JOURNAL OF RARE EARTHS, Vol. 30, No. 6, June 2012, P.

586

Synthesis, characterization and properties of some rare earth complexes

with 2,6-pyridine dicarboxylic acid and -Picolinic acid
HUANG Jin ( )1,2, XU Yinghao ()1, CHEN Xiaoke ()1, XU Dongfang ()1,
XU Yanming ()1, HE Qizhuang ()1
(1. Department of Chemistry, Shanghai Normal University, Shanghai 200234, China; 2. School of Chemistry and Chemical Engineering, Huaiyin Normal University,
Huai'an 223300, China)
Received 19 October 2011; revised 15 March 2012

Abstract: Five novel ternary complexes were synthesized by the rare earth with 2,6-pyridine dicarboxylic acid and -picolinic acid. These
complexes were characterized by elemental analysis, molar conductivity, FT-IR, UV-Vis, Raman, TG-DTA and XRD. The general formula
of the complexes was [RE(DPA)(L)(H2O)]2H2O (RE=Pr3+, Nd3+, Sm3+, Eu, Er3+; DPA=2,6-pyridine dicarboxylic acid; L=-picolinic acid).
The investigation of fluorescence properties of the Eu-complex showed that the Eu(III) ion could be sensitized efficiently by the ligand to
some extent. The antibacterial activity test indicated that all the five complexes exhibited antibacterial ability against Escherichia coli and
Staphylococcus aureus with broad antimicrobial spectrums.
Keywords: rare earth; complex; fluorescence; antibacterial

Recently, the study of the rare earth complexes with organic ligands have received considerable attention[14]. Some
rare earth complexes with organic ligands are often used as
luminescent probes for a variety of chemical and biological
studies[5,6]. The complexes of Eu(III) with 2,6-pyridine dicarboxylic acid derivatives serve as the protein labeling because of their good stability, strong fluorescence intensity
and long fluorescence lifetime[7]. Fluorescent probes have
been fully developed and some rare earth complexes with
fluorescence have been adopted as biological probes for
medical diagnosis and drug development[8,9]. Some probes
for DNA analysis have been proposed[1012]. At the same
time, rare earth complexes also have inspired many efforts
on the design and synthesis as potential antibacterial agents
because of their special electronic configuration[1214].
As the derivatives of pyridine which has good bioactivity[15,16], 2,6-pyridine dicarboxylic (DPA) acid and -picolinic acid (HL) have practical importance in biology due
to the presence of several potential donors N, O which can
inhibit the growth of bacteria[17]. The rare earth complexes
with 2,6-pyridine dicarboxylic acid have special biological
activity, for example, the complexes of gallium show higher
antibacterial activity than free ligand[18].
Because of the importance of rare earth complexes and
our interest in the synthesis of rare earth complexes[1922], we
report herein the synthesis, characterization and some properties of rare earth complexes with the primary ligand (DPA)
and the secondary ligand (HL), in continuation of our re-

search to develop some new antibacterial agents which

maybe provide useful basis for the application in biological
activities for rare earth complexes and other related fields[16].

1 Experimental
1.1 Materials and measurements
Rare earth oxides were purchased from Yue Long
Chemical Plant (Shanghai). 2,6-pyridine dicarboxylic acid
and -picolinic acid were purchased from J & K Chemical
Ltd. All reagents were of analytical grade and used without
further purification. Elemental analysis was determined on
an Elementar Vario EL III elemental analyzer. The infrared
spectra were measured at room temperature on a PK-60000
FT-IR using KBr pellets in the spectral range of 4000
400 cm1. UV-Vis spectra were measured by a PerkinElmer17. Raman spectra were recorded on a Dilor confocal
Raman system (SuperRamlab II). TG-DTA curves were recorded on a thermal oflex DTA derivatograph at a rate of 10
K/min with the samples heated in ambient atmosphere by
PerkinElmer Pyris Diamond. XRD were measured by using
Rigaku D/MaxIIIB, Cu K radial, =0.154056 nm (40 kV,
80 mA), 0.3 ()/s. Fluorescence spectra were recorded on a
Varian Cary Eclipse spectrofluorometer.
1.2 Bacterium
Staphylococcus aureus (S. aureus ATCC6358P) and Es-

Foundation item: Project supported by National Natural Science Foundation of China (20671063, 20973114), Shanghai Key Discipline Construction Project
(S30406), the Key Subjects of Shanghai Normal University (DZL711) and the Research of Shanghai Normal University (SK201048)
Corresponding author: XU Dongfang, HE Qizhuang (E-mail: xdf26@shnu.edu.cn, hqz@shnu.edu.cnTel.: +86-21-64323350)
DOI: 10.1016/S1002-0721(12)60095-7

HUANG Jin et al., Synthesis, Characterization and properties of some rare earth complexes with 2,6-pyridine dicarboxylic

cherichia coli (E. coli ATCC11229) were provided by

Shanghai Drug Institute, Chinese Academy of Sciences.
1.3 Synthesis of complexes
According to Ref. [22], rare earth chloride was prepared
from rare earth oxide. The syntheses of complexes were
prepared as follows: 5 mmol 2,6-pyridine dicarboxylic acid
and 10 mmol sodium hydroxide solid were dissolved in 50
ml distilled water. Subsequently, 5 mmol rare chlorides were
added to the above system, adjusting pH value to 6, stirred
and refluxed for 3 h keeping temperature in water- bath.
Then 5 mmol -picolinic acid solution was added dropwise,
keeping pH value at 6, stirred and refluxed for 67 h keeping
temperature in water-bath. The resulting solution was filtered, washed with distilled water for 3 times, and then dried
in a vacuum oven. Five rare earth complexes with
2,6-pyridine dicarboxylic acid and -picolinic acid were
synthesized using the above-mentioned method.
1.4 Test of antibacterial activity
1.4.1 Method of paper disc diffusion 0.005 mol/L aqueous
solution of rare earth chloride, 2,6-pyridine dicarboxylic acid,
-picolinic acid and complexes were prepared respectively
using DMSO as solvent, and the antibacterial activity of all
the compounds against S. aureus and E. coli were studied.
The bacterium suspension concentration was controlled as
51055106 cfu/ml; The diameters of filter paper were 5
mm, and for the experiments, flat plates were incubated at
37 C (bacterium) for 1824 h[15]. Their inhibition diameter
(including filter paper) was measured with a vernier caliper.
1.4.2 Method of nutrition broth dilution Nutrition broth
was employed for bacterial growth. The tested rare earth
chloride, 2,6-pyridine dicarboxylic acid, -picolinic acid and
complexes were prepared in nutrition broth medium and diluted in concentrations of the range 50800 g/ml. Inocula
containing 1106 cfu/ml were obtained from broth cultures[23]. The lowest concentration (g/ml) of compounds,
which inhibited the growth of bacteria after 24 h incubation
at 37 C was taken as the MIC (minimum inhibitory concentration).
All the experiments were repeated three times and the results were expressed in average values.

2 Results and discussion

2.1 Elemental analysis and molar conductivity

The RE (III) percentage is determined by complexometric

titration with EDTA, according to the method described by
He[15]. Analytical data of RE(III), C, H, and N percentages
(found/calculated) for the complexes are listed in Table 1.
The elemental analytical data are consistent with the calculated values of the general formula of the RE(III) complexes.
The molar conductance measurements of the complexes are
performed in DMSO (with a concentration of 1103 mol/L)
at room temperature. The values varied between 15.2 and
20.5 Scm2mol1, indicating that they are non-electrolyte in
DMSO[24]. Elemental analysis and molar conductivity of the
complexes are presented in Table 1.
2.2 FT-IR spectra
Some results of IR spectra are shown in Table 2. Compared the IR spectra of complex with DPA and HL, we can
conclude that the absence of the COO group of DPA and
HL at 1699 and 1592 cm1 suggest the coordinate of the
COO group with the rare earth ions. Two new bands at
about 1655 and 1440 cm1 can be attributed to the asymmetric and symmetric stretching vibrations, respectively. If the
separation value (=ass) in the rare earth carboxylate
complex is lower than that in the Na+ carboxylate, the coordination mode of carboxylate groups with rare earth ions is
mainly the bidentate chelating or tridentate chelating-bridging coordination[2527]. The separation value
(=ass) between as(COO) and s(COO) peaks is about
218 cm1 in the complexes, which is lower than that in DPA
(290 cm1) and larger than that of HL (210 cm1). The result
shows that the carboxylate is bidendate chelating coordination with rare earth ions for DPA and monodentate chelating
coordination for HL, respectively. Furthermore, the IR
spectra show a strong and wide band at about 3355 cm1,
which is most likely ascribed to the stretching vibration of
the crystal water molecules.
2.3 UV-Vis spectra
The UV-Vis spectra of the complexes, 2,6-pyridine dicarboxylic acid and -picolinic acid are measured in the concentration of 1104 mol/L using DMSO as solvent and the
data are listed in Table 3.
Table 3 shows the UV-vis spectra of ligands and complexes, respectively. The UV spectra of the five complexes
are similar, but different from that of the two ligands. As
seen in Table 3, no absorption is found at 400800 nm.
The absorption bands of the ligands -picolinic acid and
2,6-pyridine dicarboxylic acid are found at 269 and 264 nm,

Table 1 Elemental analysis and molar conductivity data of complexes

Complexes

RE/wt.%

C/wt.%

H/wt.%

N/wt.%

m/(Scm2mol1)

[Pr(DPA)(L)(H2O)]2H2O

29.41 (29.23)

32.65 (32.36)

2.64 (2.70)

5.99 (5.81)

20.5

[Nd(DPA)(L)(H2O)]2H2O

29.65 (29.71)

32.61 (32.14)

2.61 (2.68)

5.91 (5.77)

21.3

[Sm(DPA)(L)(H2O)]2H2O

30.28 (30.59)

31.98 (31.74)

2.55 (2.64)

5.82 (5.70)

17.6

[Eu(DPA)(L)(H2O)]2H2O

30.62 (30.81)

31.92 (31.63)

2.72 (2.64)

5.81 (5.68)

16.1

32.77 (32.90)

30.99 (30.68)

2.41 (2.56)

5.68 (5.51)

15.2

[Er(DPA)(L )(H2O)]2H2O

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JOURNAL OF RARE EARTHS, Vol. 30, No. 6, June 2012

such bands disappear while the asymmetric and symmetric

stretching vibrations of COO appear at 1593 and 1378 cm1.
The separation between them (=112 cm1) shows that the
carboxylate is bidendate chelating coordination with rare
earth ions for 2,6-pyridine dicarboxylic acid and monodentate chelating coordination for -picolinic acid[26,27], respectively.
The bands at 995 and 1008 cm1 are attributed to the pyridine ring bending vibration of two free ligands, which shift
to higher frequency at 1014 cm1 in the complexes. These
are owing to the coordination of the two nitrogens of pyridine ring with the rare earth ion. In the complexes, the bands
at 262, 273 cm1 can be attributed to the REO, REN
stretching vibration, respectively, which cannot be observed
in the IR spectra at lower frequency area (below 500 cm1).
Some results of Raman spectra are shown in Table 4.

Table 2 IR spectra data of ligands and complexes (cm1)

Groups
COOH

COO

H2O

Types

Ligands

Complexes


DPA

HL

Pr3+

Nd3+

Sm3+

Eu3+

Er3+

C=O

1699

1592

as(OCO)

1707

1612

1655

1658

1657

1654

1656

s(OCO)

1417

1402

1433

1440

1441

1433

1441

ass

290

210

222

218

216

221

215

OH

3352

3361

3359

3358

3348

Table 3 UV-Vis spectra data of ligands and complexes

Concentration/ max/nm

Compounds

max/(Lmolcm1)

(10 mol/L)
DPA

1.005

269.68

15690

HL

1.004

264.25

15978

[Pr(DPA)(L)(H2O)]2H2O

1.007

268.02

11732

[Nd(DPA)(L)(H2O)]2H2O 1.005

266.41

11850

[Sm(DPA)(L)(H2O)]2H2O 1.005

265.35

11744

[Eu(DPA)(L)(H2O)]2H2O 1.006

267.88

11723

[Er(DPA)(L)(H2O)]2H2O

267.69

11793

1.010

2.5 TG-DTA
Table 5 shows the DTA and TG curves in the temperature
range from 25 to 1000 C for the complexes. The TG-DTA
curves of the four ternary complexes are similar when heated
in air from. The weightlessness of these prepared complexes
exhibit agreement with the stoichiometry. The complexes
show the following steps, the first corresponds to the loss of
two crystal water in the temperature range of 93107 C accompanying by an endothermic effect. The second corre-

respectively, which are attributed to SS* transition of conjugated system. When the complexes are formed, the SS*
transition of 2,6-pyridine dicarboxylic acid has a blue shift
while that of -picolinic acid has a bathochromic shift. The
overlapping of the two absorption bands form a new one of
the complexes that also indicate that 2,6-pyridine dicarboxylic acid and -picolinic acid are coordinated to rare earth
ion[25]. At the same time, the max of the complexes are different from that of the free ligands, which suggest that both
2,6-pyridine dicarboxylic acid and -picolinic acid are involved in metal complexation.
2.4 Raman spectra
Raman spectra can also provide information about molecular structure. The Raman spectra, is a powerful method
for characterizing the rare earth complexes. The Raman
spectra of both the Nd-complex and the ligands are shown in
Fig. 1. The stretching vibrations of COO group in
2,6-pyridine dicarboxylic acid and -picolinic acid are assigned to the strong Raman bands at 16831552 cm1 and
17111562 cm1, respectively. In the complexes, however,

Fig. 1 Raman spectra of the Nd-complex and the ligands

(1) [Nd(DPA)(L)(H2O)]2H2O; (2) DPA; (3) HL

Table 4 Raman spectra data of ligands and complexes (cm1)

Group

Types

Ligands

Complexes


DPA

HL

Pr3+

Nd3+

Sm3+

Eu3+

Er3+

COOH

C=O

16831552

17111562

COO

as

1595

1593

1596

1597

1592
1375

s

1375

1378

1382

1385

ass

220

215

214

212

217

Bending vibration

995

1008

1021

1014

1022

1018

1009

759

839

878

858

846

865

897

394

413

432

428

430

441

418

REO

271

273

274

273

274

REN

261

262

264

265

264

N
New peak value

HUANG Jin et al., Synthesis, Characterization and properties of some rare earth complexes with 2,6-pyridine dicarboxylic

589

Table 5 TG-DTA data of the complexes

Complexes

Endothermic peak of

Endothermic peak of

Exothermic peak of

Mass loss of two

Total mass

dehydration/C

decomposition/C

decomposition/C

crystal water/%

loss/%

[Pr(DPA)(L)(H2O)]2H2O

102, 217

482

509

7.68 (7.23)

56.08 (59.33)

[Nd(DPA)(L)(H2O)]2H2O

93, 219

471

511

7.31 (7.19)

55.87 (58.92)

[Sm(DPA)(L)(H2O)]2H2O

107, 232

492

539

7.20 (7.10)

55.06 (58.18)

[Eu(DPA)(L)(H2O)]2H2O

98, 222

474

506

7.04 (7.07)

54.92 (58.00)

[Er(DPA)(L)(H2O)]2H2O

103, 218

468

501

6.77 (6.87)

54.38 (56.25)

sponds to the loss of the coordination water in the temperature range of 217232 C. This is in line with IR and elemental analysis data. It can be seen from Table 5 that endothermic peaks of framework rupture of complexes are at
471492 C. And then, the anhydrous complexes decompose
to the oxides accompanying by a strong exothermic effect
with a single peak in the temperature range of 501539 C.
The complexes decomposed completely at around 600 C
and the residues are rare earth oxide.
2.6 XRD spectra
Fig. 2 shows XRD spectra of Nd-complex and ligands. As
seen in Fig. 2, XRD spectra of the ternary complexes are different from that of the free ligands, which indicate the formation of new complexes.
Based on the above studies, we propose a tentative coordination structure for the complexes as shown in Scheme 1.

2.7 Fluorescence spectra

Lanthanides exhibit different intensity and wavelength of
the fluorescence, which is still relatively weak because of the
low absorption ion itself. The UV emission spectrum (2) of
EuCl3 at 396 nm is shown in Fig. 3. The UV emission spectrum (1) of the complex of Eu(III) with ligands including
polycarboxyl group at 396 nm is presented in Fig. 4, which
could be clearly observed the intensity of both spectra is
quite different. It is largely due to some lanthanides and organic conjugated molecules containing aromatic or heterocyclic ring can produce fluorescence. The complexes emit
the characteristic fluorescence of rare earth ions because the
ligand transmit effectively it in the near ultraviolet absorption energy for the rare earth ions.
The excitation spectrum (1) of Eu(DPA)(L)(H2O)2H2O
with an emission wavelength of 615 nm is shown in Fig. 4,
and the emission spectrum (2) of this complex with an excitation wavelength at 396 nm is shown in Fig. 4. Luminescence peaks under UV excitation at 396 nm are observed at
581.2, 591.2 and 617.0 nm, which are assigned to the transition of Eu(III) (5D07F0,5D07F1 and 5D07F2). The fluorescence intensity of the complex at 617.0 nm is distinctly
stronger than the other emission wavelength, and exhibit
bright red light. The efficient energy transfer from ligands to
centre ions is one of key factors to achieve rare earth characteristic fluorescence. The introduction of the 2,6-pyridine dicarboxylic acid and -picolinic acid enlarge theconjugated system of the complex and enhance the luminescent intensity of the complex.

Fig. 2 XRD spectra of the ternary complexes and ligands

(1) Nd-complex; (2) 2,6-pyridine dicarboxylic acid; (3) -picolinic
acid

2.8 Antibacterial activity

Scheme 1 Tentative coordination structure for the complexes (RE=

Pr3+, Nd3+, Sm3+, Eu3+, Er3+)

Fig. 3 Fluorescence spectra of the EuCl3 (1) and [Eu(DPA)(L)

(H2O)]2H2O (2)

The antibacterial activities of the complexes, LnCl3 and

590

JOURNAL OF RARE EARTHS, Vol. 30, No. 6, June 2012

Fig. 4 Excitation (1) and emission spectra (2) of the [Eu(DPA)(L) (H2O)]2H2O

the ligands are evaluated using the paper disc diffusion

method and the nutrition broth dilution method against
E. coli ATCC11229 and S. aureus ATCC6358P.
The antibacterial activitys results in the forms of diameter
of growth inhibition area in mm and the MIC (g/ml) are
listed in Tables 6, 7 and Fig. 5. The antibacterial results are
listed as follows: (1) All the tested ternary complexes exhibit
antibacterial activities against E. coli and S. aureus. (2) The
antibacterial activities of the complexes are better than that
of each free ligand. (3) In the five complexes, The Nd complex shows the relatively favorable antibacterial activity with
the diameter of growth inhibition area (17, 15 mm) and the
MIC (400, 450 g/ml) against E. coli and S. aureus among
the five complexes. So the antimicrobial spectrum of the
complexes is broad.

Table 6 Antibacterial activity expressed as diameter of growth

inhibition area
Complexes

Concentration/
(mol/L)

Diameter of growth
inhibition area/mm
E. col
S. areus
ATCC11229
ATCC6358 P

[Pr(DPA)(L)(H2O)]2H2O 0.005

15

[Nd(DPA)(L)(H2O)]2H2O 0.005

17

15

[Sm(DPA)(L)(H2O)]2H2O 0.005

15

12

[Eu(DPA)(L)(H2O)]2H2O 0.005

14

13

13

[Er(DPA)(L )(H2O)]2H2O 0.005

12

11

DPA

0.005

10

10

HL

0.005

RECl3

0.005

Table 7 Antibacterial activity expressed as MIC

Complexes

MIC/(mg/L)


[Pr(DPA)(L )(H2O)]2H2O

E. col ATCC11229

S. areus ATCC6358 P

430

470

[Nd(DPA)(L)(H2O)]2H2O 400

450

[Sm(DPA)(L)(H2O)]2H2O 450

480

[Eu(DPA)(L )(H2O)]2H2O 460

470

[Er(DPA)(L)(H2O)]2H2O

500

550

DPA

700

750

HL

>800

>800

RECl3

>800

>800

The increase in antibacterial activity of the complex may

be due to the effect of complexation which considerably reduces the polarity of the metal ion because of partial sharing
of its positive charge with the donor groups. And we know
that the -electron delocalization in this chelating ring also
increases the lipophilic nature of the central metal atom,
which inclines to its permeation through the lipid layers of
cell membrane[19,27,28]. The antibacterial mechanism of the
rare earth ternary complexes was hypothesized on their effect on the cell division of bacteria as well as cell wall, protein, and/or DNA biosyntheses[29].
Fig. 5 Diameter of the growth inhibition area of La-complex against
E.col (a) and S. aureus (b)
a: [Nd(DPA)(L)(H2O)]2H2O; b: DPA; c: HL; d: NdCl3; e: DMSO

3 Conclusions
The synthesis and characterization of five rare earth com-

HUANG Jin et al., Synthesis, Characterization and properties of some rare earth complexes with 2,6-pyridine dicarboxylic

plexes with antibacterial and antitumor were achieved. The

antibacterial activity test showed that the complexes exhibited antibacterial ability against E. coli and S. aureus than the
free ligands. In the five complexes, the Nd-complex showed
the relatively favorable antibacterial activity. The introduction of the 2,6-pyridine dicarboxylic acid and -picolinic
acid enlarged the -conjugated system of the complex and
enhanced the luminescent intensity of the Eu-complex.

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