J Therm Anal Calorim (2018) 131:1699–1707
https://doi.org/10.1007/s10973-017-6643-3
Crystal structures, luminescent and thermal properties
of lanthanide complexes with 3,4-dimethylbenzoic acid
and 2,20 -bipyridine
Pan-Pan Shen1,2 • Ning Ren3 • Jian-Jun Zhang1,2 • Li-Na Geng2 • Shu-Ping Wang2
Shi-Kao Shi2
Received: 11 April 2017 / Accepted: 12 August 2017 / Published online: 31 August 2017
 Akadémiai Kiadó, Budapest, Hungary 2017
Abstract Two lanthanide complexes [La(3,4-DMBA)3]n
(1) and [Tb(3,4-DMBA)3(DIPY)2]2 (2) (where 3,4-
DMBA = 3,4-dimethylbenzoate, DIPY = 2,20 -bipyridine)
have been synthesized and then characterized. The single
crystals of complexes 1 and 2 were obtained. Complex 1
adopts a distorted monocapped square antiprismatic
molecular geometry, while complex 2 forms a distorted
square antiprism. Complex 1 is stitched together by edge
sharing through carboxylate ligands to form 1D chains
along the b axis. The structure of complex 2 consists of 1D
chains along the c axis by two kinds of pp stacking
interactions. Two complexes were characterized by ele-
mental analysis, powder X-ray diffraction and IR spectra.
The complex 2 shows typical green luminescence in the
solid state. Thermal decomposition mechanisms of com-
plexes were discussed by TG–DTG techniques. In the
temperature range from 257.15 to 413.15 K, the molar heat
capacities of the complexes were measured by DSC. The
smoothed heat capacities and thermodynamic functions of
Electronic supplementary material The online version of this
article (doi:10.1007/s10973-017-6643-3) contains supplementary
material, which is available to authorized users.
& Ning Ren
ningren9@163.com
& Jian-Jun Zhang
jjzhang6@126.com
1
Testing and Analysis Center, Hebei Normal University,
Shijiazhuang 050024, People’s Republic of China
2 and aromatic carboxylic acids [17].
College of Chemistry and Material Science, Hebei Normal
University, Shijiazhuang 050024, People’s Republic of China
3 excellent organic ligand [18] due to their high affinity to
College of Chemical Engineering and Material, Handan
University, Handan 056005, Hebei Province, People’s
Republic of China
•
complexes were calculated on the basis of fitted polyno-
mial and thermodynamic equations.
Keywords Lanthanide complexes  Crystal structures 
Luminescent  Thermal properties  Heat capacities
Introduction
In recent years, lanthanide complexes have attracted
intense interest due to their diverse structures [1–3] and
intriguing photoluminescence [4]. The former profits are
the diverse coordination geometries and plentiful coordi-
nation numbers of Ln(III) ions, while the latter benefits are
high luminous lifetimes and extremely sharp characteristic
4f–4f emission bands arising from the electronic transitions
between the 4f energy levels [5]. The lanthanide complexes
are widely used in various fields such as magnet [6], optical
materials [7], catalysis [8], optical telecommunication
devices [9], sensors, as well as labels in biological systems
[10]. However, the application of such lanthanide ions
systems is usually blocked due to their very inefficient
direct absorption of the f–f excited states. What is more, the
luminescence intensity of lanthanide complexes is relied on
the efficiency of energy transfer from the ligands to the
lanthanide ions [11]. In order to overcome this drawback,
the numerous suitable ligands are used to sensitize the
luminescence of lanthanide ions via the effective energy
transformation, which is called ‘‘antenna effect’’ [12, 13].
And the ligands include pyridine [14], b-diketones [15, 16]
Aromatic carboxylic acids are often selected as a kind of
the central lanthanide ions and various coordination modes:
monodentate, chelating, bridging and bridging–chelating
123
1700
[19]. Hence, lanthanide monocarboxylate complexes can
exhibit mononuclear, dinuclear or polymeric chain. Addi-
tionally, the introduction of a neutral ligand as the auxiliary
ligand in the lanthanide monocarboxylate complexes can
not only reinforce the fluorescence emission intensities
[20], but also substitute for the coordination of solvent
molecules.
So 3,4-dimethylbenzoic acid (3,4-DMHBA) as the main
ligand and 2,20 -bipyridine (DIPY) as the auxiliary ligand
are selected in this study. We have synthesized two kinds
of lanthanide complexes [La(3,4-DMBA)3]n (1) and
[Tb(3,4-DMBA)3(DIPY)2]2 (2). They are both 1D chains.
In addition, the solid-state luminescent property of com-
plex 2 has been investigated. The thermal decomposition
processes of title complexes were studied by the TG/DSC-
FTIR technology, and the molar heat capacities of com-
plexes were measured by DSC.
Experimental
Materials and methods
LnCl36H2O was acquired by the reaction of La2O3 and
Tb4O7, respectively (Ln = La, Tb, Beijing Lanthanide
Innovation Technology Co., Ltd, 99.9%), and hydrochloric
acid in aqueous solution. The other analytically pure
chemicals were purchased and used without further
purification.
Elemental analyses of C, H, N were performed on a
Vario-EL II element analyzer. The IR spectra were mea-
sured in the range of 4000–400 cm-1 on a Bruker TEN-
SOR 27 spectrometer using KBr medium pellets. Powder
X-ray diffraction identification was carried out by a Bruker
D8 ADVANCE X-ray diffractometer in the scanning range
of 5–50 (2h) with Cu Ka radiation (k = 1.5418 Å). The
single-crystal X-ray diffraction data of complexes were
collected by a Smart-1000 (Bruker AXS) diffractometer
with monochromated Mo Ka radiation (k = 0.71073 Å) at
298 K. The structures were solved using the SHELXS-97
program and refined with full-matrix least squares on F2
using the SHELXL-97 program. The luminescence spectra
were measured on an F-4500 Hitachi Spectrophotometer.
TG and DTG analyses were performed with a heating rate
of 10 K min-1 (simulated air atmosphere) using a
NETZSCH STA 449 F3 instrument. The molar heat
capacities of the complexes 1 and 2 were measured
between 257.15 and 413.15 K on a Netzsch DSC 200 F3
(nitrogen atmosphere) using an indirect measurement
method.
123
P.-P. Shen et al.
Synthesis
LnCl36H2O (Ln = La (1), Tb (2); 0.2 mmol) was dis-
solved in water. The ligands of 3,4-DMHBA (0.6 mmol)
and DIPY (0.2 mmol) were dissolved in ethanol (95%),
and pH was adjusted in a range of 6–7 with the prepared
NaOH solution (1 mol L-1). Then, add the mixed ligands
solution to LnCl36H2O (0.2 mmol) aqueous solution under
stirring and deposit it for 12 h. The resulting precipitate
was filtered off, washed with 95% ethanol and then dried.
Element analysis: Calcd (%) for C54H54La2O12: C
55.30, H 4.64, La 23.69; found (%): C 55.02, H 4.59, La
23.46. Calcd (%) for C74H70N4O12Tb2: C 58.27, H 4.63, N
3.67, Tb 20.84; found (%): C 57.81, H 4.59, N 3.64, Tb
20.65.
Results and discussion
Infrared spectra
The IR spectra data of the ligands and complexes are listed in
Table 1. As shown in Table 1, the m(C=O) stretching frequency
of 3,4-DMHBA at 1678 cm-1 completely disappears in the
IR spectra of complexes 1 and 2; meantime, two new
absorption peaks appear, which are attributed to the mas(COO–)
(1585–1558 cm-1) and ms(COO–) (1421–1418 cm-1) of the
carboxylic group, indicating the oxygen atoms of the car-
boxyl groups coordinated with the Ln(III) ions [21]. In
addition, the appearance of absorption peak at 419, 438 cm-1
is attributed to mLn–O, which also shows the coordination of
carboxylate ligands and Ln(III) ions. The bands of mC=N and
dC–H in the spectra of complex 2 shifted to higher
wavenumbers compared with the free ligand DIPY. This may
be because the ring’s breathing vibration is blocked, resulting
in increased energy [22], which indicates that the nitrogen
atoms of the DIPY were also coordinated to the Tb(III) ions.
X-ray powder diffraction
The powder X-ray diffraction patterns of the title com-
plexes and two ligands were measured at room tempera-
ture. As shown in Fig. 1, the diffraction peaks of
complexes 1 and 2 (c and d) are very different from those
of two ligands (a and b) and the patterns of two complexes
are not the mechanical adduct of the ligands peaks,
showing that new phases have been produced. Addition-
ally, the patterns of complexes indicate that two complexes
have different structures [23, 24], which was further proved
by single-crystal X-ray diffraction.
Crystal structures, luminescent and thermal properties 1701

Table 1 IR absorption for the ligands and complexes (cm-1)

Ligand/complexes mC=N/cm-1 dC–H/cm-1 mC=O/cm-1 mas(COO–)/cm-1 ms(COO–)/cm-1 m(Ln–O)/cm-1

3,4-DMHBA – – 1678 – – –
DIPY 1585 991,756 – – – –
1 – – – 1558 1418 419
2 1611 997,775 – 1585 1421 438

Table 2 Crystallographic data for complexes 1–2

a
Complex 1 2

Molecular formula C54H54La2O12 C74H70Tb2N4O12

b fw/g mol-1 1172.79 1525.18
Intensity/a.u.

T/K 298(2) 298(2)

Wavelength/Å 0.71073 0.71073
c Crystal system Monoclinic Triclinic
Space group P2(1)/c Pı̄
a/Å 13.1709(12) 14.3146(12)
d b/Å 7.7140(7) 15.7095(13)
c/Å 26.674(2) 19.8348(17)
a/() 90 71.2760(10)
10 20 30 40 50
2θ /° b/() 108.408(2) 79.748(2)
c/() 90 78.509(2)
Fig. 1 XRD patterns of ligands and complexes. a 3,4-DMHBA, Volume/Å3 2571.4(4) 4108.3(6)
b DIPY, c complex 1, d complex 2
Z, calculated density/ 2, 1.515 2, 1.233
Mgm-3
Description of structures Absorption coefficient/ 1.699 1.761
mm-1
X-ray crystallographic data and structural refinement F(000) 1176 1536
parameters of the complexes are listed in Table 2, which Crystal size/mm 3
0.13 9 0.05 9 0.04 0.18 9 0.14 9 0.11
indicate that the structures of them are different. h range for data 2.63–25.02 2.18–25.02
collection/
Crystal structure of [La(3,4-DMBA)3]n (1) Limiting indices -15 B h B 15 -13 B h B 17
-9 B k B 5 -12 B k B 18
Single-crystal X-ray diffraction reveals that complex 1 -31 B l B 29 -21 B l B 23
crystallizes in monoclinic system and space group P2(1)/c. Reflections collected/ 12,270/4526 21,074/14,253
The structure of complex 1 (Fig. 2a) reveals that each unique [R(int) = 0.2155] [R(int) = 0.0728]
asymmetric unit contains one unique La(III) ion and three Completeness to 99.9% 98.4%
3,4-DMBA molecules. All ligands have only one coordi- h = 25.02
nation mode: bridging tridentate. As a result, the nine-co- Max. and min. 0.9351 and 0.8093 0.8299 and 0.7423
transmission
ordination La(III) ion center adopts a distorted
Data/ 4526/0/313 14,253/0/841
monocapped square antiprismatic molecular geometry restraints/parameters
(Fig. 2b). The La…La distance is 3.9737(5) Å. The La–O Goodness of fit on F2 1.038 1.064
bond lengths are in the range from 2.500(9) to 2.704(8) Å.
R1 0.0857 0.0859
The aforementioned polyhedron is connected by edge
wR2 0.1379 0.1958
sharing through carboxylate O2, O3, O4, O5 to generate
R1 (all data) 0.1805 0.1514
1D infinite chains along the b axis (Fig. 2c). This structure
wR2 (all data) 0.1532 0.2123
is similar to the complex [La(apca)3]n (apca = 3-
Largest diff. peak and 1.235 and -1.358 2.358 and -1.598
aminopyrazine-2-carboxylate) [25]. The apca ligands act as hole/(e Å-3)
l2-bridging mode to link the complex into 1D ‘‘snowflake’’

123
1702 P.-P. Shen et al.

Fig. 2 a Perspective view of the (a) (b)

asymmetric unit of complex 1.
b Coordination geometry of
La(III) ion. c 1D infinite chains
along the b axis O6
La1

O5
O3 O2

O4
La1
O1

(c)
c b

chains along the a axis, with the adjacent La…La separa-
tion is 3.983(8) Å. That is different from the complex 1,
which may be due to the difference in carboxylic acid
ligands.
Crystal structure of [Tb(3,4-DMBA)3(DIPY)]2 (2)
X-ray structure analyses indicate that asymmetric unit of
complex 2 crystallizes in the triclinic system Pı̄ space
group with two Tb(III) ions, six 3,4-DMBA molecules and
two DIPY molecules. Figure 3a shows a perspective view
of the structure with atom labels. Both Tb1 and Tb2 have
the same coordination environment, each Tb(III) ion is
eight-coordinated by six carboxylic oxygen atoms of 3,4-
DMBA ligands which have two coordination modes:
bidentate chelating and bridging bidentate, and two nitro-
gen atoms from DIPY ligands taking the bidentate chelat-
ing way. The coordination geometry around the Tb(III) ion
can be viewed as being a distorted square antiprism which
is shown in Fig. 3b. The distance of Tb–Tb is 4.2801(8) Å.

Fig. 3 a Perspective view of the (a) (b)

asymmetric unit of complex 2.
b Coordination geometry of
Tb(III) ion

O11

O12 O4 O8

O7 N2
N3 Tb2 O3
Tb1
N4 O6 O9
O2 O5
O1 N1

O10

123
Crystal structures, luminescent and thermal properties 1703

Fig. 4 1D infinite chains along a

the c axis c
b

The Tb–O bond lengths are in the range from 2.264(9) to 5 7

600 D F
2.461(8) Å, and the Tb–N distances are in the range of 4 5
2.572(11)–2.634(11) Å. The average bond distance of Tb– 500
O (2.350 Å) is shorter than that of Tb–N (2.606 Å);

Intensity/a.u.
400
therefore, the DIPY is always lost earlier than 3,4-DMBA
in thermal decomposition process [26]. 300
5 7
As shown in Fig. 4, the packing diagram for complex 2 D F
4 6
reveals the presence of a 1D chain along the c axis direc- 200
tion which is linked through two kinds of offset face-to- 5 7 5 D 7F
100 D F
face pp stacking interactions [27, 28] between DIPY 4 4 4 3
rings, with the relevant distances: Cg…Cg…3.7100(3) and 0
3.8089(3) Å.
To a certain extent, the structure of the complex 2 is 450 500 550 600 650
Wavelength/nm
similar to that of complex [Tb(3,4-DEOBA)3DIPY]2DIPY
(3,4-DEOBA = 3,4-diethoxybenzoate) [29]. The complex Fig. 5 Emission spectrum of complex 2 (kex = 297 nm)
crystallizes in triclinic crystal system and Pı̄ space group,
which is the same as complex 2. The 3,4-DEOBA adopts
expected, the complex 2 exhibits green emission with the
two kinds of coordination modes: bidentate chelating and
typical bands of Tb(III) ion attributed to the electronic
bridging bidentate, and the complex forms 1D chain and
transitions 5D4 ? 7FJ (J = 6, 5, 4 and 3) [30]. The four
2D layer supramolecular structures via pp stacking
characteristic emission bands of complex 2 are at 488,
interactions, while the complex 2 via two kinds of offset
543, 582 and 622 nm, respectively (Fig. 5). The ligand-
face-to-face pp stacking interactions to form 1D chain
based emissions are not observed, indicating the effective
supramolecular structures.
sensitization from the ligands to the central Tb(III) ion
under photoluminescence [31]. The hypersensitive tran-
Structure comparison
sition (5D4 ? 7F5) at 544 nm is the most intense transi-
tion, which dominates the characteristic green
Although two complexes were obtained from the same
luminescence of terbium complex [32]. The transition
starting materials and experimental method, it is interesting 5
D4 ? 7F6 at 488 nm is the second strong luminescence
to find that the auxiliary ligands in complex 1 did not
peak. The transitions 5D4 ? 7F4 and 5D4 ? 7F3 have
participate in the coordination and they have different
weak intensity. So we could presume that the efficient
structures, owing to the different Ln radii. What is more,
energy transfer from organic ligands to Tb(III) ion can
the general trend for reducing Ln–O bond lengths and
take place, and it can be used for the study of luminescent
coordination numbers is presented on account of the
materials [33].
decrease in the ionic radii of Ln(III) ions.

Luminescence studies Thermal analysis

The solid-state emission spectrum of complex 2 was Thermal analysis of complexes was performed in order to
studied at room temperature with excitation wavelength of study their thermal stability and decomposition mechanism
297 nm, and the emission spectrum is shown in Fig. 5. As under dynamic simulated air atmosphere with a heating

123
1704 P.-P. Shen et al.

(a) DTG/% min–1 (b) DTG/% min–1

20 10
100 DSC DSC
0 100
0 0 0

DSC/mW mg–1
DTG –5 DTG

DSC/mW mg–1
80
–20 –10
80

Mass/%
Mass/%

–10 –5
60 –40 –20
–15
60
–60
40 –20 –10 –30

Exo
Exo
TG –80 40
–25 TG –40
20
–15
–30 –100 –50
400 600 800 1000 1200 400 600 800 1000 1200
Temperature/K Temperature/K

Fig. 6 TG/DTG/DSC curves of complex 1(a) and complex 2(b)

Table 3 Thermal analytical data for complexes 1–2

Complexes Temperature range/K Tp DTG/K Mass loss rate/% Probable expelled groups Residue
Found Calculated

1 545.15–748.15 635.05 4.69 – x(3,4-DMBA) La(3,4-DMBA)3-x

748.15–878.15 819.55 62.68 – y(3,4-DMBA) La(3,4-DMBA)3-x-y
878.15–1039.15 940.55 2.87 – z(3,4-DMBA) La2O3 ? carbon compound
70.24a 76.31b
2 475.15–745.15 564.65 4.01 – x(DIPY) Tb2(3,4-DMBA)6(DIPY)2-x
745.15–1056.15 831.85 63.46 – 2-x(DIPY) ? 6-x(3,4-DMBA) 1/2Tb4O7 ? carbon compound
67.47a 79.16b
a
Experimental total mass loss rate
b
Theoretical total mass loss rate

2000 they undergo gradual decomposition with increasing

temperature.
complex 1
1800 In Fig. 6a, we could find that there are three thermal
complex 2
Heat capacity/J/mol/K

decomposition processes of complex 1 according to the

1600
relevant DTG curve. The first step occurs within tem-
1400
perature range 545.15–748.15 K assigned to the release of
a small number of 3,4-DMBA molecules with a mass loss
1200 of 4.69%. There is obvious mass loss of 62.68% because
of the decomposition of part of 3,4-DMBA molecules at
1000 temperature of 748.15–878.15 K in the second step. The
third step occurs in the temperature range of
800 878.15–1039.15 K with a mass loss of 2.87%. In sum-
260 280 300 320 340 360 380 400 420
Temperature/K
mary, the total mass loss of 70.24% corresponds to the
loss of 3,4-DMBA molecules (calc. = 76.31%), indicat-
Fig. 7 The molar heat capacities of complexes 1 and 2 with the ing that complex 1 is decomposed into the metal oxides
varying temperature (La2O3) and part of the carbon compound.
The thermal behavior of complex 2 can be divided into
rate of 10 K min-1. The TG–DTG curves of complexes are two steps according to the TG–DTG curves (Fig. 6b). The
shown in Fig. 6, whereas their thermal analytical data are first decomposition step occurs in the temperature range
presented in Table 3. Thermal analysis demonstrates that of 475.15–745.15 K with the mass loss of 4.01%, which

123
Crystal structures, luminescent and thermal properties
is attributed to the release of part of DIPY molecules. But
there is a slight mass gain (0.22%) in the temperature
range of 527.15–609.15 K. Meanwhile, there is a small
exothermic peak according to the DSC curve. However,
the experimental results are consistent after many exper-
iments. But the reason remains to be discussed further.
The second step takes place with a mass loss of 63.46%
at the range of 745.15–1056.15 K, on account of the
decomposition of the release of the rest of DIPY and
aromatic carboxylic acid ligands. However, the total mass
loss (67.47%) is lower than the calculated value
(79.16%), which reveals that the complex 2 is not
decomposed completely.
Molar heat capacities of complexes
The molar heat capacities of the complexes 1 and 2 were
obtained by DSC technology in the temperature range of
257.15–413.15 K at a heating rate of 10 K min-1 under
the nitrogen atmosphere. The experimental average
molar heat capacities of complexes are listed in Table S1
and plotted in Fig. 7. As shown in Fig. 7, the average
molar heat capacities of the title complexes gradually
increase with the increasing temperature, indicating that
there is no phase change or any other heat anomaly in
the temperature range of 257.15–413.15 K. In addition,
at the same temperature the Cp, m of complex 2 is
higher than that of the complex 1, which may be due to
their different structures.
The average molar heat capacities were fitted to the
polynomial equation of heat capacities at reduced tem-
perature (x) by the method of least squares [34, 35]. And
the reduced temperature x is calculated by the following
equation:
x ¼ ½T  ðTmax þ Tmin Þ=2=½ðTmax  Tmin Þ=2 ð1Þ
where T stands for the experimental temperature, Tmax is
the highest temperature, Tmin is the lowest temperature
[36]. The fitted polynomial equations, coefficient (R2) and
standard deviation (SD) results are listed in the following:
Complex 1 [La(3,4-DMBA)3]n:
T ¼ 257:15413:15 K
Cp; m=J mol1 K1 ¼ 1260:61419 þ 197:5231x
þ 36:06733x2 þ 239:42326x3
 102:51317x4  373:78892x5 þ 57:30048x6
þ 189:06818x7
R2 ¼ 0:99993; SD ¼ 1:16814
1705
Complex 2 [Tb(3,4-DMBA)3(DIPY)]2:
T ¼ 257:15413:15 K
Cp; m=J mol1 K1 ¼ 1559:66386 þ 237:79368x
62:93209x2 þ 257:97007x3
þ 165:90844x4  154:7745x5  87:65514x6
R2 ¼ 0:99994; SD ¼ 1:42754
Thermodynamic functions of the complexes 1 and 2
The smoothed molar heat capacities and thermodynamic
functions of the title complexes were calculated on the basis
of the fitted polynomial and the following thermodynamic
equations [37], and the data are listed in Table S2 and S3.
Z T
HT  H298:15 K ¼ Cp; mdT ð2Þ
298:15
Z T
ST  S298:15 K ¼ Cp; mT 1 dT ð3Þ
298:15
Conclusions
In summary, two kinds of complexes based on the 3,4-
dimethylbenzoic acid, 2,20 -bipyridine ligands have been
prepared and characterized. The crystal structure of
complex 1 forms 1D infinite chains by edge sharing
through carboxylate ligands, while complex 2 forms an
interesting 1D chains via pp stacking interactions. The
luminescence property of complex 2 was investigated in
detail. It shows the characteristic emission of Tb(III) ion
due to 4fn–4fn transitions. The thermal decomposition
mechanism of complexes can be obtained from the ther-
mal decomposition data, and the results show that two
complexes are thermally stable. The heat capacities,
smoothed heat capacities and thermodynamic functions of
complexes 1 and 2 were also obtained.
Supporting information
The numbers of the two complexes CCDC
1542616–1542617 contain the supplementary crystallo-
graphic data for this paper, which can be obtained free of
charge from the Cambridge Crystallographic Data Centre
via www.ccdc.cam.ac.uk/data_request/cif. Experimental
molar heat capacities of complexes 1–2 are shown in
Table S1, and smoothed molar heat capacities and ther-
modynamic functions of complexes 1–2 are shown in
Table S2 and S3, respectively.
123
1706
Acknowledgements The research work was supported by the
National Natural Science Foundation of China (No. 21473049) and the
Natural Science Foundation of Hebei Province (No. B2016205207).
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