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1. 兰州大学化学化工学院, 甘肃兰州730000
2. 广西民族学院化学化工系, 广西南宁530006
收稿日期:2001-06-20,
修回日期:2001-12-07,
纸质出版日期:2002-03-20
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尹显洪, 谭民裕, 韩超, 冯艳华. Y<sup>3+</sup>对水溶液聚合结构中Eu<sup>3+</sup>的荧光增强作用[J]. 发光学报, 2002,23(2): 157-161
YIN Xian-hong, TAN Min-yu, HAN Chao, FENG Yan-hua. Fluorescence Enhancement Effect of Yttrium(Ⅲ) on Europium(Ⅲ) within the Polymeric Structure in Aqueus Solution[J]. Chinese Journal of Luminescence, 2002,23(2): 157-161
尹显洪, 谭民裕, 韩超, 冯艳华. Y<sup>3+</sup>对水溶液聚合结构中Eu<sup>3+</sup>的荧光增强作用[J]. 发光学报, 2002,23(2): 157-161 DOI:
YIN Xian-hong, TAN Min-yu, HAN Chao, FENG Yan-hua. Fluorescence Enhancement Effect of Yttrium(Ⅲ) on Europium(Ⅲ) within the Polymeric Structure in Aqueus Solution[J]. Chinese Journal of Luminescence, 2002,23(2): 157-161 DOI:
合成了两种双功能的配体2
2'
6
6'-四羧基-4
4'-联吡啶(BDPA)和双(2
6-二羧基-4-吡啶基)硫醚(SDPA)。观察到Y
3+
能明显提高水溶液聚合结构中Eu
3+
的荧光强度。荧光增强机制表明
Eu
3+
、Y
3+
和配体所构成的水溶液聚合结构
有利于使Y
3+
配合物中的配体所吸收的能量有效地转移给Eu
3+
。
The aim of our work is to produce enhanced Eu
3+
luminescence in aqueous solution by using energy transfer between ligands
which are linked together by Y
3+
without other additives and micelle formation. We synthesized two bifunctional complexing agents 2
2'
6
6'-tetracarboxy-4
4'-bipyridine (BDPA) and bis(2
6-dicarboxy-4-pyridyl) sulfide (SDPA). In this polymeric network the enhancement of Eu
3+
luminescence is based on two factors. First
a great excess of energy donors (ligands) relative to energy acceptors (Eu
3+
) was used. Excess of ligands was added to obtain maximum absorption and excess of Y
3+
was added to link the ligands and enhance intersystem crossing to triplet state in these ligands. Secondly
the energy absorbed by ligands coordinated to Y
3+
is transferred toward Eu
3+
via triplet-triplet migration. One Eu
3+
is able to be excited either with the energy absorbed by three ligands coordinated to Y
3+
or by several other ligands coordinated directly. This means that when energy is lost non-radiatively during the energy transfer process from the ligand to the Eu
3+
thus Eu
3+
can still be excited by energy transfer process from other ligands coordinated to Y
3+
. The luminescence intensity of the Eu
3+
was plotted against time after mixing of BDPA
Y
3+
and Eu
3+
. The growth of the luminescence signal was quite rapid at the beginning
but slowed down 3min later. The SDPA system showed the same phenomenon. The ligand concentration
Y
3+
concentration and pH were optimized. In two systems with different ligands the effect of pH was investigated in the range 3~11. The luminescence signal was observed to be highest at pH9. The effects of Y
3+
concentration and BDPA concentration on Eu
3+
luminescence were studied respectively. In the case of BDPA
the luminescence intensity of Eu
3+
was highest when the Y
3+
:BDPA ratio was close to the theoretical value 2:3. When the luminescence intensity of Eu
3+
was plotted against the concentration of Eu
3+
it can be seen that there is a quite good linearity within 1
3+
10
-10
~5
3+
10
-7
mol/L range
which enables to be a method used for determination of trace amounts of Eu
3+
.It can be seen that adding of Y
3+
will increase Eu
3+
luminescence greatly. The enhanced Eu
3+
luminescence is most likely due to the presence of efficient energy migration from the ligands coordinated to Y
3+
to the Eu
3+
. The Eu
3+
(Y
3+
)-BDPA system reached the highest luminescence intensity. It might be the result of several factors. The BDPA has a symmetric
conjugated structure. This structure has the shortest distance between different Y
3+
centers and its triplet energy level is suitable for transferring energy to the resonance level of Eu
3+
. It is totally conjugated and planar
which enables the effective energy transfer between ligands. However
the SDPA does not has a conjugated structure
and this may be responsible for the diminished energy transfer compared with that of the BDPA system. The effect of replacing Y
3+
with other lanthanides such as Gd
3+
La
3+
and Lu
3+
was also studied. The sequence of the enhancement is: Gd
3+
>
Y
3+
>
Lu
3+
>
La
3+
. It is noticed that Tb
3+
also enhances Eu
3+
luminescence in this polymer structure.
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