Thermochimica Acta 659 (2018) 242–252

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Thermochimica Acta
journal homepage: www.elsevier.com/locate/tca

Preparation, spectral properties and thermal decomposition of new ternary T

complexes of La(III), Ce(III), Pr(III) and Nd(III) ions with N-
phenylanthranilic acid and 1,10-phenanthroline
⁎
Lidia Zapałaa, , Małgorzata Kosińskaa, Elżbieta Woźnickaa, Łukasz Byczyńskib, Wojciech Zapałac,
Jan Kalembkiewicza
a
Department of Inorganic and Analytical Chemistry, Faculty of Chemistry, Rzeszow University of Technology, Al. Powstańców Warszawy 6, 35-959 Rzeszow, Poland
b
Department of Polymers and Biopolymers, Faculty of Chemistry, Rzeszow University of Technology, Al. Powstańców Warszawy 6, 35-959 Rzeszów, Poland
c
Department of Chemical and Process Engineering, Faculty of Chemistry, Rzeszow University of Technology, Al. Powstańców Warszawy 6, 35-959 Rzeszów, Poland

A R T I C L E I N F O A B S T R A C T

Keywords: The new ternary complexes of the formula Ln2(nfa)5(phen)(OH)·nH2O (where n = 1 or 1.5; nfa – N-phenylan-
Lanthanide complexes thranilate anion (C13H10NO2), phen – 1,10-phenanthroline (C12H8N2), Ln = La(III), Ce(III), Pr(III) and Nd(III))
N-phenylanthranilic acid were synthesized and characterized by elemental analysis, complexometry, infrared spectroscopy, XRD tech-
1,10-phenanthroline nique, simultaneous thermogravimetry and differential scanning calorimetry (TG–DSC), evolved gas analysis by
Thermal analysis
TG–DSC coupled with FTIR and MS spectroscopy. The detailed thermogravimetic analysis showed that thermal
Pyrolysis
EGA
decomposition of the complexes in nitrogen and air atmosphere occurs in several stages including water elim-
ination, neutral ligand loss and N-phenylanthranilate anion decomposition, respectively. It was found that the
thermal stability and the decomposition path of the studied compounds depend on the metal ion and the applied
atmosphere. Low values of the dehydration enthalpies indicate that dehydration is connected with the release of
crystallization water. By the use of the coupled TG–FTIR–MS techniques the decomposition pathways of the
synthesized compounds were examined and the gaseous products released during pyrolysis and thermal oxi-
dation of the complexes were identified.

1. Introduction as rigid structure, high dipole moment, stiffness, bidentate coordination

During the past decades considerable attention has been paid to the
chemistry of lanthanide complexes. They are widely used in optical and
magnetic materials, as catalysts as well as they are useful in biomedi-
cine [1,2]. Among numerous studies on lanthanide complexes, the
properties of mixed-ligand complexes have become an important topic.
The interest in this field is not only due the fact, that they form intri-
guing supramolecular frameworks [3]. Several studies confirm that the
presence of a secondary ligand enhances stability [1,4] as well as in
important way luminescent [1,4,5] or biological properties [5,6] of the
complexes.
A survey of the literature reveals that among the different neutral
ligands 1,10-phenanthroline and its derivatives have been the subject of
special attention in ternary lanthanide complexes [1–9]. It is well know
that lanthanides behave as typical hard acids and prefer donor atoms
with the preference O > N > S and F > Cl. In the presence of water,
complexes with nitrogen donors are unstable and are readily hydro-
lysed [10]. Thus strongly chelating ligands are needed. Several features,
and the π-π stacking interaction of phenanthroline rings cause that
1,10-phenanthroline can coordinate lanthanide ions rapidly. These
properties also provide a stability of the lanthanide complexes with
phenanthroline [2,7]. This is the reason why this heterocyclic com-
pound is a good candidate for the synthesis of ternary lanthanide
complexes. Noteworthy is the fact that heterocyclic compounds con-
taining nitrogen have attracted attention, because of their biological
importance as well as their significance for the development of the
supramolecular chemistry [2,8,9,11–13]. Additionally, they are ex-
cellent antenna unit for lanthanide luminescence [2].
Fenamates are N-substituted anthranilic acid derivatives that are
clinically used as nonsteroidal anti-inflammatory drugs (NSAIDs) for
the treatment of fever, pain, and inflammation [14]. The title N-phe-
nylanthranilic acid is the leading structure in the group of fenamates
[14] and it is industrially used as the starting material for the synthesis
of biologically active compounds and medicaments [15]. What is more,
it is used in comparative medical research and for metal ion determi-
nation in analytical chemistry [16]. The interest in the complexes of

⁎
Corresponding author.
E-mail address: lzapala@prz.edu.pl (L. Zapała).

https://doi.org/10.1016/j.tca.2017.12.012
Received 25 September 2017; Received in revised form 3 December 2017; Accepted 6 December 2017
Available online 07 December 2017
0040-6031/ © 2017 Elsevier B.V. All rights reserved.
L. Zapała et al. Thermochimica Acta 659 (2018) 242–252

Fig. 1. Molecular structure of the ligands: a) N-phe-

nylanthranilic acid, b) 1,10-phenanthroline.

Table 1
Analytical (complexometric), thermoanalytical (TG) and elemental analyses (EA) data of Ln(III) complexes with N-phenylanthranilic acid and 1,10-phenanthroline where:
nfa = C13H10NO2, phen = C12H8N2.

Compound Molecular mass/g mol−1 Ln C H N H2O

EDTA calc. EA calc. EA calc. EA calc. TG calc.

La2(nfa)5(phen)(OH)·H2O (La-nfa-phen) 1554.14 17.60 17.88 59.84 59.50 3.87 3.96 6.63 6.31 1.29 1.16
Ce2(nfa)5(phen)(OH)·1.5H2O (Ce-nfa-phen) 1565.57 17.77 17.90 58.96 59.07 3.93 3.99 6.25 6.26 1.91 1.73
Pr2(nfa)5(phen)(OH)·1.5H2O (Pr-nfa-phen) 1567.15 18.35 17.98 58.22 59.01 3.96 3.99 6.26 6.26 1.78 1.72
Nd2(nfa)5(phen)(OH)·1.5H2O (Nd-nfa-phen) 1573.82 18.58 18.33 57.58 58.76 3.79 3.97 6.52 6.23 1.76 1.72

Furthermore, there are no literature reports regarding the systematic

investigation of thermal behaviour and pyrolysis study of binuclear
ternary lanthanide complexes with N-phenylanthranilic acid. It is ex-
pected that this type of compounds give frameworks with more diverse
structures compared to mononuclear complexes and will exhibit dif-
ferent thermal properties and biological activity. Therefore, their exact
characteristic using thermal analysis and evolved gas analysis is ne-
cessary [19–22].These techniques provide important information which
allow correctly characterize thermal stability and propose thermally
induced decomposition mechanisms [20–22]. Furthermore, they make
it possible to estimate shelf life and the possibility of remediation of an
environment or a destruction of metal complexes treated as potential
drugs [19].
In this work, we present the preparation of unreported previously
binuclear ternary complexes of lanthanide ions (La(III), Ce(III), Pr(III)
and Nd(III)) with N-phenylanthranilic acid and 1,10-phenanthroline
(Fig. 1) and their characteristics based on elemental analysis, gravi-
metry, infrared spectroscopy, X-ray powder diffraction (XRD) and
thermoanalytical techniques (TG/DTG-DSC, TG-FTIR-MS).
Fig. 2. X-ray powder diffraction patterns of the complexes of Ln(III) ions with N-phe-
nylanthranilic acid and 1,10-phenanthroline.
2. Experimental section
lanthanide ions and fenamates is due to the fact that both components
2.1. Chemicals and materials
of these compounds exhibit biological activity. Experimental data on
the mixed lanthanide complexes containing fenamates and phenan-
All the chemicals were obtained from commercial sources and used
throline as ligands are scarce. Until now, the research on ternary
without further purification. N-Phenylanthranilic acid with 99.0%
mononuclear lanthanide complexes with N-phenylanthranilic acid and
purity was obtained from Fluka Chemika. 1,10-phenanthroline
1,10-phenanthroline [17,18] have been already published.
(C12H8N2·H2O), methanol, sodium hydroxide and hydrochloric acid

Table 2
IR data for the ligands (N-phenylanthranilic acid, 1,10-phenanthroline), sodium N-phenylanthranilate [18] and obtained complexes.

Compound ν(NeΗ) ν(C]O) νas(COO−) νs(COO−) Δν* δ(NH) ν(CeN) δ(CeH) ν(LneO)

N-phenylanthranilic acid 3334 1655 1578, 1510 1324

Sodium N-phenylanthranilate 3322 1610 1386 224 1317
Phenanthroline 853, 738
La2(nfa)5(phen)(OH)·H2O 3284 1614 1394 220 1578, 1507 1317 841, 730 433
Ce2(nfa)5(phen)(OH)·1.5H2O 3286 1611 1394 217 1578, 1507 1317 841, 730 434
Pr2(nfa)5(phen)(OH)·1.5H2O 3283 1613 1394 219 1579, 1507 1317 842, 730 439
Nd2(nfa)5(phen)(OH)·1.5H2O 3289 1613 1394 219 1579, 1507 1317 842, 730 440

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L. Zapała et al.
Fig. 3. Thermogravimetric curves of the compounds in nitrogen: (a) La-nfa-phen (2.3579 mg), (b) Ce-nfa-phen (2.0870 mg), (c) Pr-nfa-phen (3.5010 mg), (d) Nd-nfa-phen (4.9830 mg)
and in air: (e) La-nfa-phen (2.2090 mg), (f) Ce-nfa-phen (2.0590 mg), (g) Pr-nfa-phen (3.5440 mg), (h) Nd-nfa-phen (2.4220 mg).
were obtained from POCH, Poland whereas DMSO was from Merck. La
(III) and Nd(III) chlorides were prepared by treating the appropriately
weighted amounts of their oxides with concentrated hydrochloric acid
(d = 1.19 kg dm−3) while Ce(III) was used as nitrate and Pr(III) as
chloride.
2.2. Experimental equipment and conditions
Carbon, hydrogen and nitrogen contents were determined with a
Vario EL elemental analyzer (Elementar, Germany). Metal ions contents
and hydration water in the obtained complexes were determined based
on the TG curves. The metal ions contents were also determined by
complexometric titration using standard EDTA solution, after miner-
alization of the complexes by perchloric acid. The Schöniger method
was used to determine the chlorine content. FT-IR spectra were re-
corded in KBr pellets with an Alpha FT-IR spectrophotometer (Bruker,
Germany) in the range 4000–400 cm−1. X-ray diffraction (XRD) pat-
terns were collected on solid complexes samples in a Bruker D2 Phaser
powder diffractometer with Cu Kα radiation, λ = 1.5406 Å (position
sensitive detector: 0° ≤ 2θ ≤ 28°). The DSC curves in nitrogen atmo-
sphere were obtained using Mettler Toledo DSC‐822e (heating rate of
10 K min−1).
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Thermochimica Acta 659 (2018) 242–252
Simultaneous TG-DSC curves were recorded using a TGA/DSC1
apparatus (Mettler Toledo) in temperature range of 298.15–1273.15 K,
using a heating rate of 20 K min−1. The measurements were conducted
in dynamic nitrogen and air atmospheres (flow rate 50 mL min−1).
TG-FTIR analyses were performed in air and nitrogen atmosphere
with the use of Mettler Toledo TGA/DSC1 instrument that was coupled
online with FTIR apparatus (Nicolet iS10 − Thermo Scientific) by a
transfer line heated at 493.15 K. The FTIR spectra of the evolved gases
were acquired in the range 4000–400 cm−1 with resolution of 4 cm−1.
The evolved gases were then transferred by a quartz capillary heated at
473.15 K into mass spectrometer ThermoStar™ (Pfeiffer Vacuum) where
the selected m/z signals were monitored.
2.3. Preparation of the complexes
The synthesis of the ternary complexes of La(III), Ce(III), Pr(III) and
Nd(III) ions with N-phenylanthranilic acid and phenanthroline was
carried out in methanol-aqueous solutions (1:1) at
cM:cHnfa:cphen = 1:2:3 (where: cM, cHnfa, cphen – molar concentration of
metal ions, N-phentylanthranilic acid and phenanthroline, respec-
tively). The aliquots of 1,10‐phenanthroline were added to adequate
hot (343.15 K) solutions of lanthanide ions (1 · 10−2 mol dm−3). The
L. Zapała et al. Thermochimica Acta 659 (2018) 242–252

Table 3
Thermal decomposition data for the complexes of Ln(III) ions with N-phenylanthranilic acid and 1,10‐phenanthroline in nitrogen atmosphere (where: nfa = C13H10NO2,
phen = C12H8N2).

Complex Stage Temperature range/K T DTG

max. /K
Δm/% Probable removed moieties Residue/% Found (calc.)

Found Calc.

La2(nfa)5(phen)(OH)·H2O I 303.15–458.15 332.15 1.29 1.16 H2O 22.17 (22.51) La2O3 + 2C

II 458.15–563.15 533.15 2.80 2.90 0.25phen
III 563.15–698.15 682.15 37.16 37.30 0.75phen + C30H24N2O2
IV 698.15–855.15 726.15 30.70 30.47 C31H27N3O2
V 855.15–1273.15 928.15, 1197.15 5.88 5.66 2CO2
77.83a 77.49a

Ce2(nfa)5(phen)(OH)·1.5H2O I 303.15–453.15 341.15 1.91 1.73 1.5H2O 22.14 (21.98) 2CeO2

II 453.15–703.15 692.15 41.34 41.50 phen + C32H25N2O2
III 703.15–863.15 728.15 29.33 29.04 C31H24N3O
IV 863.15–1273.15 937.15, 1144.15 5.28 5.75 CO2 + CO + H2O
77.86a 78.02a

Pr2(nfa)5(phen)(OH)·1.5H2O I 303.15–458.15 344.15 1.78 1.72 1.5H2O 25.06 (24.80) ⅓Pr6O11 + 4C

II 458.15–620.15 578.15 10.00 9.77 0.85phen
III 620.15–823.15 724.15 55.65 55.97 0.15phen + C58H51N5O2
IV 823.15–1273.15 942.15, 1170.15 7.51 7.74 ⅓(7CO2 + 2CO)
74.94a 75.20a

Nd2(nfa)5(phen)(OH)·1.5H2O I 303.15–458.15 345.15 1.44 1.72 1.5H2O 24.40 (24.42) Nd2O3 + 4C

II 458.15–617.15 591.15 9.11 9.16 0.80phen
III 617.15–815.15 722.15 58.58 57.96 0.20phen + C59H49N5O3
IV 815.15–1273.15 935.15, 1221.15 6.47 6.74 2CO2 + H2O
75.60a 75.58a

a
Total mass loss.

Table 4
Thermoanalytical data for dehydration processes of the complexes of Ln(III) ions with N-phenylanthranilic acid and 1,10‐phenanthroline.

Complex Dehydration temperature range (DSC)/K Onset temperature (DSC)/K Peak temperature (DSC)/K Dehydration enthalpy/kJ mol−1

La2(nfa)5(phen)(OH)·H2O 303.15–458.15 333.15 358.15 15.62

Ce2(nfa)5(phen)(OH)·1.5H2O 303.15–453.15 326.15 356.15 16.16
Pr2(nfa)5(phen)(OH)·1.5H2O 303.15–458.15 327.15 359.15 20.11
Nd2(nfa)5(phen)(OH)·1.5H2O 303.15–458.15 330.15 353.15 18.95

Table 5 Subsequently, pH values of the reaction mixtures were adjusted to

Thermal decomposition data for the complexes of Ln(III) ions with N-phenylanthranilic about 5 (using 0.5 mol dm−3 NaOH solution) and stirred for 1 h at
acid and 1,10‐phenanthroline in air atmosphere.
343.15 K.
Complex Stage Temperature Δm/% Residue/%
The obtained compounds were left at room temperature for 24 h.
T DTG
max. /K
range/K found Afterwards, the precipitates were filtered, washed with deionized water
(calc.) and methanol. The obtained coloured products were air-dried at room
temperature.
La2(nfa)5(phen) I 303.15–463.15 332.15 1.19 21.25
(OH)·H2O II 463.15–558.15 540.15 2.48 (20.96)
III 558.15–623.15 594.15 4.80
IV 623.15–757.15 700.15 39.23 3. Result and discussion
V 757.15–848.15 788.15 28.79
VI 848.15–1273.15 948.15 2.26
3.1. Analytical results and general characterization
Ce2(nfa)5(phen) I 303.15–448.15 339.15 1.81 22.89
(OH)·1.5H2O II 448.15–578.15 527.15 2.23 (21.99)
III 578.15–693.15 681.15 19.86 A series of new lanthanide complexes with N-phenylanthranilic acid
IV 693.15–1273.15 742.15 53.21 and phenanthroline have been prepared. The molecular formula of the
Pr2(nfa)5(phen) I 303.15–443.15 344.15 1.59 23.21 obtained ternary complexes is Ln2(C13H10NO2)5(C12H8N2)(OH)·H2O for
(OH)·1.5H2O II 443.15–618.15 579.15 8.55 (21.73)
III 618.45–763.15 697.15 39.56
La(III) and Ln2(C13H10NO2)5(C12H8N2)(OH)·1·5H2O for Ce(III), Pr(III)
IV 763.15–1273.15 798.15 27.09 and Nd(III) ions, where Ln is the lanthanide cation, C13H10NO2 is N-
Nd2(nfa)5(phen) I 303.15–463.15 344.15 1.37 22.41 phenylanthranilate anion (nfa) and C12H8N2 is 1,10‐phenanthroline
(OH)·1.5H2O II 463.15–621.15 596.15 6.90 (21.38) (phen). The stoichiometry of the synthesized compounds was de-
III 621.15–757.15 700.15 42.39
termined on the basis of elemental, complexometric and thermal ana-
IV 757.15–847.15 793.15 24.42
V 547.15–1273.15 889.15 2.44 lyses and the obtained results are presented in Table 1. Additionally,
elemental analysis excluded the presence of chlorine in the obtained
compounds.
resulting mixtures were maintained at this temperature and stirred until As is well known, lanthanides in aqueous solutions undergo hy-
complete dissolution of phenanthroline. Then methanolic solution drolysis. This phenomenon leads to the formation of different mono-
(1 · 10−2 mol dm−3) of N-phenylanthranilic acid (heated to the same nuclear and binuclear hydroxo complexes [23,24]. The studied com-
temperature) was added and the reaction mixtures were diluted with plexes were synthesized at pH about 5 when in aqueous solution mainly
water in order to obtain the ratio of methanol to water equal 1:1. Ln(OH)2+, Ln2(OH)33+ and Ln3+ ions are present [25], so formation of

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L. Zapała et al. Thermochimica Acta 659 (2018) 242–252

Table 6
Assignments of m/z signals detected in mass spectra of the evolved gases.

m/z Fragments m/z Fragments

1 H+ 50 C4H2+
2 H2+ 51 C4H3+
12 C+ 52 C4H4+
16 O+ 63 C5H3+
17 OH+/NH3+ 65 C5H5+
18 H2O+ 66 C4H4N+
26 C2H2+ 76 C6H4+
28 CO+ 77 C6H5+
30 NO+ 78 (C6H5 + H)+
39 C3H3+ 79 (C6H5 + 2H)+
44 CO2+ 92 C6H6N+
46 NO2+/12C18O16O+

Fig. 4. Gram–Schmidt curves of the ternary Nd(III) complex in nitrogen and air atmo-
sphere.

complexes with Ln(OH)2+ ions is possible.

As shown by the presented data all the complexes were obtained as
hydrates. They are insoluble in water and sparingly soluble in me-
thanol, DMSO and other polar solvents. Based on the powder X-ray
diffraction patterns of the ligands and the obtained complexes (Fig. 2),
is possible to stated that the obtained compounds are isostructural and
of low crystallinity.

3.2. Infrared spectra

All the complexes prepared in this work, have been studied by in-
frared spectra. The IR spectra of N-phenylanthranilic acid and phe-
nanthroline were also recorded for comparative purposes. In the ab-
sence of the powerful technique such as X-ray crystallography, to verify
the formation of the complexes, the evidence was obtained by com-
paring the infrared spectra of the free ligands and the synthesised
compounds. The spectral data registered in the range 4000–400 cm−1
for all obtained complexes are similar. This fact indicates that the
synthesized compounds are isostructural, as it was proved by XRD
analysis. The most characteristic bands for N-phenylanthranilic acid,
1,10-phenanthroline and the obtained complexes as well as their as-
signments are given in Table 2.
The IR spectra of the complexes exhibit a broad band in the range
3700–3100 cm−1, which is not present in the spectrum of N-pheny-
lanthranilic acid. This band corresponds to the asymmetric and sym-
metric stretching vibrations of water. The presence of water in these
complexes was confirmed by the thermal analysis.
Moreover, the OeH bands observed in the spectrum of the free li-
gand at 2860, 2732, 2640 and 2564 cm−1 disappear in the spectra of
the complexes, indicating that the carboxylic acid proton is removed in
Fig. 5. EGA-FTIR for ternary Nd(III) complex in nitrogen atmosphere: a) stacked plot of
the FTIR spectra of the evolved gases, b) the FTIR spectra of the evolved gases produced at
different temperatures (ν – stretching vibrations, π – deformation out-of-plane vibra-
tions).
order to form the N-phenylanthranilate anion as a result of complexa-
tion [26]. Deprotonation is also confirmed by the disappearance of the
bands in the spectra of the complexes that correspond to deformation
COeH (1437 cm−1), stretching CeO (1325 cm−1) and bending OeH
(out of plane) (905 cm−1) vibrations in the spectrum of free ligand. On
the other hand, the absence of large systematic shifts of the ν(NH) and
δ(NH) bands in the spectra of the obtained compounds compared with
those of the N-phenylanthranilic acid may indicate that the amino
group of N-phenylanthranilate ligand does not participate in the metal
ion coordination [27–29].
The absorption band derived from stretching vibrations ν(C]O) of
COOH group of N-phenylanthranilic acid is present at 1656 cm−1
whereas, in the obtained compounds this band is replaced by the two
characteristic bands of the stretching asymmetrical νas(COO−) and
stretching symmetrical vibrations νs(COO−) of the carboxylate group
occurring around 1613–1614 cm−1 and 1394–1395 cm−1, respectively.

246
L. Zapała et al.
Fig. 6. Ion currents for selected fragments with the corresponding DTG curve for ternary Nd(III) complex in nitrogen.
Simultaneously, in the spectra of the complexes, the new characteristic
absorption band from stretching vibrations of Ln–O bond (ν(Ln-O)) ap-
pears in the range of 433–440 cm−1. These facts indicate that the car-
boxylate groups of N-phenylantranilate ligands have formed co-
ordinative bonds with the investigated lanthanide ions [26,30,31].
Taking into consideration the values of Δν (νas(COO−) − νs(COO−)) for
all studied complexes, which are slightly lower than that of the sodium
N-phenylanthranilate, we concluded that bidentate bridging coordina-
tion takes place [29]. What is more, asymmetrical bidentate chelating
mode of the coordination may occur due to the comparable values of Δν
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Thermochimica Acta 659 (2018) 242–252
for obtained complexes and sodium N-phenylanthranilate [32]. More-
over, mixed bridging– chelating character of the carboxylate group can
not be also excluded [33].
Furthermore, the IR spectra of the complexes show two bands as-
signed to CeH stretching vibration δ(CeH) of phenanthroline ring in the
range of 841–842 cm−1 and at 730 cm−1, respectively. These bands are
red shifted compared to the free 1,10-phenanthroline from 853 cm−1
and 738 cm−1, respectively. This fact indicates that 1,10-phenanthro-
line is involved in the formation of these complexes and is coordinated
by two nitrogen atoms [34]. The presented analysis leads to the
L. Zapała et al.
conclusion that both ligands are coordinated to metal ions thus the
ternary complexes have been received.
3.3. Thermal behaviors of the synthesized complexes
The thermal decomposition processes of the obtained in solid state
ternary lanthanide complexes were investigated in air and nitrogen
atmosphere by simultaneous TG-DSC technique. The TG, DTG and DSC
curves obtained in both atmospheres are presented in Fig. 3 and dis-
cussed separately as follows.
3.3.1. Thermal decomposition of the complexes in nitrogen atmosphere
The simultaneous TG/DTG-DSC curves of the ternary complexes in
nitrogen atmosphere are presented in Fig. 3a–d. These results show that
La(III) complex decomposes in five steps while for the complexes with
Ce(III), Pr(III) and Nd(III) four decomposition stages are observed. The
thermal decomposition data are summarized in Table 3.
The first mass loss observed between 303.15 and 458.15 K takes
place without significant thermal event on the simultaneous registered
DSC curves and is attributed to the dehydration. In case of lanthanum
complex, 1 molecule of water is lost (1.29%; calc. = 1.16%) while in
case of cerium (1.91%; calc. = 1.73%), praseodymium (1.78%;
calc. = 1.72%) and neodymium (1.44%; calc. = 1.72%) complexes 1.5
molecules of water are lost. On the DSC curves there are no en-
dothermic peaks assigned to the dehydration step. This is probably
because of that the mass loss occurs slowly and the heat involved in this
step is not sufficient to cause such thermal event [35].
In order to accurate analysis of the nature of water molecules and
the stability of the obtained complexes the DSC curves were ad-
ditionally recorded in nitrogen atmosphere in temperature range of
233.15–383.15 K and the broad, weak endothermic peaks are observed.
Both low values of the dehydration enthalpies per one molecule of
water and the range of dehydration temperature (Table 4) confirm that
for all investigated compounds, the dehydration is connected with the
release of the weakly bonded water molecules [36].
On the basis of the onset dehydration temperatures it can be stated
that the thermal stability of the series of the ternary lanthanide com-
plexes is as follows:
Ce ∼ Pr < Nd < La
The second decomposition step of the investigated compounds, ex-
cept for cerium complex, occurs below 593.15 K. The mass loss is
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Thermochimica Acta 659 (2018) 242–252
Fig. 7. Thermal decomposition pathways of ternary
lanthanide complexes in nitrogen.
connected with medium and broad peaks on the DTG curves centered at
533.15 K (La), 578.15 K (Pr) and 591.15 K (Nd). Similar degradation
stage has already been reported for ternary lanthanide complexes with
phenanthroline ligand and assigned to the release of phenanthroline
and part of secondary ligand [1,20,37] or partial phenanthroline de-
composition [19]. The percentage weight loss allows to suggest partial
loss of phenanthroline in case of La(III) (TG = 2.80%; calc. = 2.90%),
Pr(III) (TG = 10.00%; calc. = 9.77%) and Nd(III) (TG = 9.11%;
calc. = 9.16%) complexes. In case of cerium ternary complex, the
phenantroline partial loss is not connected with distinguishable peak on
DTG curve and is overlapped by next degradation stage.
The next step of the decomposition process connected with the
biggest mass loss (in range 55.65–70.67%) is observed between
563.15–855.15 K (La), 453.15–863.15 K (Ce), 620.15–823.15 K (Pr),
617.15–815.15 K (Nd). For the complexes with La(III) and Ce(III) two
overlapping steps, characterized by narrow peaks on the DTG curves at
682.15 and 726.15 K (La) or 692.15 and 728.15 K (Ce) are observed,
whereas for Pr(III) and Nd(III) compounds this process occurs in the
two hardly distinguishable steps. This stage is related to loss of the
remaining phenanthroline molecule [19] and degradation of nfa ligands
[38,39]. Above 853.15 K the TG profiles show two consecutive steps
which correspond to small mass losses and weak, broad peaks on the
DTG curves at 938.15 and 1197.15 K (La), 937.15 and 1144.15 K (Ce),
942.15 and 1170.15 K (Pr) or 935.15 and 1221.15 K (Nd). Their pre-
sence confirms that during thermal decomposition of these complexes
formation of stable intermediate solid products is observed [39–44]. It
is postulated formation of carbonate derivatives (La oxycarbonate,
basic carbonates of Ce and Nd, Pr carbonate) and carbon (in case of
lanthanum, praseodymium and neodymium complexes) based on the
found amounts of the intermediate residues as well as mass losses
(Table 3) [41,42,44–47].
The amount of the final solid residue at 1273.15 K estimated from
the TG curve of Ce(III) ternary complex is suitable to cerium oxide
(CeO2) [35]. The solid residues obtained for La(III), Pr(III) and Nd(III)
complexes are considerably higher than these calculated for the ap-
propriate oxides (La2O3, Pr6O11 and Nd2O3) and they contained a black
solid which may be carbon derived from undecomposed nfa ligand.
These facts suggest that the final products of thermal decomposition
consist of the metal oxides and carbon, resulting from the uncompleted
pyrolysis of the La(III), Pr(III) and Nd(III) complexes [43,48–50].
3.3.2. Thermal decomposition of the complexes in air atmosphere
The simultaneous TG/DTG-DSC curves of the ternary complexes in
L. Zapała et al. Thermochimica Acta 659 (2018) 242–252

nitrogen atmosphere, it can be assigned to the partial release of phe-

nanthroline ligand. On the contrary to investigation in nitrogen atmo-
sphere, for Ce ternary complex, the phenanthroline partial loss is con-
nected with distinguishable peak in the DTG curve. In case of
lanthanum ternary complex, the partial loss of phenanthroline, occurs
in two steps with small mass loss. Both dehydration as well as partial
loss of N-donor ligand in air atmosphere occur without significant
thermal event in the simultaneously registered DSC curves.
From the above analysis, as well as results obtained in inert atmo-
sphere, it can be concluded that in the case of ternary complexes the
bonds between lanthanide ions and N-donor ligand break firstly (apart
from the release of weakly bounded water molecules) in the TG ex-
periments. It clearly confirms the weaker bond energy of Ln–N than that
of Ln–O, which can be explained by the lanthanides preference more to
oxygen than nitrogen donor atoms and longer bond of Ln–N than that of
Ln–O [5,20].
In a dynamic air atmosphere, in temperature range of
623.15–823.15 K the mass loss takes place in two overlapping steps for
all obtained compounds. They are characterized by the strong, narrow
peaks on the DTG curves. The first one is centered at 700.15 K (La),
681.15 K, (Ce), 697.15 K (Pr) or 700.15 K (Nd) and is connected with
39.23% (La), 19.86% (Ce), 39.56% (Pr) and 42.39% (Nd) mass loss. The
DSC curves show no peak corresponding to this decomposition step and
only the second, strongly exothermic peak is visible. On the DTG curves
this second one is centered at 788.15 K (La), 742.15 K, (Ce), 798.15 K
(Pr) and 793.15 K (Nd) and corresponds to 28.79% (La), 53.21% (Ce),
27.09% (Pr) and 24.42% (Nd) mass loss.
Similarity to the thermoanalytical profiles of ternary complexes
reported in the literature [5,20] suggests that the first mass loss is
connected with the degradation of the ligands and the next one corre-
sponds to degradation and oxidation process.
Above 823.15 K on the DTG curves of lanthanum and neodymium
ternary complexes one additional step connected with small mass loss
at 948.15 K (La) and 889.15 K (Nd) appears. Thus, the oxidation of the
organic matter in case of these ternary complexes leads to formation of
carbonaceous residue and/or derivative of the lanthanide carbonate as
intermediate products. On the other hand, in the case of cerium and
praseodymium complexes the DTG profiles do not exhibit any addi-
tional peaks related to mass loss and after oxidation of the organic
matter the final products of the thermal degradation are formed.
The percentage of solid residues indicates that ternary complexes in
air atmosphere were completely degraded into appropriate lanthanide
oxides (La2O3, CeO2, Pr6O11, Nd2O3).

3.4. Evolved gas analysis

Fig. 8. EGA-FTIR for ternary Nd(III) complex in air atmosphere: a) stacked plot of the
FTIR spectra of the evolved gases, b) the FTIR spectra of the evolved gases produced at
different temperatures. The gaseous products evolved during the thermal decomposition of
the ternary complexes in air and nitrogen atmosphere were studied by
applying simultaneous TG-FTIR and TG-MS techniques (the assign-
air atmosphere are presented in Fig. 3 e–h. Under air atmosphere, six
ments of the mass fragments detected by using TG-MS technique are
steps of thermal degradation were noted for La(III) complex and five for
summarized in Table 6). Due to the fact, that the gases released in this
Nd(III) complex. However, complexes with Ce(III) and Pr(III) exhibit
process are the same for all studied compounds, only the results ob-
four steps of decomposition. It is worth noting that in air atmosphere
tained for the neodymium complex were presented.
thermal degradation of all the tested compounds is completed up to
The Gram-Schmidt curves shown in Fig. 4 reveal that elimination of
933.15 K. The details of the thermal decomposition stages in air are
gaseous species generates the variation trend of spectral intensity with
listed in Table 5.
time and the intensities of the Gram-Schmidt traces increase as soon as
The comparison of the thermoanalytical profiles of the complexes
the domains in DTG curves are detected. In Gram-Schmidt profile in
that have been registered in inert and oxidizing atmosphere reveals that
nitrogen six maxima can be distinguished, which are associated with
change of atmosphere has no significant influence on the first (for all
four steps of thermal decomposition of neodymium complex, while
complexes) and second (for Pr and Nd complexes) thermal degradation
Gram-Schmidt curve in air atmosphere shows one significant over-
steps under 623.15 K. Thus, the first stage that corresponds to the loss of
lapped maximum. The first and the last steps of complex degradation in
the water molecules occurs between 303.15 and 463.15 K for all in-
oxidative conditions are not clearly observed, probably due to small
vestigated complexes.
amount of released gas. Evolved gases analysis will be described in
The next decomposition step, below 623.15 K, is connected with
detail below.
two peaks (La) or one peak (Ce, Pr, Nd) on DTG curves. Similarly as in

249
L. Zapała et al.
Fig. 9. Ion currents for selected fragments with the corresponding DTG curves for ternary Nd(III) complex in air.
3.4.1. EGA for Nd-nfa-phen in nitrogen
Stacked plots of the FTIR spectra of the gaseous species for neody-
mium complex during decomposition in nitrogen are shown in Fig. 5a.
Selected FTIR spectra of the gaseous species in different temperature
are presented in Fig. 5b.
During heating in the temperature range 303.15–458.15 K, the mass
spectra and the FTIR spectra of evolved gaseous products show signals
and absorption bands characteristic only for water molecules that prove
the release of the crystal water and this fact is consistent with the TG
experiment.
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Thermochimica Acta 659 (2018) 242–252
Whereas, in the FT-IR spectrum at 591.15 K the low-intensity ab-
sorption bands of CO2 (doublet at 2358 and 2321 cm−1, 669 cm−1) are
observed, the signals corresponding to second step of the thermal de-
composition are hardly distinguishable in the MS spectra (Fig. 6). The
lack of the bands characteristic for other small molecules may indicate
that the aromatic rings of the organic ligands have not been broken.
In the temperature range 617.15-815.15 K, where the main mass
loss is noted, in mass spectra the signals with m/z 12, 16, 44 and 46
(Fig. 6b, e) were detected, related to CO2, but no evolution of hydro-
carbons was detected by EGA-MS. In the FT-IR spectrum at 722.15 K,
L. Zapała et al.
besides the bands in the range 2400–2250 cm−1 and 750–600 cm−1
attributed to carbon dioxide, also the bands characteristic for aromatic
hydrocarbons were noted at 3057, 1597, 1507, 1302, 742 and
720 cm−1 [51]. The similar effect was observed in the case of pre-
viously reported binary complexes [39]. The signals with m/z 26, 39,
50, 51, 52, 63, 65, 66, 76, 77, 92 (Fig. 6c, d) are diagnostic for benzene
ring compounds as well as the products of the fragmentation of the
aromatic ligands and they were detected slightly above the third tem-
perature of maximum mass loss. The EGA-MS and EGA-FTIR analyses
confirm that decomposition of intermediate derivate of lanthanide
carbonate in the next step of the thermal degradation is connected with
the evolution of CO2. Additionally, the FTIR spectrum at 895.15 K
shows simultaneous emission of the carbon monoxide at this stage. The
presence of these bands with the intensity almost equal to the intensity
of CO2 bands, confirms the influence of the size of the evolved mole-
cules on variations in the time of their detection in inert atmosphere
[52].
In the temperature range 1073.15-1273.15 K the fragments related
to carbon dioxide are noted in MS spectra. In the FT-IR spectrum at
1221.15 K only the bands derived from CO2 and CO are detected. Thus,
the mass spectra as well as the FT-IR spectra clearly confirm that inert
flow of nitrogen does not give a constant final residue at 1273.15 K and
slow pyrolysis of the charred residue is not completed.
Taking into account results of both thermoanalytical techniques
(TG-DTG-DSC, TG- FTIR-MS) the decomposition pathways for the stu-
died compounds in nitrogen atmosphere have been proposed and
shown in Fig. 7.
3.4.2. EGA for Nd-nfa-phen in air
The EGA-3D FTIR spectra and the FT-IR evolution curves of the
gaseous species recorded as absorbance vs. temperature are shown in
Fig. 8, while the EGA-MS evolution curves as ion currents of the
characteristic mass fragments are presented in Fig. 9.
The pathway of thermal decomposition of the ternary complex in
the temperature range 303.15–613.15 K in air and nitrogen atmosphere
is very similar. On the basis of EGA-MS and EGA-FTIR analyses it was
confirmed that in the first and second steps of the thermal decom-
position only the evolution of water and carbon dioxide takes place.
However, the atmosphere change has significant impact on the next
degradation stages. In temperature range corresponding to third step of
mass loss, in MS spectra (Fig. 9b, f and d, respectively), the signals
originate from the evolution of both CO2 (m/z 12, 16, 44 and 46) and
NO (m/z 30) were detected. The FT-IR spectrum recorded at 700.15 K
shows characteristic bands attributed to carbon dioxide molecules. No
signals and bands diagnostic for aromatic compounds were detected.
Fig. 9 shows that during the next decomposition step, except the
signals deriving from release ions with m/z 12, 16, 44, 46 and 30
(Fig. 9b, d, f), the fragments with m/z 1, 2, 17, 39, 50, 51, 52, 76, 77
and 78 also occur (Fig. 9c, e, f). The presence of these species in the
evolved gases (Table 6) indicates that in the fourth degradation step the
bonds of the ligands were ruptured together with oxidation of some
moieties. The weak bands at 966 and 929 cm−1, 2179 and 2102 cm−1
in the IR spectrum at 793.15 K confirm presence of ammonia and
carbon monoxide in the evolved gaseous products. Additionally, the
FTIR spectrum recorded at 793.15 K allows suggest that the main
amount of CO2 is produced in this step.
According to MS spectra, the evolution of CO2 ends the last stage of
thermal decomposition of ternary complex in air. On the other hand, in
the FTIR spectrum at 889.15 K, except the bands derived from CO2 also
the bands characteristic for aromatic fragments are still detectable in
the evolved gases.
4. Conclusion
Four novel ternary complexes of La(III), Ce(III), Pr(III) and Nd(III)
ions with N-phenylanthranilic acid and 1,10-phenanthroline as ligands
251
Thermochimica Acta 659 (2018) 242–252
have been synthesized and their spectroscopic properties as well as
thermal decomposition were characterized. The characteristics of the
complexes were done based on elemental analysis, gravimetry, infrared
spectroscopy, X-ray powder diffraction and thermoanalytical techni-
ques. The following general formula of the obtained complexes was
proposed: Ln2(nfa)5(phen)(OH)·nH2O (where nfa – N-phenylan-
thranilate anion; phen – 1,10‐phenanthroline). XRD analysis indicated
that these compounds are amorphous.
The infrared spectroscopic data of obtained complexes demon-
strated that in coordination of lanthanide ions the oxygen atoms of the
carboxylate group of N-phenylanthranilate ligand and nitrogen atoms
of the neutral ligand – phenanthroline are involved. The values of Δν
suggest a bridging bidentate or mixed bridging–chelating mode for the
N-phenylanthranilate ions.
The TG/DTG-DSC analysis provided, previously unreported in-
formation, about the thermal stability and thermal decomposition of
these compounds as well as indicated that complexes are stable at room
temperature. During thermal decomposition firstly occurred the dehy-
dration and then phenanthroline ligand was decomposed.
The final solid residues of thermal decomposition were lanthanide
oxides Ln2O3 (Ln = La, Nd), CeO2 and Pr6O11 in air atmosphere. In
nitrogen atmosphere it was CeO2 or mixture of lanthanide oxide (La2O3,
Nd2O3, and Pr6O11) and carbon resulting from the uncompleted de-
composition of the La(III), Pr(III) and Nd(III) complexes. The thermal
stability of the obtained complexes is slightly different due to the nature
of the metal ion and also depends on the applied atmosphere.
The EGA analysis by TG-FTIR and TG-MS proved that gaseous
products formed during thermal decomposition of the studied com-
plexes were the same. These gases included water, carbon monoxide,
carbon dioxide, diphenylamine, fragments from partial decomposition
of organic ligands in nitrogen atmosphere and water, carbon monoxide,
carbon dioxide, nitrogen monoxide, ammonia, fragments from partial
decomposition of organic ligands in air atmosphere.
Acknowledgements
The authors are grateful to Dr Beata Mossety-Leszczak from
Department of Industrial and Materials Chemistry, Rzeszow University
of Technology for performance of DCS analyses.
We thank also Piotr Szałański for made X-ray analysis in the
Laboratory of Spectrometry, Faculty of Chemistry, Rzeszow University
of Technology.
References
[1] G.-C. Zong, J.-X. Huo, N. Ren, J.-J. Zhang, X.-X. Qi, J. Gao, L.-N. Geng, S.-P. Wang,
S.-K. Shi, Preparation, characterization and properties of four new trivalent lan-
thanide complexes constructed using 2-bromine-5-methoxybenzoic acid and 1,10-
phenanthroline, Dalton Trans. 44 (33) (2015) 14877–14886.
[2] Y. Wang, C.-W. Jin, S.-M. He, N. Ren, J.-J. Zhang, Five novel lanthanide complexes
with 2-chloroquinoline-4-carboxylic acid and 1,10-phenanthroline: crystal struc-
tures, molecular spectra, thermal properties and bacteriostatic activities, J. Mol.
Struct. 1125 (2016) 383–390.
[3] M. Chen, M. Hu, W.-M. Xu, E.C. Sañudo, S.-M. Fang, C.-S. Liu, Six lanthanide su-
pramolecular frameworks based on mixed m-/p-hydroxybenzoic acid and 1,10-
phenanthroline tectons: syntheses, crystal structures, and properties, Polyhedron
113 (2016) 132–143.
[4] N.S. Kariaka, V.A. Trush, P. Gawryszewska, V.V. Dyakonenko, S.V. Shishkina,
T.Yu. Sliva, V.M. Amirkhanov, Spectroscopy and structure of [LnL3bipy] and
[LnL3phen] complexes with CAPh type ligand dimethylbenzoylamidophosphate, J.
Lumin. 178 (2016) 392–399.
[5] J.-Y. Liu, N. Ren, J.-J. Zhang, C.-Y. Zhang, H.-H. Song, Crystal structures, thermal
behavior and biological activities of lanthanide compounds with 2,4-di-
chlorobenzoic acid and 1,10-phenanthroline, Sci. China Chem. 57 (2014)
1520–1531.
[6] X. Qi, N. Ren, D. Zhang, J. Zhang, Synthesis, spectroscopic, thermochemical
properties of lanthanide complexes with 3,4-diethoxybenzoic acid and 1,10-phe-
nanthroline, Chem. Res. Chin. Univ. 31 (2015) 1039–1045.
[7] Nibha, B.P. Baranwal, G. Singh, C.G. Daniliuc, Synthesis, characterization and
thermolysis of lanthanide metal nitrate complexes with 1, 10-phenanthroline, Part-
95, J. Rare Earth 32 (2014) 545–552.
[8] G. Zhao, F. Li, H. Lin, H. Lina, Synthesis characterization and biological activity of
L. Zapała et al.
complexes of lanthanum(III) with 2-(10 −phenyl- 20 −carboxyl-30 −aza-n-butyl)-
1,10-phenanthroline and 2-(10 −p-phenol-20 −carboxyl-30 −aza-n-butyl)- 1,10-
phenanthroline, Bioorg. Med. Chem. 15 (2007) 533–540.
[9] F.-H. Li, G.-H. Zhao, H.-X. Wu, H. Lin, X.-X. Wu, S.-R. Zhu, H.-K. Lin, Synthesis,
characterization and biological activity of lanthanum(III) complexes containing 2-
methylene–1,10-phenanthroline units bridged by aliphatic diamines, J. Inorg.
Biochem. 100 (2006) 36–43.
[10] E. Nieboer, C.K. Jørgensen, R.D. Peacock, R. Reisfeld, Rare earths, in: J.D. Dunitz,
P. Hemmerich, R.H. Holm, J.A. Ibers, C.K. Jørgensen, J.B. Neilands, D. Reinen,
R.J.P. Williams (Eds.), Structure and Bonding, Springer-Verlag, New York
Heidelberg, Berlin, 1975, pp. 1–47.
[11] A. Bencini, V. Lippolis, 1,10-Phenanthroline: a versatile building block for the
construction of ligands for various purposes, Coord. Chem. Rev. 254 (2010)
2096–2180.
[12] Y.-H. Tan, J.-B. Xiong, J.-X. Gao, Q. Xu, C.-W. Fu, Y.-Z. Tang, S.-P. Yang, H.-R. Wen,
Synthesis, crystal structures, and properties of three metal complexes with N-phe-
nylanthranilic acid, J. Mol. Struct 1086 (2015) 49–55.
[13] Q. Yang, S. Chen, S. Gao, Syntheses characterization and thermal properties of the
lanthanide complexes with 2-mercaptonicotinic acid and 1,10-phenanthroline,
Russ. J. Phys. Chem A 83 (2009) 357–360.
[14] P. Garg, M.C. Sanguinetti, Structure-activity relationship of fenamates as Slo2.1
channel activators, Mol. Pharmacol. 82 (2012) 795–802.
[15] Y. Sarrafi, M. Mohadeszadeh, K. Alimohammadi, Microwave-assisted chemoselec-
tive copper-catalyzed amination of o-chloro and o-bromobenzoic acids using aro-
matic amines under solvent free conditions, Chin. Chem. Lett. 20 (2009) 784–788.
[16] L. Zapała, J. Kalembkiewicz, Studies on the distribution of N-phenylanthranilic acid
in two-phase system: aromatic solvent–water, Talanta 69 (2006) 601–607.
[17] B. Yan, H.J. Zhang, G.L. Zhou, J.Z. Ni, Different thermal decomposition process of
lanthanide complexes with N-phenylanthranilic acid in air and nitrogen atmo-
sphere, Chem. Pap. 57 (2003) 83–86.
[18] B. Yan, H. Zhang, S. Wang, J. Ni, Synthesis, characterization, and photophysical
properties of rare earth complexes of N-Phenyl-2-aminobenzoic acid and 1,10-
Phenanthroline, Monatsh. Chem. 129 (1998) 567–575.
[19] Y.-Y. Zhang, N. Ren, S.-L. Xu, J.-J. Zhang, D.-H. Zhang, A series of binuclear lan-
thanide(III) complexes: crystallography, antimicrobial activity and thermo-
chemistry properties studies, J. Mol. Struct. 1081 (2015) 413–425.
[20] J.-F. Wang, H. Li, J.-J. Zhang, N. Ren, K.-Z. Wu, Crystal structures and thermal
decomposition mechanism of four lanthanide complexes with halogen-benzoic acid
and 1,10-phenanthroline, Sci. China Chem. 55 (2012) 2161–2175.
[21] R. Risoluti, D. Piazzese, A. Napoli, S. Materazzi, Study of [2-(2’-pyridyl)imidazole]
complexes to confirm two main characteristic thermoanalytical behaviors of tran-
sition metal complexes based on imidazole derivatives, J. Anal. Appl. Pyrolysis 117
(2016) 82–87.
[22] J.A. Teixeira, A.B. Siqueira, Thermal and spectroscopic characterization, anti-
oxidant evaluation and pyrolysis of losartan with some bivalent metals, J. Anal.
Appl. Pyrolysis 117 (2016) 17–24.
[23] Z. Zheng, Ligand-controlled self-assembly of polynuclear lanthanide–oxo/hydroxo
complexes: from synthetic serendipity to rational supramolecular design, Chem.
Commun. 24 (2001) 2521–2529.
[24] D.E. Chirkst, O.L. Lobacheva, N.V. Dzhevaga, Ion flotation of lanthanum(III) and
holmium(III) from nitrate and nitrate-chloride media, Russ. J. Inorg. Chem. 85
(2012) 25–28.
[25] E. Bentouhami, G.M. Bouet, J. Meullemeestre, F. Vierling, M.A. Khan,
Physicochemical study of the hydrolysis of Rare-Earth elements (III) and thorium
(IV), C. R. Chim. 7 (2004) 537–545.
[26] M. Taş, O.Z. Yeşilel, O. Büyükgüngör, Novel copper(II) complexes of N-phenylan-
thranilic acid containing ethanol and hydroxo ligands, J. Inorg. Organomet. Polym.
20 (2010) 298–305.
[27] A. Topacli, S. Ide, Molecular structures of metal complexes with mefenamic acid, J.
Pharm. Biomed. Anal. 21 (1999) 975–982.
[28] H. Bojarowicz, Z. Kokot, A. Surdykowski, Complexes of Fe(III) ions with mefenamic
acid, J. Pharm. Biomed. Anal. 15 (1996) 339–342.
[29] K. Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination
Compounds, fourth ed., John Wiley & Sons, New York, 1986.
[30] H.-W. Gu, S.-X. Xiao, H.-Y. Xiao, Y. Xiao, A.-T. Li, X.-L. Hu, Q.-G. Li, Synthesis
characterization, and thermodynamic properties of the rare earth coordination
complex [Sm(C6H4NO2)2∙C9H6NO], Ind. Eng. Chem. Res. 51 (2012) 4797–4803.
[31] G.-C. Zong, N. Ren, J.-J. Zhang, X.-X. Qi, J. Gao, Lanthanide complexes with 3-
bromine-4-methyl benzoic acid and 1,10-phenanthroline. Synthesis, crystal struc-
tures, thermal properties and bacteriostatic activities, J. Therm. Anal. Calorim. 123
(2016) 105–116.
252
Thermochimica Acta 659 (2018) 242–252
[32] W. Brzyska, K. Borzechowski, Preparation, properties and thermal decomposition of
Y(III) and lanthanide(III) complexes with 2-amino-5-chlorobenzoic acid, Polish J.
Chem. 71 (1997) 1518–1524.
[33] C.-H. Huang, Rare Earth Coordination Chemistry: Fundamentals And Applications,
John Wiley & Sons, Singapore, 2010.
[34] G. Sharma, A.K. Narula, Eu3+, Yb3+ and Eu3+-Yb3+ complexes with salicylic acid
and 1,10-phenanthroline: synthesis, photoluminescent properties and energy
transfer, J. Fluoresc. 25 (2015) 355–360.
[35] F.J. Caires, D.J.C. Gomes, A.C. Gigante, M. Ionashiro, Thermal investigation and
infrared evolved gas analysis of solidtrivalent lanthanide and yttrium −hydro-
xyisobutyrates in N2 and CO2 atmospheres, J. Anal. Appl. Pyrolysis 107 (2014)
313–322.
[36] M.R. Anoop, K.R. Jisha, S. Suma, M.R. Sudarsanakumar, Synthesis spectral char-
acterization, thermal and biological studies of lanthanide(III) complexes of oxy-
phenbutazone, J. Rare Earth 32 (2014) 43–51.
[37] N. Ren, J.-J. Zhang, S.-L. Xu, R.-F. Wang, S.-P. Wang, Synthesis, crystal structure
and thermal decomposition mechanism of complex [Sm(o-MBA)3phen]2,
Thermochim. Acta 438 (2005) 172–177.
[38] L. Zapała, M. Kosińska, E. Woźnicka, Ł. Byczyński, W. Zapała, Synthesis, spectral
and thermal study of La(III), Nd(III), Sm(III), Eu(III), Gd(III) and Tb(III) complexes
with mefenamic acid, J. Therm. Anal. Calorim. 124 (2016) 363–374.
[39] L. Zapała, M. Kosińska, E. Woźnicka, Ł. Byczyński, W. Zapała, J. Kalembkiewicz,
Spectroscopic study, thermal investigation and evolved gas analysis (EGA) during
pyrolysis and oxidative decomposition of new binuclear complexes of La(III), Ce
(III), Pr(III) and Nd(III) with N-phenylanthranilic acid, J. Anal. Appl. Pyrolysis 123
(2017) 1–11.
[40] D.A. Gálico, T.F.C. Fraga-Silva, J. Venturini, G. Bannach, Thermal, spectroscopic
and in vitro biological studies of the lanthanum complex of naproxen, Thermochim.
Acta 644 (2016) 43–49.
[41] F.X. Campos, A.L.C.S. Nascimento, T.A.D. Colman, D.A. Galico, A.C.S. Carvalho,
F.J. Caires, A.B. Siqueira, M. Ionashiro, Thermal behavior, Spectroscopic studies
and Free radical scavenging potential of some mefenamate trivalent lanthanides
(Sm Eu, Gd, Tb and Dy), Thermochim. Acta 651 (2017) 73–82.
[42] J.-C. Grivel, M.J. Suarez Guevara, Y. Zhao, X. Tang, P.G.A.P. Pallewatta,
J. Bednarčík, A. Watenphul, Thermal behavior and decomposition of cerium(III)
butanoate, pentanoate and hexanoate salts upon heating in argon, J. Anal. Appl.
Pyrolysis 126 (2017) 77–87.
[43] R. Łyszczek, H. Głuchowska, B. Cristóvão, B. Tarasiuk, New lanthanide biphenyl-
4,4-diacetates – hydrothermal synthesis, spectroscopic, magnetic and thermal in-
vestigations, Thermochim. Acta 645 (2016) 16–23.
[44] A.L.C.S. Nascimento, J.A. Teixeira, W.D.G. Nunes, F.X. Campos, O. Treu-Filho,
F.J. Caires, M. Ionashiro, Thermal behavior spectroscopic study and evolved gas
analysis (EGA) during pyrolysis of picolinic acid, sodium picolinate and its light
trivalent lanthanide complexes in solid state, J. Anal. Appl. Pyrolysis 119 (2016)
242–250.
[45] A. Mercandante, M. Ionashiro, L.C.S. De Oliveira, C.A. Ribeiro, L. Moscardini
D'Assunção, Preparation and thermal decomposition of solid state lanthanide(III)
and yttrium(III) chelates of ethylenediaminetetraacetic acid, Thermochim. Acta 216
(1993) 267–277.
[46] L. Moscardini D'Assunção, M. Ionashiro, D.E. Rasera, I. Giolito, Thermal decom-
position of the hydrated basic carbonates of lanthanides and yttrium in CO2 at-
mosphere, Thermochim. Acta 219 (1993) 225–233.
[47] L. Moscardini D'Assunção, I. Giolito, M. Ionashiro, Thermal decomposition of the
hydrated basic carbonates of lanthanides and yttrium, Thermochim. Acta 137 (2)
(1989) 319–330.
[48] C.-W. Jin, Q.-Q. Zhao, N. Ren, J.-J. Zhang, L.-N. Geng, S. Wang, S.-K. Shi,
Preparation crystal structures and properties of a series of novel lanthanide com-
plexes based on 2,3-dimethoxybenzoic acid and 1,10-phenanthroline, Polyhedron
135 (2017) 206–215.
[49] X.-X. Qi, J.-C. Wu, N. Ren, C.-L. Zhao, J.-J. Zhang, G.-C. Zong, J. Gao, Novel lan-
thanide complexes constructed from 3,4-dimethoxybenzoic acid: crystal structures,
spectrum and thermochemical properties, Thermochim. Acta 615 (2015) 1–7.
[50] J.-Y. Liu, N. Ren, J.-J. Zhang, C.-Y. Zhang, Preparation thermodynamic property
and antimicrobial activity of some rare-earth (III) complexes with 3-bromo-5-io-
dobenzoic acid and 1,10-phenanthroline, Thermochim. Acta 570 (2013) 51–58.
[51] R.M. Silverstein, F.X. Webster, D.J. Kiemle, Spectrometric Identification of Organic
Compounds, seventh ed., Wiley, New York, 2005.
[52] F.X. Campos, A.L.C.S. Nascimento, T.A.D. Colman, D.A. Gálico, O. Treu-Filho,
F.J. Caires, A.B. Siqueira, M. Ionashiro, Synthesis, characterization and thermal
behavior of solid state of some mefenamate of trivalent lanthanides (La, Ce, Pr and
Nd), J. Therm. Anal. Calorim. 123 (1) (2016) 91–103.