Spectrochimica Acta Part A 74 (2009) 2629

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Spectrochimica Acta Part A: Molecular and

Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa

Study of the luminescence properties of a novel rare earth complex

Tb(DPC)2 2H2 O
Yuguang Lv a, , Qiuping Li a , Chunhui Shi b , Hairan Liu a , Fenghua Liu a , Lili Wu a ,
Dongmei Wu a , Hong Liu a , Jie Xie c
a
b
c

The Provincial Key Laboratory of Biomaterials, College of Chemistry and Pharmacy, Jiamusi University, Jiamusi 154007, China
Clinic Medical College, Jiamusi University, Jiamusi 154002, China
Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, China

a r t i c l e

i n f o

Article history:
Received 21 September 2008
Received in revised form 6 April 2009
Accepted 15 April 2009
Keywords:
Organic compound
Thin lms
Electroluminescence
Energy transfer

a b s t r a c t
Rare earth complex Tb(DPC)2 2H2 O was synthesized by introducing Pyridine-2,6-dicarboxylic
acid(H2 DPC) as the ligand and characterized by UV, uorescent and infrared spectra as well as elemental analysis. The complex exhibited ligand-sensitized green emission, and it has the higher sensitized
luminescent efciency and longer lifetime. The effect and mechanism of the ligand (H2 DPC) on the luminescence properties of terbium complex was discussed. In device ITO/PVK/Tb(DPC)2 2H2 O/Al, Tb3+ may
be excited by intramolecular energy transfer from ligand as observed by electroluminescence. The main
emitting peak at 545 nm can be attributed to the transition of 5 D4 7 F5 of Tb3+ ion and this process results
in the enhancement of green emission from electroluminescence device.
2009 Elsevier B.V. All rights reserved.

1. Introduction
Recently, considerable of studies have been focused on the
design and assembly of uorescent rare earth complexes [14]. Tb3+
ion, the complexes of which emit green light, is one of the rare
earth ions that show the best luminescence property. The ligands
are usually called antennas absorb and transfer energy to the rare
earth ions and consequently increase their luminescence intensity.
Many rare earth complexes have been developed as the emitters
in organic photoluminescence and electro-luminescence devices
[516]. In order to improve the luminescence properties of rareearth complexes, the choosing of ligands is very important. Though
much work has been done, the effect the ligands on the luminescence properties of rare-earth complexes still needs to be further
studied. Pyridine-2,6-dicarboxylic acid (H2 DPC) possess biological
active in the body of the animal and plant. Its derivatives and complexes were extensively and deeply studied and were used to all
sorts of elds [17,18]. But very little discussions were reported in
organic photoluminescence and electroluminescence.
In this paper, we have successfully synthesized rare earth complex Tb(DPC)2 2H2 O with remarkably sharp green emission bands.
In PVK/Tb(DPC)2 2H2 O blend, the green emission of terbium complex was enhanced and PVK emission was quenched. Results show

Corresponding author. Tel.: +86 0454 6822098.

E-mail addresses: yuguanglv@163.com, lvyuguang@yahoo.cn (Y. Lv).
1386-1425/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.saa.2009.04.009

that the complex of Tb (III) emits strong green luminescence when

excited by UV light.

2. Experiments
2.1. Reagents and apparatus
Tb4 O7 (99.99%), pyridine-2,6-dicarboxylic acid (H2 DPC) and
other chemicals were analytical reagent grade and used without
further purication. TbCl3 6H2 O was prepared by dissolving terbium oxides in hot hydrochloric acid (and evaporating excess HCl
and water).
Elemental analyses were performed on a Perkin-Elmer 240C
analytical instrument. Infrared spectra were recorded in the range
of 4000400 cm1 by a prostige-21IR spectrophotometer in KBr
ake. UVvis spectra were performed on a UV-2501PCS double spectrophotometer. The excitation and emission spectra were
recorded on a Shimadzu 5301 spectrouorophotometer equipped
with a 150W xenon lamp as the excitation source. Spectra were
recorded using monochromator slit widths of 1.5 nm on both excitation and emission sides. Lifetimes were measured with a Spex
1934D phosphorimeter using a 450-w ash lamp as the excitation source (pulse width = 3 s). The EL spectra were measured on
a uorolog-3 Spectrophotometer of the American SPEX Company.
The luminance was measured by PR-650 spectra-scan spectrometer.

Y. Lv et al. / Spectrochimica Acta Part A 74 (2009) 2629

Fig. 1. Infrared spectra of the complex Tb(DPC)2 2H2 O ( = 4004000 nm) (1, DPC; 2,
Eu(DPC)2 2H2 O; 3, Tb(DPC)2 2H2 O)

27

Fig. 2. UV spectra of ligand and complex Tb(DPC)2 2H2 O.

2.2. Electroluminescence device preparation

The device structure of the complex Tb(DPC)2 2H2 O was
fabricated according to the literature method [19,20]. Poly(Nvinylcar-bazole) (PVK) was dissolved in chloroform with a
concentration of 10 mg/ml. In order to improve the performance
of Tb(DPC)2 2H2 O thin lm, Tb(DPC)2 2H2 O was doped into PVK
at weight ratio of 1:5. The PVK:Tb(DPC)2 2H2 O thin lm was
fabricated on the top of cleaned ITO coated glass substrate by spincoating method. 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline
(BCP) and aluminum quinoline (Alq3 ) lms were fabricated by thermal evaporation at a rate of about 0.3 /s under high vacuum of
2 106 Torr.
2.3. Synthesis of the complexes
The Tb (III) complex was synthesized by mixing the TbCl3 6H2 O
and the ligand (H2 DPC) in ratio 1:2 in ethanol under stirring. The
precipitation produced by adding ammonia. The precipitation was
then ltered, washed with water and ethanol and dried, then stored
in a silica-gel drier.

Fig. 3. Typical emission spectra of the complex Tb(DPC)2 2H2 O excited at 330 nm.

3.2. UV absorption spectra analysis

UV absorption spectra of ligand and complex in DMF solution
(5 105 mol/L) are shown in Fig. 2. They all exhibit domain absorption peaks in the ultraviolet region (200400 nm). The results show
that UV spectra of the Tb (III) complex with the ligand are similar.

3. Results and discussion

3.1. IR spectra analysis
The spectra for the ligand H2 DPC and the corresponding Tb3+
complex are shown in Fig. 1. The spectra of the Tb3+ complex with
the ligand are not similar. The characteristic absorption bands for
H2 DPC at 1661 cm1 (C O) and 32002500 cm1 (-OH) disappeared in the Tb3+ complexes. The presence of carboxylate groups in
the various complexes was denitely conrmed by both the asymmetric stretching bands (asCOO) at about 1585 cm-1 and the
symmetric stretching (sCOO) at about 1420 cm1 . The elemental
analysis data of the terbium complex were listed in Table 1.

3.3. Luminescent properties of the complex

The excitation spectra for the complex Tb(DPC)2 2H2 O were
recorded by monitoring the Tb3+ luminescence at 545 nm in the
range of 200450 nm. The emission spectra were recorded in the
range of 400700 nm by monitoring the maximum excitation wavelength (in Fig. 3). The results show that Tb(DPC)2 2H2 O emits the
typical sharp emission bands corresponding to the transitions of
the Tb3+ ion 5 D4 7 F6 , 5 D4 7 F5 , 5 D4 7 F4 and 5 D4 7 F3 , respec-

Table 1
The results of analytical data of complexes.
Complex

Tb(DPC) 2 2H2 O

Tb (%)

30.27 (30.29)

Analytically found (calculated) (%)

C

32.12 (32.09)

1.89 (1.91)

5.35 (5.33)

30.46 (30.48)

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Y. Lv et al. / Spectrochimica Acta Part A 74 (2009) 2629

Table 2
The luminescence properties of rare earth complex.
Matter
Tb(DPC) 2 2H2 O

ex (nm)
330

em (nm)
545

Relative intensities (a.u.)

1025

Lifetimes (s)
885

stant depend on the energy differences between the triplet level of

the ligands and the resonant emissive energy level of RE3+ .
To the complex Tb(DPC)2 2H2 O, the fact of steric hindrance
effect and the fact of the energy transfer both increase the energy
transfer efciency between the ligand and the Tb3+ . The complex
Tb(DPC)2 2H2 O exhibits strong luminescence intensity.
3.4. Electroluminescence
Fig. 4 is electroluminescent spectrum of the complex
Tb(DPC)2 2H2 O at a driving voltage of 8 V. The electroluminescence intensity dependence on the driving voltage is obtained
by using the time-base spectra. In the structural device, electro
-luminescence intensity sharply increases when the driving voltage goes beyond 12 V. This process resulted in the enhancement
of green emission from electroluminescent device, which is made
from metal complexes.
Fig. 5 is powervoltage curves for the complex Tb(DPC)2 2H2 O of
structure devices at 8 V. The electron current in the Tb(DPC)2 2H2 O
device sharply increases when the driving voltage goes beyond
10 V. It is found that the Tb(DPC)2 2H2 O structural device effectively
improves the electroluminescence intensity of lanthanide ions.

Fig. 4. EL spectra of the complex Tb(DPC)2 2H2 O at various driving voltages.

tively. The relative intensity of the emission at 5 D4 7 F5 is stronger

than other luminescence emissions. Moreover, the emission peak
positions of the complex indicated that there is a typical Tb3+ luminescence emission. More importantly, the complex Tb(DPC)2 2H2 O
shows also long lifetime in Table 2 (about 885 s).
The results show that the ligand absorbs and transfers energy
to Tb3+ [21,22]. The luminescence properties of the complex are
inuenced by the interaction between the ligands. It indicates
that luminescence properties of the complex depend on the ligand. The intramolecular energy transfer efciency from organic
ligands to RE3+ is the most important factor which inuencing
the luminescence properties of rare-earth complexes. According to
the intramolecular energy mechanism, the intramolecular energy
transfer efciency depends chiey on two energy transfer processes: the rst one comes from the triplet level of ligands to the
emissive energy level of the RE3+ by Dexters resonant energy transfer interaction; the second one is just an inverse energy transfer by
a thermal deactivation mechanism. Both energy transfer rate con-

Fig. 5. Powervoltage curves for the complex Tb(DPC)2 2H2 O at various driving voltages.

4. Conclusion
In summary, it is concluded that by using a chemical coprecipitation method, the novel terbium complex Tb(DPC)2 2H2 O has
successfully been synthesized and characterized for it structural
and photoluminescence and electroluminescence properties. The
complex has higher sensitized luminescent efciency and longer
lifetime. The present study shows great promise for the design of a
new type electroluminescence device conguration.
Acknowledgments
This work was supported by emphasis research fund for Jiamusi
University (Szj2008-018, 2008-017), research fund for the Provincial Key Laboratory of Biomaterials Jiamusi University (E08050204,
E08050207), Education Commission of Hei Long Jiang Province
(10541221, 11521288) and Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences.
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