.26 d (2H, H2, H6,
4-СН3OC6H4, 3J = 8.7 Hz), 8.41 s (1H, H3), 8.61 d (1H,
H5, J = 8.6 Hz), 13.99 br. s (1H, COOH). 13С DEPTQ
NMR spectrum, δС, ppm: 55.4* (MeO), 114.4* (C3, C5,
4-СН3OC6H4), 118.7* (C3), 123.1 (C4а), 125.4* (C5),
127.4* (C6), 128.7* (C2, C6, 4-СН3OC6H4), 129.6*
(C8), 130.2* (C7), 130.3 (C1, 4-СН3OC6H4), 137.5 (C4),
148.4 (C8a), 155.5 (C2), 160.9 (COMe), 167.7 (COOH).
15N NMR spectrum: δN 312.0 ppm. Found, %: С 73.13;
H 4.75; N 4.98. C17H13NO3. Calculated, %: С 73.11; H
4.69; N 5.02.
Tb(quin-OCH3)3·7H2O (5). Yield 0.7584 g
(68%). IR spectrum, ν, cm–1: 1608 [νas(COO‒)], 1390
[νs(COO‒)]. Found, %: С 54.51; H 4.78; N 3.76; Tb 14.17.
TbC51H53N3O16. Calculated, %: С 54.55; H 4.76; N 3.74;
Tb 14.15.
Eu(quin-OCH3)3·5H2O (6). Yield 0.7268 g (67%). IR
spectrum, ν, cm–1: 1601 [νas(COO‒)], 1402 [νs(COO‒)].
Found, %: С 56.74; H 4.65; Eu 14.09; N 3.85.
EuC51H49N3O14. Calculated, %: С 56.72; H 4.57; Eu
14.07; N 3.89.
2-(4-Bromophenyl)quinoline-4-carboxylic acid (2).
Yield 10.60 g (95%). IR spectrum, ν, cm–1: 1586 (С=С,
C=N),1713(C=O).1НNMRspectrum,δ,ppm:7.69‒7.73m
(1H, H6), 7.75 d (2H, H3, H5, 4-BrC6H4, J = 8.5 Hz),
7.83‒7.87 m (1H, H7), 8.16 d (1Н, Н8, J = 8.3 Hz), 8.25 d
(2Н, Н2, Н6, 4-BrC6H4, J = 8.5 Hz), 8.46 s (1H, H3),
Gd(quin-Br)3·7H2O (7). Yield 0.7039 g (56%). IR
spectrum, ν, cm–1: 1603 [νas(COO‒)], 1420 [νs(COO‒)].
Found, %: С 45.50; H 3.55; Gd 12.43; N 3.29.
GdC48H44Br3N3O13. Calculated, %: С 45.48; H 3.50; Gd
12.40; N 3.31.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 12 2019

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KOTLOVA et al.
metric and Luminescent Methods for the Determination
Tb(quin-Br)3·6H2O (8). Yield 0.9342 g (75%). IR
spectrum, ν, cm–1: 1615 [νas(COO‒)], 1402 [νs(COO‒)].
Found, %: С 46.05; H 3.44; N 3.38; Tb 12.68.
TbC48H42Br3N3O12. Calculated, %: С 46.07; H 3.38; N
3.36; Tb 12.70.
of Lanthanides), Kiev: Naukova Dumka, 1989.
3. Grosby, G.A., Whan, R.E., and Freeman, J.J., J. Chem.
Phys., 1962, vol. 66, p. 2493.
https://doi.org/10.1021/j100818a041
4. Weissman, S.A., J. Chem. Phys., 1942, vol. 10, p. 214.
Eu(quin-Br)3·7H2O (9). Yield 1.0646 g (84%). IR
spectrum, ν, cm–1: 1585 [νas(COO‒)], 1404 [νs(COO‒)].
Found, %: С 45.65; H 3.58; Eu 12.07; N 3.35.
EuC48H44Br3N3O13. Calculated, %: С 45.67; H 3.51; Eu
12.04; N 3.33.
https://doi.org/10.1063/1.1723709
5. Panyushkin, V.T., Spektrokhimiya koordinatsionnykh
soedinenii RZE (Spectrochemistry of REE Coordination
Compounds), Rostov-on-Don: Rostovsk. Univ., 1984,
p. 128.
Gd[quin(CH2)4]3·5H2O (10). Yield 0.3845 g
(41%). IR spectrum, ν, cm–1: 1593 [νas(COO‒)], 1396
[νs(COO‒)). Found, %: С 54.26; H 5.37; Gd 16.94; N
4.53. GdC42H49N3O11. Calculated, %: С 54.30; H 5.32;
Gd 16.93; N 4.52.
6. De Bettencourt-Dias, A., Dalton Trans., 2007, vol. 22,
p. 2229.
https://doi.org/10.1039/B702341C
7. Yan, B., Zhang, H., Wang, S., and Ni, J., J. Photochem.
Photobiol. (A), 1998, vol. 116, p. 209.
Tb[quin(CH2)4]3·10H2O (11). Yield 0.7477 g
(73%). IR spectrum, ν, cm–1: 1594 [νas(COO‒)], 1399
[νs(COO‒)]. Found, %: С 49.43; H 5.86; N 5.80; Tb
15.57. TbC42H59N3O16. Calculated, %: С 49.42; H 5.83;
N 4.12; Tb 15.57.
https://doi.org/10.1016/S1010-6030(98)00307-4
8. Sokolov, M.E., Repina, I.N., Raitman, O.A., Koloko-
lov, F.A., and Panyushkin, V.T., Russ. J. Phys. Chem. (A),
2016, vol. 90, p. 1097.
https://doi.org/10.7868/S0044453716050320
9. Devolb, I., Bardeza, E., J. Colloid Interface Sci., 1998,
vol. 200, p. 241.
Eu[quin(CH2)4]3·6H2O (12). Yield 0.7051 g
(76%). IR spectrum, ν, cm–1: 1587 [νas(COO‒)], 1404
[νs(COO‒)]. Found, %: С 53.55; H 5.49; Eu 16.13; N
4.49. EuC42H51N3O12. Calculated, %: С 53.56; H 5.46;
Eu 16.14; N 4.46.
https://doi.org/10.1006/jcis.1997.5356
10. Kuz’mina, L.G., Kukina, G.A., and Ashaks, Ya.V., Zh.
Neorg. Khim., 1995, vol. 40, no. 11, p. 1817.
11. Bankovskii, Yu.A., Bel’skii, V.K., Pech, L.Ya., and
Ashaks, Ya.V., Zh. Neorg. Khim., 1993, vol. 38, no. 12,
p. 1988.
FUNDING
This study was financially supported by the Ministry
of Education and Science of Russian Federation (proj-
ect no. 4.5547.2017/8.9, V.V. Dotsenko, I.V. Aksenova;
project no. 4.1196.2017/4.6, N.A. Aksenov) and carried
out using the equipment of Research Center “Diagnostics
of Structure and Properties of Nanomaterials – Center
for Collective Usage” and Center for Collective Usage
“Ecological-Analytical Center” (universal identifier
RFMEFI59317X0008) of Kuban State University.
12. Yu, H., Liu, Y., Zhao, S., Guo, X., and Qu, S.,
Thermochim Acta, 2004, vol. 409, p. 195.
https://doi.org/10.1016/S0040-6031(03)00362-9
13. Yu, H., Liua, Y., Tan, Z., Donga, J., Zoua, T., Huanga, X.,
and Qua, S., Thermochim Acta, 2003, vol. 401, p. 217.
https://doi.org/10.1016/S0040-6031(02)00566-X
14. Zhang, H., Fan, R., Wang, P., Wang, X., Gao, S., Dong, Y.,
Wang, Y., and Yang, Y., RSC Adv., 2015, vol. 5, p. 38254.
https://doi.org/10.1039/C5RA01796C
CONFLICT OF INTEREST
No conflict of interest was declared by the authors.
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