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JOURNAL OF RARE EARTHS 25 (2007) 679 - 683 www.elsevig.mddqre

Synthesis and Fluoxtscence Pmpeities of Eumpium, Teltoium Doped

Zn2' , Cd2+ and C$+ Complexes
Wen Xiaochun (%*%)I, Zhang Mei (% *)I,
Zhao Yonghang ( & 7 i ( % ) l * 2 * , Wang Lianmeng (Xi%%?)',
Gao Deqing (&i%-&)3
( I . College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021, China; 2. State
Key Laboratory of Rme Earth Materials Chembtry and Applications, Peking University, Beijing 100871, China;
3. Wuppertal University, Wuppertal42119, Germany)

Received 1 February 2007; revised 10 April 2007

Abstract: Europium and terbium complexes with strong fluorescence intensity and long fluorescence lifetime were pre-
pared. By replacing half of the europium or terbium ion with M (M =Zn2', Cd2+,and Cr3+)using the doped method,
and then incorporating it with 18-crown4 ether and terephthalic acid, six heteronuclear samples EuZnLL'CI, 3H20(1), -
- -
EuCdLL,'Cl, 5H20(2), EuCrLL'CI, 4H20(3), TbZnLL'Cl, 4H20(4), TbCdLL',Cl, 4H20(5), and TbCrLL',C14 -
4H20(6)(L = terephthalic acid, L' = 18-Crownd ether) were obtained. The elemental analysis, molar conductivities, rare
earth complexometry, Fourier Transform Infrared Spectroscopy (FT-IR), ultraviolet (UV), TGA, fluorescence intensity,
and fluorescence lifetime of the samples were measured. The results showed that there were good luminescence properties
for heteronuclear complexes (l), (2), (4), and ( 5 ) , which were even stronger than those of the homonuclear complexes
-
Eu,LL',Cl, 4 H 2 0 and Tb,LL',CI, 4 H 2 0 , but the luminescence properties of EuCrLL'Cl, * 4 H 2 0 , TbCrLL'Cl, -
4 H 2 0 were very weak. A possible luminescence mechanism was suggested by the organic-inorgpnic doped mechanism and
the law of intramolecular energy transfer.
Key wolds: europium complex; terbium complex; terephthalic acid; crown ether; rare earths
CU: numben 0641.4; 0641.33 Document code: A Alticle ID: 1002 - 072 1(2007p6 - 0679 - 05

Luminescent lanthanide comp lexes have found
wide applications in luminescent display phosphores-
cence, laser, electroluminescent optical devices, and in
probes of chemical and biological molecules, because
their luminescence exhibits high fluorescent efficiency,
with very sharp emission bands, and excellent mono-
chromatocity"]. Rare earth complexes with organic
ligpnds, especially those containing Eu3+ and T b 3 + ,
often display efficient luminescence because of the
strong absorption of the organic ligands and efficient
energy transfer from the triplet state of ligands to rare
earth ions'". During the last decade, the interest in
doped complexes has been growing on account of
their enhanced fluorescent properties. Many investi-
@ions have been reported on the energy match and
energy transfer between the triplet state energy of p-
diketones and the resonant energy level of the central
rare earth ions in the rare earth P-diket~nes'~]. How-
ever, little attention has been paid to the rare earth
complexes that doped the transition metals with aro-

* Colresponding author(E-mail: nmgLy1100@ 163.com)

Foundation item: Project supported by the National Natural Science Foundation of China (20461002); Cbun Hui Plan Foundation of MOE
(22004-2-1 5029)
Biopphy: Wen Xiaochun (1978- ), Female. Master; Research field: Rare earth luminescence materials

Copyright @2007, by Editorial Committee of Journal of the Chinese Rare Earths Society. Published by Elsevier B.V. All rights reserved.
 680 JOURNAL OF RA RE E4 RTHS, VoL25, N0.6, Dec. 2007

matic carboxylic acidsr4].The rare earth complexes of FT-IR spectra data of these complexes are recor-
aromatic carboxylic acids have higher stability than ded in Table 2, and they are similar. The 1550 and
those of (3-diketones because of their infinite chain 1405 c m - ' peaks are assigned to asymmetric stretc-
structure of chelation"]. On the other hand, the exist- hing vibrations v, (COO ) and symmetric stretching
ence of an OH group will result in a luminescence vibrations v,(COO - ) of COO - respectively, which are
quenching actionr6"]. To overcome this negative influ- explained by the existence of bidentate coordination
ence, second ligand 18-crown-6 ether was added. Re- forms of the COO- g r o ~ p [ ~ " ~ ] . Tsplit
h e at 1112 -
garding the role of the introduced Zn2' or Cd2+ , the 1073 cm- ' v,(C-0-C) and 960 cm-' v,(C-0-C) indi-
dope made the ligands twice that of the rare earth ions cated that metal ions were loaded on complexes and
in mole ratio, which means that the triplet level ener- coordinated by crown ethers, and both the RE and
gy from terephthalic acid is double compared to the Zn", Cd2+or Cr3+ions coordinated with the ligands.
pure europium or terbium complexes. In this article, Based on the earher results, it could be seen that they
four excellent luminescent hybrid complexes of Eu3+ were 3:l or 4:l style electrolytes from molar conduc-
or T b 3 + ,low-cost M2+(Zn,Cd), and two weaker lu- tivities"']. UV spectra of the complexes were similar,
minescent hybrid complexes of Eu3+ or Tb3+ and the UV spectra of terephthalic acid and the complex
c r 3+ were prepared successfully. (1) are given in Fig. 1 . The spectrum of terephthalic
acid exhibited two major bands, the absorption peaks
1 Experimental at 264.3 and 281.7 nm corresponded to T+T* transi-
tion. Moreover, it was noteworthy that the absorp-
1.1 Prepamtion
tion intensity of these complexes was stronger than
The materials EuCI, and TbCI, were prepared that of terephthalic acid. The peak moved to
and crystallized from the corresponding rare earth ox- 264.1 nm, and the 281.7 nm peak disappeared, that is,
ides of high purity (99.99%); other reagents (A. R.) it contributed to the rise of T * energy after the car-
were obtained commercially. In principle, the adopted bony1 groups cooperated with the metal ions. The dif-
preparation method for the complexes was very simi- ferent spectra indicated that the coordination reactions
lar to the previous studies"]. had taken place between terephthalic acid and rare
earth ions. The TG-DTA curves (the determination
1 2 Spectmscopy measmments -
range of temperature was 20 600 "c) showed that
The determinations of C and H were performed the complexes were stable below 300 "c, when the
by a PE-2400 elemental analysis instrument and the temperature rose to over 330 "c, where decomposi-
contents of rare earth elements were obtained by ED- tion and oxidization occurred.
TA titration. Molar conductivities were measured
2 2 Fluomcence pmpeities
using DDS-11A and DJS-1 Pt electrode at room tem-
.
perature, with DMF as the solvent (I mmol L - I ) . The excitation spectrum of the Tb3 series com-
Luminescence spectra were measured on a Shimadzu plexe shows a wide band from 230 to 340 nm with a
RF-5301PC spectrophotometer, using the xenon lamp maximum peak at 302 nm, up to the Eu3' series com-
as the excitation source. The luminescence lifetimes plexes, for which the band is from 220 to 330 nm and
were recorded by an Edinburgh Analytical Instrument the maximum peak is at 271 nm, which ;s assigned to
F-900; FT-IR spectra were measured in the 4000 - the ligind - metal energy transfer band through the
400 an-'region on a Nexus 670 FT-IR spectropho-
Table 1 Composition analysis and molar conductivities A,
tometer with KBr pellet technique; UV spectra were
recorded on a Tu-1901 spectrophotometer, using
- -
( S cm' ml-', 25 r) of complexes
DMF as the solvent; TGA was recorded by the Shi- ci% HPh Wh A"
complexes
madzu DTG-50 thermal analysis instrument, the heat- Found Cal. Found cal. Found Cal. Found
ingratewas 10°C s r n i n - ' . h2LL',C4 '4H2O 3192 31.74 489 494 25.11 25.49 166
EuZnLL'C13 -3H,O 2955 2979 429 422 2692 2654 145
2 Results and Discussion EucdLL',CI, *5H,O 3297 33% 486 497 2291 2293 169
EuCrLL'CI, * 4 H 2 0 2864 2838 422 425 24.41 24.11 151
2.1 Chamcterization of complexes Tb2LL'ZCb '4H2O 3098 3138 496 490 2603 2595 176
TbZnLL'CI, .4H,O 29.15 2889 4.41 433 2695 2696 163
The compositions of the complexes were con-
TbCdLL'2CI3 '4H2O 3299 33.11 4.78 494 2357 23.77 180
fmed by C, H elemental analysis and rare earth com- TbCrLL'Ch * 4 H 2 0 28M 28.14 454 422 24.71 24.76 155
plexometry (Table 1).
Wen X C et d Europium, Terbium Doped Zn", Cd' and CI?' Comphm 681

Table 2 Major IR spectm data of I@&

and coordination compounds(cm-')
"0-H yas y, "as ">
IR
(H2O) (COO - ) (COO - ) (C-0-C) (C-0-C)
L' 1101(s) 965(m)
NaL 1560(s) 1397(s)
TbZnLL'CI, * 4H20 3422(s) 1550 m 1405 m 1112, 1073(s) 960(m)

T b 3 + ,and 25160 c m - ' to the triplet of terephthalic

I(b) 264.1
0.8001
0.800-
acidr3'.The triplet energy of terephthalic acid is a lit-
tle higher than the excitation energy of Tb and Eu
2
.- . 264.3 ions, thus, it is possible to make an energy transfer
-e
I
YI
0.500- from terephthalic acid to Eu3+ or Tb3+ through
-COO -RE - OOC - bonds. In the case of T b se-
ries complexes, their maximum absorption peak at a-
, \,'. '. -*
J ..h'*,.'
, '.
h.*,.l

bout 302 nm, can be assigned to the efficient IT-WT'

220.0 260.0 310.0 220.0
Wavelengthhm
Fig. 1 UV spectra: terephthalic acid (a) and complex EuZnLL'
-
CI, 3H20(b)
-COO -RE - 0 O C - bond"" (Figs. 2 and 3 ).
Therefore, the authors chose 302 and 271 nm as the
excitation wavelengths respectively, to measure the
fluorescence spectra of the complexes, and this is
summarized in Table 3 . It can be seen that the fluo-
rescence intensities of both pure Tb,LL',Cl, 4H20
and Eu2LLf2C1,* 4 H 2 0 complexes are good. All Zn,
and Cd doped complexes are enhanced, and some of
them are very much better than the pure Tb2LLf2Cl,
- 4 H 2 0 or Eu2LLf2C14 4 H 2 0 complexes. However,-
the Cr"doped complexes are very week. The fluores-
cence intensities are possibly related to the interaction
between the ligands and metal ions as well as the dif-
ferent environments for the rare earth ions.
3 Luminescence Mechanism
3.1 Contribution of terephthalic acid
There may exist an intramolecular energy transfer
process within the terephthalic acid and the RE ion.
The intramolecular energy transfer efficiency depends
chiefly on two energy transfer processesr4]: The first
is from the lowest triplet level of ligands to the emis-
sive energy level of the Ln ion by the Dexter's reso-
nant exchange interactionri2] ; the second is just an in-
verse energy transfer by the thermal deactivation
mechanism. Both energy transfer rate constants are
dependent on the energy difference between the low-
est triplet level energy of ligands and the resonant em-
issive energy of Ln. It is well known that the 5D, en-
ergy of Eu3+ is 17250, 20430 c m - 'to the 'D, of
260.0 3 10.0
transition, based on the conjugated terephthalic acid
groups. Green emissions are observed in the emission
spectra, indicating that the surrounding carboxy1 lig-
ands absorbed energy and transferred it efficiently to
the chelated terbium ion. There is an efficient energy
transfer from ligands to RE ions"31. The emission
spectra intensities of the complexes are given in Table
3. As seen from Table 3 , the strong emission spectra
consist of four line-emissions at 490 nm ('D4-'Fs),
- 543 nm (5D4-7F5),583 nm (5D4-7F4),and 622 nm
('D,-'F,), based on Tb". This indicates that there
are some carboxyl radicals in hybrid compounds. This
phenomenon has also been verified by the IR spectra.
The same mechanism has been used for the Eu series
complexes. For its spectra see Table 3 . The 'Do ener-
gy of Eu3+differs from the 'D, energy of Tb", the
triplet of the terephthalic acid fits in more with the
Tb3' ion. The T b series complexes are better sensi-
tized compared to the Eu series.
On the basis of the data of excitation and emis-
sion spectra of pure Tb,LL',Cl, -
4 H 2 0 and
Eu,LL',Cl, * 4 H 2 0 (Figs. 2 and 3), it can be pre-
sumed that the luminescence mechanism is similar to
the doped luminescence principle in an inorganic sub-
stance . Organic ligands absorb energy and transfer it to
1
0.000
220.0 300.0 500.0 600.0
Wavclcngthhm Wavelcngthinm
-
Fig 2 Excitation and emission spectra of Tb2LL',C1, 4 H 2 0
 682 J O U m A L OF RARE EARTHS, VoLZS, N o h , Dec. 2007

Table 3 Emission SD&II-I data of comlexes

Complexes Alnm I Alnm I Alnm I Alnm I Alnm I Lifetimeslks
Eu2LL’,C14 * 4 H 2 0 578.6 5.8 592.0 14.8 613.6 522 618.4 77.0 650.4 1.5 369.4
EuZnLL”C1, * 3 H 2 0 579.0 11.7 590.2 342 6132 78.8 618.4 77.0 649.4 2.6 387.3
EuCdLL”’C1, * 5 H 2 0 579.0 9.9 5902 18.9 5932 20.8 615.4 69.9 618.4 15.7 357.9
EuCrLL’CI, * 4 H 2 0 578.4 1.9 613.2 2.4 688.0 2.3
Tb2LL‘2C14 4H2O 490.0 83.5 543.6 214.9 546.6 175.7 583.8 13.8 6212 6.7 952.1
TbZnLL‘CI, 4 H 2 0 489.6 100.4 543.2 267.1 546.3 205.7 582.8 17.3 623.0 12.7 1137.8
TbCdLL‘,CI, * 4 H 2 0 489.6 94.1 543.2 253.7 582.6 16.4 6212 6.6 1025.5
-
TbCrLL’CI, 4H,O 489.6 3.0 5432 6.7 546.4 5.8

sity of 5 D 4 - + 7 Fof5 the former, are all higher than the

1 latter. The results are similar to those of the doped Eu

series (Table 3). Therefore, it can be stated that perhaps
this is an active function as rare earth ions are replaced
by Zn or Cd ions. This process makes the l i p d s twice
that of the rare earth ions in mole ratio, which means
that the energy from the terephthahc acid is doubled
500.0 600.0 700.0
compared to the pure europium or terbium complexes.
Wavelcngthlnm Wavelcngthlnm The other reason is that these metal ions (Zn” and
Fig 3 kitation and emission spectra of Eu2LL’CL 4 H 2 0 Cd2’) have no unsaturated d-layer electron, because the
emission wavelengths of Eu and Tb are just in this re-
the rare earth ion in the luminescence center, and pro- gion of d-d transition (wavelength from 330 to 10oO run).
duce a characteristic spectrum. The charg transfer bands To confirm the earlier prediction, two other doped Cr”
play an important role in its luminescence properties. -
complexes TbCrLL’C14 4 H 2 0 and EuCrLL’C14 4 H 2 0
32 Role of 18-cmwn-6 ether were prepared, their fluorescence intensity data and pos-
sible luminescence mechanism are given in Table 3 and
When l8-crownd ether is introduced as a second Fig. 4. Fluorescence intensity of the complexes was very
l i p d , it will influence the luminescence properties. It is weak, as a part of the emission energy of RE was ab-
well known that luminescence lifetime and intensity are sorbed by the d-d transfer of Cr3+ionr7].In conclusion,
related strongly to the vibration of nearby groups such those ions will heavily quench the luminescence of RE i-
as the OH group. The high-energy vibration of the OH ons if the energy bands of the transition-metal ions’ d-d
in the H 2 0 molecules will heavily quench the lumines- transfer and RE emission are in the superposition or
cence of the RE i ~ n s ‘ ~because
. ~ ] , the vibration may ab- partial superposition.
sorb the excitation energy of RE, which leads to the de-
crease in RE3’ fluorescence lifetime and intensity. To o-
vercome this drawback, 18-mwn-6 ether with lower vi-
bration frequency was used to substitute some H 2 0
molecules. Therefore, the decrease of H 2 0 molecules in
the doped complexes and the relatively rigid structure,
restrict the vibration of the l i p d s around RE3’ and en-
hance the luminescence intensity of RE3’. Another rea-
son for choosing 18-crown4 ether with six oxygm at-
oms is that it is a gwd electron donor, which can com-
pete with H,O to cooperate with the RE ions. These
properties make it a gwd candidate for replacing coordi-
nated H 2 0 . Finally, those aim complexes were obtained.
3 3 h l e s of doped zn” and cb2+
-d
For example, the doped TbZnLL’ CI, 4H,O 067. Ih C‘r
1 ) and TbCdLL’,Cl, 4H,O (253.7), pure terbium com-
-
plex Tb2LL’,C14 4H20(214.9), and the emission inten-
Fig 4 Luminescence quenching mechanism of Cr” to Tb3’
Wen X C ei d Europium, Terbium Doped Zn", Cd' and Cj' CompleL\l?s
4 Conclusion
A series of strong enhancement rare earth lumines-
cent complexes of Eu and Tb doped with other nonfluo-
rescent metals (Zn2', Cd2') at room temperature were
reported. These spectra data were explained on the basis
of enhand excitation efficiency, based on energy trans-
fer from the triplet state of terephthalic acid to the 4f
shell of Eu or Tb center ion. In addition, the crown e-
thers and metal ions (Zn", Cd2') played a sensitive
h c t i o n in enhancing the energy transfer, but metal ion
Cr" played a quenching function. All these complexes
had higher thermal stability at 300 T.
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