Investigation of desolvation process in lanthanide dinicotinates

Article abstract of DOI:10.1007/s10973-010-1106-0

The desolvation process in lanthanide pyridine-3,5-dicarboxylates of the formulae [Tb₂pdc₃(dmf)₂]?dmf (1), [Ho ₂pdc₃(dmf)₂]?dmf (2), [Erdc ₃(dmf)₂]?dmf (3), and [Yb₂pdc ₃(dmf)₂]?dmf (4) where pdc-C₅H ₃N(COO) ₂ ^2-, dmf-N,N′-dimethylformamide) has been investigated by means of the TG-DSC, TG-FTIR, IR and XRD methods. Heating of the complexes in the range 30-260 °C lead to evolution of weakly bonded dmf molecules included in the channels as well those directly bonded with lanthanide atoms. The kinetic analysis revealed a multistep desolvation pattern.

Full text of DOI:10.1007/s10973-010-1106-0

J Therm Anal Calorim (2011) 103:633–639
DOI 10.1007/s10973-010-1106-0
Investigation of desolvation process in lanthanide dinicotinates
•
R. Łyszczek M. Iwan
Received: 1 June 2010 / Accepted: 13 October 2010 / Published online: 3 November 2010
´
´
Ó Akademiai Kiado, Budapest, Hungary 2010
Abstract The desolvation process in lanthanide pyridine-
3,5-dicarboxylates of the formulae [Tb2pdc3(dmf)2]ꢀdmf
(1), [Ho2pdc3(dmf)2]ꢀdmf (2), [Erdc3(dmf)2]ꢀdmf (3), and
[Yb2pdc3(dmf)2]ꢀdmf (4) where pdc-C5H3N(COO)22-, dmf-
N,N0-dimethylformamide) has been investigated by means
of the TG–DSC, TG–FTIR, IR and XRD methods. Heating
of the complexes in the range 30–260 °C lead to evolution
of weakly bonded dmf molecules included in the channels
as well those directly bonded with lanthanide atoms. The
kinetic analysis revealed a multistep desolvation pattern.
topology and porosity of the target materials. The resulting
complexes are in the form of 1-, 2- or 3-D structures, with or
without channels, filled by solvent molecules or co-crys-
tallizing organic molecules incorporated during synthesis
[6, 7]. These molecules can be regarded as templates
exterminating the pore sizes and shapes. Usually, these
guest molecules can be removed upon heating of ‘as-made’
sample under reduced pressure and the obtained framework
retains the initial structure, resulting in a porous material
[8–10]. On the other hand, the removal of the included in
cavities molecules can lead to structure collapsing that
results in formation of amorphous phases. For some com-
plexes this process is reversible and the amorphous-to-
crystal transformation can take place [11].
Keywords Lanthanide dinicotinates ꢀ Desolvation ꢀ
Thermal analysis ꢀ Analysis of products ꢀ Kinetic analysis
Taking into consideration behaviour of metal–organic
frameworks during activation, coordination polymers can
be divided into three categories: (1) the first generation of
coordination polymers is of the microporous structures
which show irreversible framework collapse after removal
of the guest molecules. (2) The second generation of
metal–organic frameworks remains porous and crystalline
without any guest molecules in the pores. (3) The third
generation of coordination polymers is of dynamic and
flexible structures which respond to external stimuli (like
guest molecules, light and electric field) in changing their
structures) to change shape and size of channels. The
transformation in the second and third generations is
named ‘crystal-to-crystal’ [12, 13].
Introduction
There has been considerable interest in coordination poly-
mers known as metal–organic frameworks (MOFs) due to
their promising applications such as the molecular recog-
nization and separation from the gaseous and liquid mix-
tures, storage of gases, catalysis and drug delivery [1–3].
Coordination polymers can also be designed as multifunc-
tional materials with the additional physical properties like
magnetism, luminescence and optoelectronics [4, 5]. The
construction of architectures of metal–organic frameworks
consists of the assembly of highly coordinated metal cen-
tres/clusters with multifunctional organic linkers. The
structural properties of the components determine the
The solvent molecules used in the synthesis of coordi-
nation polymers, not only occupy free space in the chan-
nels, but also may take part in the coordination process
being directly bonded with the metal centre [14–19]. N,N0-
dimethylformamide (dmf) is a very popular solvent applied
in the synthesis of lanthanide coordination polymers.
Polarity of dmf molecules is crucial in the growth process
R. Łyszczek (&) ꢀ M. Iwan
Department of General and Coordination Chemistry, Faculty of
Chemistry, University of Maria Curie-Skłodowska, Sq. M.C.
Skłodowskiej 2, 20-031 Lublin, Poland
e-mail: renata.lyszczek@poczta.umcs.lublin.pl
123

634
R. Łyszczek, M. Iwan
of crystals. Dmf dissolves well not only most of the organic
ligands but also inorganic lanthanide species that facilitates
formation of crystalline forms of complexes.
The X-ray powder diffractions of the studied complexes
were recorded on a HZG 4 diffractometer using Ni filtered
CuKa radiations. Measurements were taken over the range
of 2h = 5–70°.
The aim of this study was to investigate the desolvation
process in the complexes of selected heavy lanthanides(III)
with the pyridine-3,5-dicarboxylate ligand. These metal–
organic frameworks were obtained by solvothermal method
from the N,N0-dmf solution. The complexes were previously
investigated in detail by means of elemental analysis, infra-
red spectroscopy, X-ray powder and single crystal diffrac-
tions as well as different methods of thermal analysis [20].
The investigated complexes form the three-dimensional
expanded polymeric network with one-dimensional chan-
nels occupied by solvent molecules. The coordination
environment of central atoms consists of carboxylate
oxygen atoms from pyridine-3,5-dicarboxylate moieties. In
addition, the coordination sphere of metal centres is com-
pleted by oxygen atom from dmf molecules. The com-
plexes reported herein possess 1-D channels along the
crystallographic a axis occupied by disordered dmf mole-
cules [17, 18]. The complexes decompose in two well-
separated weight loss steps. The first one is connected with
the removal of solvent molecules included in the channels
as well as coordinated with metal centres. The second stage
is attributed to the decomposition and burning (air) of the
desolvated form of complexes.
Thermal analysis of prepared complexes was carried out
by the TG–DSC method using SETSYS 16/18 analyser
(Setaram). The samples (about 5–7 mg) were heated in a
ceramic crucible up to 850 °C at a heating rate of 10 °C
min-1 in dynamic air atmosphere (v = 0.75 dm3 h-1). For
kinetic measurements, the heating rates: 5, 2.5 and 1.25 °C
min-1 were applied.
The TG–FTIR coupled measurements have been carried
out using a Netzsch TG apparatus coupled with a Bruker
FTIR IFS66 spectrophotometer. The samples of about
30 mg were heated up to 950 °C at a heating rate of 10 °C
min-1 in flowing argon atmosphere.
The samples of as-made complexes of about 0.1 g were
heated at 100 and 250 °C during 2 h in drying apparatus
Binder.
Results and discussion
The investigations of desolvation process of heavy lantha-
nides [Tb(III), Ho(III), Er(III) and Yb(III)] complexes with
pyridine-3,5-dicarboxylic acid of the formulae: [Tb2pdc3
(dmf)2]ꢀdmf, [Ho2pdc3(dmf)2]ꢀdmf, [Erdc3(dmf)2]ꢀdmf, and
[Yb2pdc3(dmf)2]ꢀdmf (where pdc-C5H3N(COO)22-, dmf-
N,N0-dimethylformamide) molecules have been carried out.
The complexes in question have been obtained as unstable
needle monocrystals. When transparent crystals are exposed
to the air, they partially lose solvent molecules that can be
observed by making crystals dull.
Transformation of coordination polymers into their
porous form is preceded by the activation process, con-
nected with removal of solvent molecules from the chan-
nels as well as rearrangement of their crystal structures.
Activation of lanthanide complexes with pyridine-3,5-
dicarboxylic and dmf molecules occurs after the loss of
free and coordinated solvent molecules that results in for-
mation of crystalline stable Ln2pdc3 frameworks. These
materials are porous and can effectively adsorb nitrogen as
well as benzene molecules [18].
Thermal analysis
In addition, this article deals with the determination of
kinetic parameters of desolvation step connected with
release of coordinated dmf molecules determined using the
AKTS Thermokinetics Software program [21].
The thermal stability of the investigated complexes has been
studied in the air as well as in the argon atmosphere using the
TG–DSC and TG–FTIR methods. It could be mentioned that
during heating of the complexes in the temperature range
30–450 °C, they behave in the same manner under both the
conditions. Thermal properties as well as kinetic investiga-
tions of the studied complexes were performed in air. As can
be seen in Fig. 1, the complexes are stable up to about 30 °C
and then start to decompose. Under air condition, on the TG
curves in the temperature range 30–260 °C weight losses of
22.42, 20.42, 20.64, 21.17 and 21.00% for complexes 1, 2, 3
and 4, respectively, were found. This stage matches well the
removal of solvent molecules from the crystal structures
(calculated mass losses are 20.93, 20.97, 20.89 and 20.67%
for 1, 2, 3 and 4, respectively). Mass loss observed in the
lower temperature range 30°–100 °C, is connected with
release of weakly bonded dmf molecules included in the
Experimental
The studied compounds were synthesized via solvothermal
method in 150 mL teflon-lined autoclaves. The 1.5 mmol
of pyridine-3,5-dicarboxylic acid (dinicotinic acid)
(250 mg) with lanthanide(III) chloride hydrates (obtained
by dissolving of 0.5 mmol of lanthanide oxide in hydro-
chloric acid) were dissolved in 10 mL of N,N0-dmf. The
autoclaves were heated in oven for 5 days at 140 °C and
then cooled to room temperature for 24 h. Needle-shaped
crystals were separated from a clear solution.
123

Investigation of desolvation process
635
2849 cm-1 were assigned to the asymmetric and sym-
metric stretching vibrations of the CH bond from the CH3
groups. Methyl groups of dmf molecules also give char-
acteristic bands derived from asymmetric and symmetric
deformation vibrations at 1482 and 1382 cm-1, respec-
tively. The band located at 1724 cm-1 can be attributed to
the stretching vibrations of the carbonyl CO group. The
band at 1493 cm-1 was assigned to stretching vibrations of
the CN bond [22]. The highest intensity of these bands is
observed at about 220 °C. Removal of dmf molecules
distributed within channels and those coordinated resulted
in the formation of Ln2pdc3 compounds relatively stable in
the temperature range 260–460 °C that is confirmed by the
absence of any bands on the FTIR spectra. Next, collapse
and decomposition of the frameworks take place. Decom-
position of the desolvated form of the complexes is con-
nected with evolution of carbon dioxide molecules giving
characteristic doublet bands at 2359, 2343 cm-1 and those
in the range 750–600 cm-1 ascribed to the valence and
deformation vibrations, respectively (530 °C) [23]. At little
higher temperature, further gaseous products of thermal
decomposition were recorded. The bands at 3075, 3017 and
1217, 1152 cm-1 were assigned to the stretching and
deformation vibrations of C–C and C–N groups from the
free pyridine ring. The double-band with the maxima at
2177 and 2113 cm-1 was derived from carbon monoxide.
Moreover, some unidentified hydrocarbons were released
due to the presence of bands at 3071, 1605, 1484 and
1448 cm-1 [24].
50
40
30
20
10
0
TG
0
Exo
–20
–40
DSC
–60
100 200 300 400 500 600 700 800
Temperature/°C
Fig. 1 TG–DSC curves of [Ho2pdc3(dmf)2]ꢀdmf recorded in air
(solid line) and argon (dashed line)
channels of the crystal frameworks. Further heating of the
complexes resulted in dissociation of bonds between
carbonyl oxygen from dmf molecules and lanthanide
atoms. The dmf molecules release from the coordination
environments of lanthanide ions is accompanied by distinct
endothermic effects on the DSC curves (111–60 kJ/mol) at
temperatures 257, 252, 253 and 252 °C (peak top) for
compounds 1, 2, 3 and 4, respectively. Further heating
cause decomposition of desolvated forms of complexes
which is accompanied with burning of organic ligand (air
atmosphere). As the solid residue of thermal decomposi-
tion, the corresponding oxides: Tb4O7, Ho2O3, Er2O3 and
Yb2O3 (in air) or mixture of oxides and carbon (in argon
atmosphere) are formed [20].
The TG–FTIR technique was applied as the method
providing more information about the reaction sequences
and the relevant products of decomposition especially in
the temperature range of desolvation. Since the pathways
of degradation under both conditions up to 450 °C are the
same, the results obtained by means of the TG–FTIR
method were applied to the data obtained from the ther-
mogravimetric analysis in air condition.
The most interesting stage during thermal decomposi-
tion of the studied complexes is release of solvent mole-
cules from the crystal structures of the complexes. Heating
the complexes up to 250 °C in air atmosphere under
atmospheric pressure leads to cracking of crystals. They are
still crystalline but still intransparent that excludes them in
further single crystal X-ray measurements. The infrared
spectra of the obtained compounds confirm release of dmf
molecules from the crystal structures. The IR spectra of
desolvated complexes do not show characteristic bands
derived from the dmf molecules compared with as-made
complexes. There are not observed stretching vibrations of
As can be seen from the FTIR spectrum of gaseous
products of the desolvation process (Fig. 2) recorded at
175 °C, there are bands derived from gaseous N,N0-
dimethylformamide molecules. The bands at 2939 and
Fig. 2 Stacked plot of FTIR
spectra of the evolved gases for
[Ho2pdc3(dmf)2]ꢀdmf
ν(CO)
ν(CO2)
δsCH3
rCH3
νCO
δaCH3
νCH
νCN
530 °C
220 °C
175 °C
4000
3500
3000
2500
2000
1500
1000
Wavenumber/cm–1
123

636
R. Łyszczek, M. Iwan
Fig. 3 IR spectra of complex
a [Ho2pdc3(dmf)2]ꢀdmf; b after
heating at 250 °C
(a)
(b)
120
4000 3600 3200 2800 2400 2000
1800
1600
1400
1200
1000
800
600
400
Wavenumber/cm–1
Table 1 Most characteristic bands (cm-1) in the IR spectra of 1, 2, 3
and 4 complexes and their desolvated forms
(c)
mCH3
mCO (dmf) mas COO
msym COO
1632, 1600 1384
1604 1380
[Tb2pdc3(dmf)2]ꢀ 3062, 2940 1668
dmf (1)
Tb2pdc3
–
–
[Ho2pdc3(dmf)2]ꢀ 3092, 2928 1680, 1651 1632, 1612 1388
dmf (2)
Ho2pdc3
–
–
1608
1384
(b)
(a)
[Er2pdc3(dmf)2]ꢀ 3092, 2928 1688, 1656 1640, 1612 1388
dmf (3)
Er2pdc3
–
–
1604
1384
[Yb2pdc3(dmf)2]ꢀ 3092, 2928 1688, 1656 1640, 1610 1380
dmf (4)
Yb2pdc3
–
–
1608
1388
10
15
20
25
30
35
40
CH3 groups in the wavenumber range 3000–2900 cm-1 as
well as stretching vibrations from carbonyl group in the
range 1690–1650 cm-1 derived from the dmf molecules
(Fig. 3). Moreover, as can be seen from Table 1, the
characteristic bands derived from stretching asymmetric
and symmetric vibrations of carboxylate groups in the
infrared spectra of desolvated complexes are shifted com-
pared with those in as-made complexes. In addition, the
bands of the asymmetric stretching vibrations of COO
groups observed in IR spectra of heated complexes are not
split as it takes place for as-made complexes.
2θ
Fig. 4 XRD patterns of a original solid [Ho2pdc3(dmf)2]ꢀdmf; b after
heating at 100 °C for 2 h; c after heating at 250 °C for 2 h
Comparison of the XRD results of as-made complexes with
the heated samples leads to the conclusion that departure of
the guest molecules and the coordinated dmf molecules
does not cause the collapse of the crystal structures. This
result indicates formation of stable frameworks composed
of lanthanide atoms and dinicotinate ligands during heat-
ing. As can be seen in Fig. 4, the most intense reflexes in
the heated sample are observed at slightly higher values of
2h (6.26, 10.95, 11.45, 12.35 and 18.70) compared with
those of as-made complexes (6.05, 10.35, 10.75, 12.10 and
18.25). This data may point to some transformation in their
crystal structures that is indicative for crystal-to-crystal
transformation. Since, the dmf molecules were bonded
with lanthanide ions, their removal from the coordination
The powder X-ray diffractions were performed for the
as-synthesized samples, and those heated at 100 and
250 °C. The XRD patterns for the samples heated at
100 °C are similar to those of as-made samples, which
indicates that release of guest molecules from the channels
does not lead to collapse of the crystal structure (Fig. 4).
The X-ray powder diffraction patterns of the samples
heated at 250 °C revealed that they remain crystalline.
123

Investigation of desolvation process
637
environment of metals resulted in rearrangement of coor-
dination mode of carboxylate groups.
The TG signals after correction of the baseline were
used to estimate the reaction progress. Figure 5 presents
the reaction rate as a function of temperature for lanthanide
dinicotinate desolvation. Comparison of the experimental
(symbols) and the simulated courses of the reaction (lines)
indicated a very good fit when the kinetic analysis was
used. The rate maximum falls in the range of 210–230 °C.
It coincides with the highest intensity of dmf bands in the
FTIR spectra of gaseous products of thermal decomposi-
tion. Figure 6 illustrates the results of the Friedman
analysis, and Fig. 7 shows the activation energies and pre-
exponential factors for the desolvation of the compounds
investigated. The changes in the values of E and A during
the course of the reaction indicate a complex multistep
desolvation pattern [29]. They account well for the two
consecutive stages of dmf molecule release from the
compounds investigated.
The kinetic investigations
The TG data collected during non-isothermal decomposi-
tion of the sample with the heating rates of 1.25, 2.5 and
5 °C min-1 in the dynamic air atmosphere were used for
determination of the kinetic parameters of the dmf removal
reaction. The data were analysed by the AKTS Therm-
okinetics Software using the model-free method, called the
Friedman method [21, 25–28]. The calculations were made
within the temperature range of 100–260 °C. It corre-
sponds to the loss of coordinated dmf molecules. The first
step of thermal decomposition of lanthanide dinicotinates
(30–100 °C), i.e., the stage of release of the weakly bonded
solvent molecules, is not appropriate for kinetic accounts.
Fig. 5 Reaction rate as a
function of temperature for
terbium a, holmium b, erbium
c and ytterbium d dinicotinate
desolvation. Experimental data
are represented as symbols and
(a)
(b)
–3.79E–19
–3.79E–19
2E–4
2E–4
4E–4
6E–4
4E–4
6E–4
8E–4
1E–3
1.2E–3
1.4E–3
1.6E–3
1.8E–3
2E–3
2.2E–3
2.4E–3
1.3
1.33
8E–4
1E–3
2.62
2.63
1.2E–3
1.4E–3
1.6E–3
1.8E–3
2E–3
2.2E–3
2.4E–3
the calculated signals as solid
lines. Notation on curves: the
5.32
5.33
heating rate in °C min-1
80 100 120 140 160 180 200 220 240 260
Temperature/°C
60 80 100 120 140 160 180 200 220 240 260
Temperature/°C
(c)
(d)
–4.07E–19
–3.79E–19
2E–4
1E–4
2E–4
3E–4
4E–4
5E–4
6E–4
7E–4
8E–4
9E–4
1E–3
1.1E–3
1.2E–3
1.3E–3
1.4E–3
1.5E–3
1.6E–3
1.7E–3
1.8E–3
4E–4
6E–4
8E–4
1E–3
1.2E–3
1.4E–3
1.6E–3
1.8E–3
2E–3
2.2E–3
2.4E–3
1.31
2.63
1.33
2.65
5.33
4.28
80 100 120 140 160 180 200 220 240 260
Temperature/°C
80 100 120 140 160 180 200 220 240 260
Temperature/°C
Fig. 6 Friedman analysis for
the desolvation of terbium a,
holmium b, erbium c and
ytterbium d dinicotinates
(a)
(b)
–6
–6.5
–7
–6
–6.5
–7
–7.5
–8
–8.5
–9
–7.5
–8
0.8
0.7
0.9
0.6
0.5
0.7
0.80.6
0.5
0.4
0.95
0.98
0.99
–8.5
–9
–9.5
–10
0.4
0.9
0.3
0.95
0.98
0.3
0.2
0.2
0.1
–9.5
–10
–10.5
–11
–11.5
–12
0.99
0.1
0.05
–10.5
–11
0.02
0.05
0.01
–11.5
–12
0.02
–12.5
–13
0.01
2
2.2
2.4
2.6
2.8
2
2.2
2.4
2.6
2.8
1000/T/100/K
1000/T/100/K
–6
(d) –6.5
(c)–6–.75
–7
–7.5
–8
–7.5
0.8
0.7
0.95
0.8
0.7
0.9 0.6
0.9
0.6
0.5
0.4
–8
–8.5
–9
0.3
0.5
0.95
0.98
0.99
0.98
0.99
–8.5
–9
–9.5
–10
–10.5
–11
–11.5
0.2
0.4
0.3
0.2
0.1
–9.5
–10
–10.5
–11
0.05
0.1
0.02
0.05
0.01
–11.5
–12
0.03
0.01
–12.5
–13
2
2.2
2.4
1000/T/100/K
2.6
2
2.2
2.4
2.6
2.8
1000/T/100/K
123

638
R. Łyszczek, M. Iwan
Fig. 7 Activation energy,
E and pre-exponential factor,
A values as a function of the
reaction progress for the
desolvation of terbium a,
holmium b, erbium c and
ytterbium d dinicotinates
(a)
(c)
(b)
105
24
23
22
21
20
19
18
17
16
15
14
13
12
11
10
9
28
26
24
22
20
18
16
14
12
10
8
130
125
120
115
110
105
100
95
90
85
80
75
70
65
60
55
50
100
95
90
85
80
75
70
65
60
55
8
6
7
6
0
10 20 30 40 50 60 70 80 90 100
0
10 20 30 40 50 60 70 80 90 100
Reaction progress α/%
Reaction progress α/%
(d)
22
21
20
19
18
23
22
21
20
19
18
17
16
15
14
13
12
11
10
9
115
110
105
100
95
110
105
100
95
90
85
80
75
70
65
17
16
15
14
13
12
11
10
9
90
85
80
75
70
65
60
60
55
8
7
55
0
10 20 30 40 50 60 70 80 90 100
0
10 20 30 40 50 60 70 80 90 100
Reaction progress α/%
Reaction progress α/%
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Conclusions
The desolvation process in the studied complexes was
investigated by means of the thermal analysis TG–DSC. It
is connected with the release of the dmf molecules from the
channels as well as those bonded with metal centres as
confirmed by the TG–FTIR analysis. The solid products of
desolvation of the formula Ln2pdc3(dmf)2 retain their
crystalline forms as follows from the XRD patterns. The
calculated values of the kinetic parameters refer to the
reaction of removal of dmf molecules from the inner
coordination sphere of lanthanide atoms. The activation
energies obtained are characteristic of the multistep process.
˚
10. Dietzel PDC, Panella B, Hirscher M, Bloom R. Fjellvag H.
Hydrogen adsorption in a nickel based coordination polymer with
open metal sites in the cylindrical cavities of the desolvated
framework. Chem Commun. 2006;9:959–61.
11. Choi HJ, Lee TS, Suh MP. Self-assembly of a molecular floral
lace with one-dimensional channels and inclusion of glucose.
Angew Chem Int Ed. 1999;38:1405–8.
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coordination polymers. J Solid State Chem. 2005;178:2420–9.
13. Kitagawa S, Uemura K. Dynamic porous properties of coordi-
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14. Wang XF, Zhang Y-B, Huang H, Zhang J-P, Chen X-M.
Microwave-assisted solvothermal synthesis of a dynamic porous
metal-carboxylate framework. Crystal Growth Des. 2008;8:
4559–63.
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