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内蒙古大学, 化学化工学院,内蒙古 呼和浩特,010021
收稿日期:2008-04-23,
修回日期:2008-06-27,
纸质出版日期:2008-09-20
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张梅, 赵永亮, 赵艳芳, 王艳, 李海燕, 魏晓燕, 刘润花. 铕及其掺杂稀土噻吩乙酸、邻菲啰啉配合物的合成、表征及荧光性能[J]. 发光学报, 2008,29(5): 827-832
ZHANG Mei, ZHAO Yong-liang, ZHAO Yan-fang, WANG Yan, LI Hai-yan, WEI Xiao-yan, LIU Run-hu. Studies on Fluorescence Property of Eu<sup>3+</sup> Dinuclear Complexes with<sub>2</sub>-Thiopheneacetic Acid and o-Phenanthroline[J]. Chinese Journal of Luminescence, 2008,29(5): 827-832
张梅, 赵永亮, 赵艳芳, 王艳, 李海燕, 魏晓燕, 刘润花. 铕及其掺杂稀土噻吩乙酸、邻菲啰啉配合物的合成、表征及荧光性能[J]. 发光学报, 2008,29(5): 827-832 DOI:
ZHANG Mei, ZHAO Yong-liang, ZHAO Yan-fang, WANG Yan, LI Hai-yan, WEI Xiao-yan, LIU Run-hu. Studies on Fluorescence Property of Eu<sup>3+</sup> Dinuclear Complexes with<sub>2</sub>-Thiopheneacetic Acid and o-Phenanthroline[J]. Chinese Journal of Luminescence, 2008,29(5): 827-832 DOI:
合成了十种以2-噻吩乙酸(TPAC)、邻菲啰啉(Phen)为配体
单一稀土Eu
3+
配合物、Eu
3+
掺杂La
3+
、Gd
3+
、Y
3+
、Er
3+
以及不同比例的Eu
3+
掺杂La
3+
异核配合物.进行了元素分析、摩尔电导、热谱、红外光谱、核磁共振及荧光性能研究.配合物的组成分别为Eu
L
3
L
'
Eu
0.5
Y
0.5
L
3
L
'
Eu
0.5
La
0.5
L
3
L
'
Eu
0.5
Gd
0.5
L
3
L
'
Eu
0.5
Er
0.5
L
3
L
'和Eu
x
La
1-x
L
3
L
'(其中
L
=TPAC
L
'=Phen).羧酸的氧原子和邻菲啰啉的氮原子与稀土离子配位
配合物为非电解质.荧光光谱的测试表明荧光惰性离子La
3+
、Gd
3+
、Y
3+
对Eu
3+
的荧光有增强作用
顺序为La
3+
>Gd
3+
>Y
3+
;Er
3+
对Eu
3+
的荧光有猝灭作用.不同比例Eu
3+
掺杂La
3+
异核配合物中
当Eu
3+
:La
3+
=0.50:0.50时敏化作用最强
荧光强度值最大.
Five solid complexes of rare earth Eu
3+
doped La
3+
Gd
3+
Y
3+
Er
3+
and five different proportion co-doped complexes(Eu
3+
:La
3+
) with 2-thiopheneacetic acid and o-phenanthroline have been synthesized and characterized.Elemental analysis
rare earth coordination titration and TG-DTA studies show that the complexes have the composition of Eu(TPAC)
3
Phen.The different dinuclear complexes are composed of Eu
0.5
RE
0.5
(TPAC)
3
Phen(
RE
3+
=La
3+
Gd
3+
Y
3+
Er
3+
);(Eu
x
La
y
)(TPAC)
3
Phen(x:y=0.10:0.90;0.30:0.70;0.40:0.60;0.70:0.30;0.90:0.10).The molar conductivity indicates that all the complexes are nonelectrolyte;IR spectra and
1
H NMR spectra show that 2-thiopheneacetic acid combined as the form of bridging dissymmetrical bidentate ligand
and the two nitrogen atoms in phen are also involved in the rare earth ion coordination for europium complex and its doped with La
3+
Gd
3+
Er
3+
and Y
3+
complexes.There are strong fluorescence intensity for all these complexes
it shows that the lowest excitation state energy level of Eu
3+
ion with the triplet state energy level of the ligands match well each other.Its fluorescence intensity is enhanced after doping with La
3+
Gd
3+
Y
3+
.The sensitization actions from La
3+
Gd
3+
and Y
3+
to Eu
3+
ion are Y
3+
<
Gd
3+
<
La
3+
.But Er
3+
make the fluorescence intensity of the europium complex weaken.We also find that as n(Eu):n(La)=1:1
the fluorescence intensity is the strongest in the complexes of(Eu
x
La
1-x
)(TPAC)
3
Phen.
5
D
0
energy level of Eu
3+
is 17 250 cm
-1
the triplet state energy of 2-thiopheneacetic acid and o-phenanthroline are 25 000 cm
-1
and 22 123 cm
-1
respectively.The triplet state energy of the two ligands are higher than the excitation energy of Eu
3+
ion
thus it is possible that energy transfer from 2-thiopheneacetic acid and o-phenanthroline to Eu
3+
through —COO—Eu—OOC— and —N—Eu—N— bonds.The absorbing energy of the ligands are effectively transferred to europium ion in the luminescence center
and producing a characterization spectrum.Some complexes of non-fluorescence rare earth can absorb the triplet energies of the ligands too
and then transfer them to Eu
3+
in this way the fluorescence intensity was enhanced.If the transition energy of non-fluorescence rare earth complexes is lower than the
5
D
0
energy of Eu
3+
the luminescence will be quenched.
0
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