Synthesis of Octafluorobiphenyl-4,4′-dicarboxylic acid and photoluminescent compounds based thereon

Article abstract of DOI:10.1134/S1070363215070075

Octafluorobiphenyl-4,4′-dicarboxylic acid (H₂L) and its complexes with Tb(III) and Eu(III) [Ln₂(H₂O)₄(L)₃·3H₂O and Ln₂(phen)₂(L)₃·2H₂O] have been prepared; their structure has been elucidated from IR spectroscopy and X-ray diffraction analysis data. Thermal properties of the compounds have been studied. The complexes of Tb(III) and Eu(III) exhibit green and red photoluminescence, respectively.

Full text of DOI:10.1134/S1070363215070075

ISSN 1070-3632, Russian Journal of General Chemistry, 2015, Vol. 85, No. 7, pp. 1617–1622. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © S.V. Larionov, L.I. Myachina, L.A. Sheludyakova, I.V. Korolkov, M.I. Rakhmanova, P.E. Plyusnin, A.S. Vinogradov, V.M. Karpov,
V.E. Platonov, V.P. Fadeeva, 2015, published in Zhurnal Obshchei Khimii, 2015, Vol. 85, No. 7, pp. 1092–1098.
Synthesis of Octafluorobiphenyl-4,4'-dicarboxylic Acid
and Photoluminescent Compounds Based Thereon
S. V. Larionova,c, L. I. Myachinaa, L. A. Sheludyakovaa, I. V. Korolkova,c,
M. I. Rakhmanovaa, P. E. Plyusnina,c, A. S. Vinogradovb,
V. M. Karpovb, V. E. Platonovb, and V. P. Fadeevab
a Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences,
pr. Akademika Lavrent’eva 3, Novosibirsk, 630090 Russia
e-mail: lar@niic.nsc.ru
b Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch,
Russian Academy of Sciences, Novosibirsk, Russia
c Novosibirsk State University, Novosibirsk, Russia
Received March 19, 2015
Abstract—Octafluorobiphenyl-4,4'-dicarboxylic acid (H2L) and its complexes with Tb(III) and Eu(III)
[Ln2(H2O)4(L)3·3H2O and Ln2(phen)2(L)3·2H2O] have been prepared; their structure has been elucidated from
IR spectroscopy and X-ray diffraction analysis data. Thermal properties of the compounds have been studied.
The complexes of Tb(III) and Eu(III) exhibit green and red photoluminescence, respectively.
Keywords: octafluorobiphenyl-4,4'-dicarboxylic acid, lanthanide, complex, photoluminescence
DOI: 10.1134/S1070363215070075
Luminescent coordination compounds of lantha-
nides (Ln) with ligands containing donor O and N
atoms have been widely applied to the production of
light emitting diodes and chemosensors [1–5]. The
presence of F atoms in the ligand enhances the lumi-
nescence [2, 6, 7]; therefore, lanthanide complexes
with aromatic perfluorinated carboxylic acids have
been thoroughly investigated. In particular, photo-
luminescent compounds containing lanthanide cations
and anions of C6F5COOH, 4-CF3C6F4COOH, and 4-
(CF3)2CFC6F4COOH have been prepared [8–11].
Later, luminescent coordination polymers of lantha-
nides (erbium, terbium, gadolinium, europium, and
lanthanum) with bridging anions of tetrafluoro-
terephthalic acid p-HOOCC6F4COOH (H2L') have
been obtained [12, 13]. We have earlier synthesized
the [Tb2(H2O)4(L')3·2H2O]n and Tb2(phen)2(L')3·2H2O
coordination polymers [14] and other compounds:
Ln2(H2O)4(L')3·2H2O and Ln2(phen)2(L')3·2H2O (Ln =
Eu, Sm, Dy; phen = phenanthroline) [15]. Synthesis of
coordination compounds of Ce, Pr, Nd, Sm, Dy, Er,
and Yb with tetrafluoroterephthalic and biphenyl-4,4'-
dicarboxylic acids has been described in [16–18].
In this work we have developed a new procedure to
obtain octafluorobiphenyl-4,4'-dicarboxylic acid (H2L)
and prepared its luminescent coordination compounds
with Tb(III) and Eu(III).
Octafluorobiphenyl-4,4'-dicarboxylic acid was
prepared as follows. First, the interaction of ethyl
pentafluorobenzoate I with zinc in the presence of
SnCl2 in DMF afforded the corresponding (4-ethoxy-
carbonyl-2,3,5,6-tetrafluorophenyl)zinc compounds II
[19] that were further transformed into diethyl
octafluorobiphenyl-4,4'-dicarboxylate III under the
action of anhydrous CuCl2 [20]. Finally, alkaline
hydrolysis of ester III afforded the target acid H2L
(IV) (Scheme 1).
Coordination compounds V–VIII were prepared
via the interaction of Ln(OH)3 (Ln = Tb or Eu) with
the acid H2L. Elemental analysis data of the prepared
products are given in Table 1; the composition of com-
pounds V and VI corresponded to the Ln2(H2O)4L3·
3H2O formula. The results coincided with the thermal
analysis data. The TG curve of compound V showed
the first stage of the mass loss at 30–110°С,
1617

1618
LARIONOV et al.
Scheme 1.
ZnX
F
CuCl2
Zn, SnCl2
F
F
F
EtOOC
COOEt
20oC
DMF, 60_65оС
COOEt
COOEt
I
II
III, 80%
(1) KOH, EtOH_H2O, 90_95oC
(2) H+, H2O
F
F
HOOC
COOH
IV, 94%
X = Cl, 4-EtOOCC6F4.
accompanied by the endothermic effect in the DTA
curve (Fig. 1). The mass loss in the first stage was
7.6%, corresponding to the elimination of seven water
molecules [the calculated mass fraction of water in
Tb2(H2O)4L3·3H2O was 7.9%]. The dehydrated compound
was stable up to 300°С, and then the second stage of
the mass loss followed; that process was accompanied
by the exothermic effect in the DTA curve and was
thus assigned to the compound decomposition. The
thermal behavior of compound VI was similar; the mass
loss in the first stage (30–140°С) accompanied by the
endothermic effect was 7.9% [the calculated water
fraction in Eu2(H2O)4L3·3H2O was 8.0%]. The onset of
the second stage assigned to the decomposition of the
dehydrated compound was observed at 280°С; that
stage was accompanied by the exothermic effect.
of water and phenanthroline content in compound VII
(21.2%). Evidently, the first stage of the compound
thermolysis corresponded to dehydration and partial
elimination of phenanthroline, the organic ligand
elimination ongoing in the second stage of the
decomposition. Further decomposition of the complex
took place above 260°С. The thermolysis of compound
VIII occurred similarly: the mass loss in the first
decomposition stage (30–180°С) was 5.4%, the second
stage was observed at 180–270°С (the total mass loss
in the two stages was 19.0%, close to the calculated
sum of the fractions of water and phenanthroline,
21.3%), and further decomposition was observed
above 270°С. The final stages of decomposition of
compounds VII and VIII were accompanied by the
exothermic effects in the DTA curves.
Elemental analysis data for compounds VII and
VIII corresponded to the Ln2(phen)2(L)3·2H2O formula.
The mass loss in the first stage of decomposition of
compound VII (30–170°С, cf. Fig. 2) was 5.5%,
significantly exceeding the content of water in the
compound of the suggested formula (1.9%). The
second stage of the decomposition was observed at
170–260°С. The total mass loss during the two decom-
position stages was 20.5%, close to the calculated sum
IR spectrum of the H2L acid contained a broad
absorption band at 3200–2300 cm–1, typical of the
carboxylic acids associated via the hydrogen bonding.
The ν(C=O) band of the acid was found at 1721 cm–1
(the similar band in IR spectrum of the acid H2L' was
observed at 1704 cm–1 [15]). Table 2 lists the major
vibration frequencies of compounds V–VIII. IR
spectra of compounds V and VI were similar and had
much in common with that of the [Tb2(H2O)4(L')3·
Table 1. Elemental analysis of compounds V–VIII
Found, %
Comp.
Calculated, %
Formula
no.
C
H
F
N
C
H
F
N
31.8
30.8
42.6
41.3
0.5
0.8
0.9
0.9
28.6
28.3
24.0
24.3
C42H14F24O19Tb2
C42H14Eu2F24O19
C66H20F24N4O14Tb2
C66H20Eu2F24N4O14
31.6
31.9
42.2
42.8
0.9
0.9
1.1
1.1
28.6
28.8
24.5
24.6
V
VI
3.0
3.0
3.0
3.0
VII
VIII
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 7 2015

SYNTHESIS OF OCTAFLUOROBIPHENYL-4,4'-DICARBOXYLIC ACID
1619
DTA, °С
m, %
DTA, °С
2.5
m, %
2.5
2.0
exo
exo
2.0
1.5
1.5
1.0
0.5
0.0
1.0
0.5
0.0
–0.5
–1.0
–0.5
–1.0
T, °C
T, °C
Fig. 1. Thermal analysis of compound V: (1) TG, (2) DTG,
and (3) DTA.
Fig. 2. Thermal analysis of compound VII: (1) TG,
(2) DTG, and (3) DTA.
2H2O]n complex characterized by X-ray diffraction
analysis [14]. IR spectra of the complexes VII and
VIII were similar as well.
IR spectra of compounds V and VI exhibited strong
bands at 1616–1555 and 1472–1394 cm–1 due to the
νas(COO) and νs(COO) vibrations of coordinated
COO– groups; similar bands were found at 1622–1619
and 1466–1464 cm–1 in the spectra of compounds VII
and VIII. The strong band observed at 1504 cm–1 in
the phenanthroline spectrum was shifted towards
higher energy range (1517 cm–1) in the spectra of
complexes VII and VIII due to the coordination of
nitrogen atoms at the Ln ions.
Narrow bands at 3650 and 3644 cm–1 and broad
strong bands at 3391 and 3363 cm–1 in the spectra of
complexes V and VI were assigned to the ν(O–H)
vibrations of crystallization and coordinated water
molecules, respectively. The spectra of compounds
VII and VIII contained broad bands at 3360 cm–1 in
the range of the ν(O–H) vibrations assigned to the
vibrations of crystallization water molecules associated
via the hydrogen bonds.
The absorption bands at 500–280 cm–1 in the
spectra of compounds V–VIII were assigned to the
Table 2. Main vibration frequencies (cm–1) in IR spectra of complexes V−VIII
V
VI
VII
VIII
Assignment
3650
3391
3644
3363
ν(O–H)
3360 br
1622
3360 br
1619
1616
1592
1555
1613
1560
νas(COO–)
1517
1464
1517
1466
phen
νs(COO–)
1472
1406
1468
1394
490 sh
490 sh
ν(Ln–O)(H2O)
ν(Ln–O)(COO)
470
413
332
292
468
413
332
292
471
414
328
287
468
413
327
287
219
215
ν(Ln–N)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 7 2015

1620
I, rel. units
LARIONOV et al.
the Ln3+ ions coordinating two phenanthroline mole-
cules instead of four water ones.
The excitation spectrum of the H2L acid contained a
pair of bands at λmах = 265 and 300 nm (Fig. 3). The
excitation at λmах 300 nm induced strong photo-
luminescence at λmах = 337 nm. The excitation spectra
at 250–360 nm were recorded for the complexes as
well (Fig. 3); their photoluminescence spectra were
registered at the excitation wavelength of 300 nm. The
photoluminescence spectra of compounds V and VII
contained narrow bands at λmах = 488, 544, 584, and
620 nm (assigned to the 5D4 → 7F6, 5D4 → 7F5, 5D4 → 7F4,
and 5D4 → 7F3 transitions in the Tb3+ ion) (Fig. 4). The
“green” band at λmах 544 nm was the strongest one.
The bands positions were almost the same as those in
the photoluminescence spectra of the [Tb2(H2O)4(L')3·
2H2O]n and Tb2(phen)2(L')3·2H2O complexes [14].
3
2
λ, nm
Fig. 3. Excitation spectra of complexes (1) V, (2) VII,
(3) VI, (4) VIII, and (5) of the acid H2L.
Photoluminescence spectra of compounds VI and
VIII contained the narrow bands at λmах = 590, 614,
the broadened band at λmах = 651 nm, and the split
band at λmах = 680 and 695 nm, assigned to the
Ln–O(COO) and Ln–O(H2O) (V and VI) vibrations;
the bands at 219 and 215 cm–1 were assigned to the
ν(Ln–N) vibrations.
5
5D0→7F1, 5D0→7F2, 5D0→7F3, and D0→7F4 transitions
The positions of the strongest lines in the X-ray
diffraction patterns of compounds V and VI as well as
of compounds VII and VIII were close, evidencing the
identical phase composition of the samples.
in the Eu3+ ion (Fig. 4). The strongest emission band
was the “red” one at λmах = 614 nm. The bands
positions were close to those in the Eu2(L')3(DEF)2
(EtOH)2·2(DEF) photoluminescence spectrum (DEF =
diethylformamide): λmах = 590, 615, 650, and 695 nm [13].
V
6.48
VI
6.48
VII
5.92
8.40
VIII
5.94
8.46
The emission bands in the spectra of compounds
VII and VIII containing phenanthroline molecules
were weaker than those in the spectra of compounds V
and VI. That result contradicted the available data on
photoluminescence of the [Tb2(H2O)4(L')3·2H2O]n,
Tb2(phen)2(L')3·2H2O [14], Eu2(H2O)4(L')3·2H2O, and
Eu2(phen)2(L')3·2H2O [15]: in the latter group, the
compounds containing phenanthroline ligand exhibited
stronger photoluminescence. The origin of the ob-
served discrepancy requires further investigation.
9.82
9.76
10.04
12.98
10.03
12.96
11.78
11.84
To conclude, X-ray diffraction, thermal analysis,
and IR spectroscopy results pointed at the pairwise
similarity of the compounds V and VI as well as VII
and VIII. Crystals of the earlier prepared complex of
Tb(III) with anions of the H2L' acid, Tb2(H2O)4(L')3·
2H2O, were constituted by the layers of coordination
2D polymer [Tb2(H2O)4(L')3]n (coordination node
TbO9) containing the bridging anions (L')2– and the
hydrate water [14]. Compounds V and VI were likely
coordination polymers as well, of the Ln2(H2O)4(L)3·
3H2O composition. Probably, the higher amount of
crystallization water molecules in complexes V and VI
as compared to the above-mentioned complex
Tb2(H2O)4(L')3·2H2O was due to another packing of
the polymeric layers containing longer bridges of the
L2– anions. Compounds VII and VIII Ln2(рhen)2(L)3·
2H2O were likely coordination polymers as well, with
To conclude, we demonstrated the easy preparation
of new photoluminescent complexes of lanthanides
with perfluorinated aromatic ligands: anions of
octafluorobiphenyl-4,4'-dicarboxylic acid.
EXPERIMENTAL
The following chemicals were used: phenanthroline
monohydrate (“analytically pure”), TbCl3·6H2O and
EuCl3·6H2O (both “pure”), concentrated aqueous ammonia
solution, organic solvents (“analytically pure”), and
rectificate EtOH.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 7 2015

SYNTHESIS OF OCTAFLUOROBIPHENYL-4,4'-DICARBOXYLIC ACID
1621
NMR spectra were recorded using a Bruker AV-
I, rel. units
300 instrument [282.4 (19F) and 300 (1H) MHz]. IR
spectra were registered using Bruker Tensor 22,
Scimitar FTS 2000, and Vertex 80 spectrometers.
Electronic spectra were obtained using a Hewlett
Packard 8453 instrument. Molecular mass and
elemental compositions of the products were
determined by means of high-resolution mass
spectrometry using a DFS instrument (nominal ioniza-
tion energy of 70 eV). GC analysis was performed
using a Hewlett Packard HP 5980 instrument equipped
with an HP-5 quartz capillary column [30 m× 0.52 mm ×
2.6 µm, poly(dimethyl/diphenyl siloxane) as the
stationary phase] and a heat conductivity detector.
Melting points were determined using a Koeffler
heating block.
300
400
500
600
700
λ, nm
The content of C, H, N, and F in compounds V–
VIII was determined as described in [14]. Thermal
analysis was performed in helium atmosphere using a
TG 209 F1 Iris ® NETZSCH microthermobalance
(specimen mass 10 mg, Al crucible, gas flow 60 mL/min,
heating rate 10 deg/min). X-ray diffraction analysis of
polycrystals of compounds V–VIII was carried out
using a Shimadzu XRD-7000 diffractometer (CuKα
radiation, Ni filter, 2θ range 5°–60°, 2θ scan step
0.03°, accumulation time 1 s). The polycrystals to be
studied were ground in an agate mortar in the presence
of heptane, and the so obtained suspension was applied
onto the polished side of the standard quartz cell. After
heptane was evaporated, a 100 µm even layer of the
substance was obtained. Similarly treated polycrys-
talline silicon was used as external reference.
Fig. 4. Photoluminescence spectra of complexes (1) V,
(2) VII, (3) VI, (4) VIII, and (5) of the acid H2L.
was filtered off, washed with cold ethanol (50 mL),
and dried in air. Yield 14.20 g (77%). 12.66 g (yield
69%) of ester III was obtained after recrystallization
from ethanol. 1.99 g of ester III with purity of 98%
(GC) was additionally obtained from the ethanolic
mother liquor after the solvent evaporation and
sublimation of the product (135–140°C, ≈4 mmHg).
Total yield of compound III 80%, mp 75.5–76.0°С
(EtOH). IR spectrum (KBr), ν, cm–1: 3464, 3009, 2993,
2951, 2912, 1745 (C=O), 1653, 1493, 1473, 1389,
1369, 1304, 1254, 1213, 1018, 978, 860, 717. UV
1
spectrum (EtOH), λmax, nm (log ε): 243 (4.26). H
NMR spectrum [(CD3)2CO + CСl4], δ, ppm: 1.44 t
(6H, CH3, J 7 Hz), 4.47 q (4H, CH2, J 7 Hz). 19F NMR
spectrum [(CD3)2CO + CСl4], δF, ppm: 23.5 m (4F),
25.2 m (4F). Mass spectrum, m/z: 442.0441 [M]+.
Found, %: C 49.02; H 2.30; F 34.33. C18H10F8O4.
Calculated, %: C 48.88; H 2.28; F 34.37. M 442.0446.
Spectra of excitation and photoluminescence of
solid compounds V–VIII were registered using a Cary
Eclipse Varian fluorescent spectrophotometer at 300 K,
the measurement conditions being the same for all
samples (V = 500 V, aperture 5 nm).
Ethyl pentafluorobenzoate I was prepared as described
in [21].
Octafluorobiphenyl-4,4'-dicarboxylic acid, H2L
(IV). 8.16 g (145.5 mmol) of KOH was added to a
solution of 12.87 g (29.1 mmol) of ester III in 195 mL
of aqueous EtOH (50 vol %), and the mixture was
heated at 90–95°С at stirring during 28 h. The reaction
mixture was diluted with water, and the admixtures
were extracted with CH2Cl2 (3 × 50 mL). The aqueous
fraction was acidified with 6 mol/L aqueous HCl. The
precipitate was filtered off, washed with water, and
dried in a desiccator over P2O5. Yield 10.50 g (94%),
mp 316–318°С (mp 318–320°С [22]). 1H NMR
spectrum (CDСl3), δ, ppm: 8.51 br. s (2H, COOH). 19F
NMR spectrum (CDСl3), δF, ppm: 23.7 m (4F), 25.0 m
Diethyl octafluorobiphenyl-4,4'-dicarboxylate (III).
13.42 g (99.8 mmol) of CuCl2 was added to a solution
of the organozinc reagent II prepared from 19.98 g
(83.2 mmol) of compound I, 16.32 g (249.6 mmol) of
Zn powder, 1.58 g (8.32 mmol) of SnCl2, and 45 mL
of anhydrous DMF [19]; the mixture was stirred during
6 h at room temperature. Then the reaction mixture
was diluted with 300 mL of water, the product was
extracted with CH2Cl2 (3 × 50 mL), the organic
solutions were separated and dried over MgSO4. After
the solvent was distilled off, the formed precipitate
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 7 2015

1622
LARIONOV et al.
pov, V.M., Platonov, V.E., Batrachenko, N.I., and
Lisoivan, V.I., Russ. J. Coord. Chem., 1997, vol. 23,
no. 6, p. 432.
(4F) [23]. Found, %: C 43.23; H 0.52; F 39.26.
C14H2F8O4. Calculated, %: C 43.55; H 0.52; F 39.36.
Tb2(H2O)4L3·3H2O (V) and Eu2(H2O)4L3·3H2O
(VI). 2.5 mL of ammonia solution was added to a
solution of 0.5 mmol of LnCl3·6H2O (Ln = Tb or Eu)
(0.185 and 0.183 g, respectively) in 15 mL of water.
After 2 h, the Ln(OH)3 precipitate was filtered off on a
glass frit filter and washed with water till neutral
reaction of the filtrate. The wet precipitate was
transferred into a beaker, and 0.29 g (0.75 mmol) of
acid IV was added. The mixture was stirred till
dissolution, and then 30 mL of a 3 : 1 acetone–MeOH
mixture was added; white precipitate was formed. The
mixture was stirred during 2 h and left overnight. The
precipitate was filtered off on a dense paper filter,
washed with EtOH and pentane, and dried in air. Yield
0.28 g (70%) (V) and 0.36 g (90%) (VI).
9. Larionov, S.V., Glinskaya, L.A., Leonova, T.G., Klev-
tsova, R.F., Uskov, E.M., Platonov, V.E., Karpov, V.M.,
and Fadeeva, V.P., Russ. J. Coord. Chem., 2009, vol. 35,
no. 11, p. 798. DOI: 10.1134/S1070328409110025.
10. Glinskaya, L.A., Leonova, T.G., Klevtsova, R.F., and
Larionov, S.V., J. Struct. Chem., 2010, vol. 51, no. 3,
p. 594. DOI: 10.1007/s10947-010-0088-x.
11. Larionov, S.V., Leonova, T.G., Uskov, E.M., Rakh-
manova, M.I., Platonov, V.E., Karpov, V.M., and
Fadeeva, V.P., Russ. J. Gen. Chem., 2013, vol. 83,
no. 6, p. 1117. DOI: 10.1134/S1070363213060194.
12. Chen, B., Yang, Y., Zapata, F., Qian, G., Luo, Y.,
Zhang, J., and Lobkovsky, E.B., Inorg. Chem., 2006,
vol. 45, no. 22, p. 8883. DOI: 10.1021/ic060568u.
13. MacNeill, C.M., Day, C.S., Marts, A., Lachgar, A., and
Noftle, R.E., Inorg. Chim. Acta., 2011, vol. 365, p. 196.
DOI: 10.1016/j.ica.2010.09.013.
14. Larionov, S.V., Myachina, L.I., Glinskaya, L.A., Ko-
rol’kov, I.V., Uskov, E.M., Antonova, O.V., Karpov, V.M.,
Platonov, V.E., and Fadeeva, V.P., Russ. J. Coord.
Chem., 2012, vol. 38, no. 12, p. 717. DOI: 10.1134/
S1070328412110036.
15. Larionov, S.V., Myachina, L.I., Sheludyakova, L.A.,
Korol’kov, I.V., Antonova, O.V., Karpov, V.M.,
Platonov, V.E., and Fadeeva, V.P., Russ. J. Gen. Chem.,
2014, vol. 84, no. 6, p. 1193. DOI: 10.1134/
S107036321406022X.
16. Seidel, C., Lorbeer, C., Cybińska, J., Mudring, A.-V.,
and Rushewits, U., Inorg. Chem., 2012, vol. 51, no. 8,
p. 4679. DOI: 10.1021/ic202655d.
17. Amghouz, Z., Garsia-Granda, S., Garcia, J.R.,
Ferreira, R.A.S., Mafra, L., Carlos, L.D., and Rocha, J.,
Inorg. Chem., 2012, vol. 51, no. 3, p. 1703. DOI:
10.1021/ic202020z.
18. Min, Z., Singh-Wilmot, M.A., Cahill, C.L., Andrews, M.,
and Taylor, R., Eur. J. Inorg. Chem., 2012, no. 28,
p. 4419. DOI: 10.1002/ejic.201200345.
19. Vinogradov, A.S., Krasnov, V.I., and Platonov, V.E.,
Russ. J. Org. Chem., 2008, vol. 44, no. 1, p. 95. DOI:
10.1134/S1070428008010119.
Tb2(phen)2(L)3·2H2O (VII) and Eu2(phen)2(L)3·
2H2O (VIII). 0.29 g (0.75 mmol) of acid IV and 0.09 g
(0.5 mmol) of phen·H2O were added to the Ln(ОН)3
precipitate prepared as described above. The mixture
was stirred till dissolution, and then 30 mL of a 3 : 1
acetone–MeOH mixture was added; white precipitate
was formed. It was filtered off on a dense paper filter,
washed with EtOH and pentane, and dried in air. Yield
0.41 g (88%) (VII) and 0.40 g (84%) (VIII).
REFERENCES
1. De Sa, G.F., Malta, O.L., de Mello Donega, C., Simas, A.M.,
Longo, R.L., Santa-Crus, P.A., and da Silva, Jr.E.F.,
Coord. Chem. Rev., 2000, vol. 196, p. 165. DOI:
10.1016/S0010-8545(99)00054-5.
2. Katkova, M.A., Bochkarev, M.N., and Vitukhnovsky, A.G.,
Russ. Chem. Rev., 2005, vol. 74, no. 12, p. 1089. DOI:
10.1070/RC2005v074n12ABEH002481.
3. Bünzli, J.-C.G., Acc. Chem. Res., 2006, vol. 39, p. 53.
DOI: 10.1021/ar0400894.
4. Armelao, L., Quici, S., Barigelletti, F., Accorsi, G.,
Bottaro, G., Cavazzini, M., and Tondello, E., Coord.
Chem. Rev., 2010, vol. 254, p. 487. DOI: 10.1016/
j.ccr.2009.07.025.
20. Miller, A.O., Krasnov, V.I., Peters, D., Platonov, V.E.,
and Miethchen, R., Tetrahedron Lett., 2000, vol. 41,
no. 20, p. 3817. DOI: 10.1016/S0040-4039(00)00527-X.
5. Katkova, M.A., Bochkarev, M.N., Dalton Trans., 2010,
vol. 39, p. 6599. DOI: 10.1039/C001152E.
21. Filler, R., White, J.F., Kacmarek, A.J., and Solomon, I.J.,
Can. J. Chem., 1966, vol. 44, no. 19, p. 2346. DOI:
10.1139/v66-353.
6. Meshkova, S.B., Topilova, Z.M., Lozinskii, O.M.,
Rusakova, N.V., and Bol’shoi, D.V., J. Analit. Chem.,
1997, vol. 52, no. 9, p. 852.
22. Tamborski, C. and Soloski, E.J., J. Org. Chem., 1966,
vol. 31, p. 746. DOI: 10.1021/jo01341a023.
23. Chen, T.-H., Popov, I., Zenasni, O., Daugulis, O., and
Miljanić, O.Š., Chem. Commun., 2013, vol. 49, no. 61,
p. 6846. DOI: 10.1039/C3CC41564C.
7. Panin, E.S., Kavun, V.Ya., Sergienko, V.I., and
Bukvetskii, B.V., Koord. Khim., 1985, vol. 11, no. 11,
p. 1539.
8. Larionov, S.V., Kirichenko, V.N., Rastorguev, A.A.,
Belyi, V.I., Sheludyakova, L.A., Fadeeva, V.P., Kar-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 7 2015