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1. 内蒙古大学, 化学化工学院, 内蒙古, 呼和浩特, 010021
3. 北京大学, 稀土材料化学及应用国家重点实验室, 北京, 100871
4. Wuppertal, University, Wuppertal, 42119, Germany
收稿日期:2006-12-25,
修回日期:2007-10-24,
纸质出版日期:2007-11-20
移动端阅览
温孝春, 赵永亮, 刘永刚, 李颖, 高德青. 掺杂稀土对铕、铽苯二甲酸-冠醚配合物发光的影响[J]. 发光学报, 2007,28(6): 959-965
WEN Xiao-chun, ZHAO Yong-liang, LIU Yong-gang, LI Ying, GAO De-qing. Fluorescence Property of Eu<sup>3+</sup>,Tb<sup>3+</sup>Terephthalic Acid and 18-Crown-6 Complexes Doped by Non-fluorescence Rare Earth[J]. Chinese Journal of Luminescence, 2007,28(6): 959-965
温孝春, 赵永亮, 刘永刚, 李颖, 高德青. 掺杂稀土对铕、铽苯二甲酸-冠醚配合物发光的影响[J]. 发光学报, 2007,28(6): 959-965 DOI:
WEN Xiao-chun, ZHAO Yong-liang, LIU Yong-gang, LI Ying, GAO De-qing. Fluorescence Property of Eu<sup>3+</sup>,Tb<sup>3+</sup>Terephthalic Acid and 18-Crown-6 Complexes Doped by Non-fluorescence Rare Earth[J]. Chinese Journal of Luminescence, 2007,28(6): 959-965 DOI:
合成了稀土Eu
3+
Tb
3+
冠醚、对苯二甲酸高氯酸盐两个系列18种固态配合物.结果表明
配合物的组成为:Eu
2
LL'
2
(ClO
4
)
4
·4H
2
O、EuReLL'
2
(ClO
4
)
4
·nH
2
O、Tb
2
LL'
2
(ClO
4
)
4
·4H
2
O和TbReLL'
2
(ClO
4
)
4
·nH
2
O(Re:掺杂离子
n=2
3
4).对苯二甲酸的羧基氧与稀土离子以对称螯合双齿配位;部分高氯酸在内界以单齿配位;配合物含有水分子.配合物的相对荧光光谱测定表明
相同配体的铽系列配合物的荧光强度明显强于铕系列.稀土离子Eu
3+
的
5
D
0
能级为12.50cm
-1
Tb
3+
的
5
D
4
能级为20.430cm
-1
而配体对苯二甲酸的三重态能级为25.160cm
-1
高于Eu
3+
和Tb
3+
离子的激发态能级
满足配合物分子内传能配体的三重态能级高于稀土离子发射能级的条件
可以提高Eu
3+
和Tb
3+
离子的特征荧光强度.但相对于Eu
3+
离子
对苯二甲酸的三重态能级与Tb
3+
离子的激发态能级(
5
D
4
)更匹配
更有利于能量的有效传递
因此
铽系列的荧光强度明显强于铕系列.Ho
3+
、Yb
3+
对Eu
3+
离子发光敏化作用最强
Ce
3+
、Sm
3+
、Dy
3+
、Er
3+
对Eu
3+
离子发光也有敏化作用
Pr
3+
、Nd
3+
离子对Eu
3+
离子的发光是猝灭的;Yb
3+
、Dy
3+
离子对Tb
3+
离子发光有较强敏化作用
而Ce
3+
、Pr
3+
、Nd
3+
、Sm
3+
、Ho
3+
、Er
3+
离子的掺入对Tb
3+
离子的发光是猝灭的.应用分子内能量传递过程对发光机理进行了探讨.
Two series of Eu
3+
Tb
3+
heteronuclear doped complexes with terephthalic acid(L) and 18-crown-6(L') have been synthesized.Elemental analysis
IR
UV absorption spectra
rare earth complexometry and fluorescence spectra have been studied respectively.The compositions of the complexes were confirmed to be Eu RELL'2(ClO
4
)
4
·nH
2
O and TbRELL'2(ClO
4
)
4
·nH
2
O(RE=Ce
3+
Pr
3+
Nd
3+
Sm
3+
Eu
3+
Tb
3+
Dy
3+
Ho
3+
Er
3+
Yb
3+
;n=2
3
4).Terbium series complexes show that there is an excitation characteristic peak
which is a wide band from 230 to 340 nm
and a maximum peak is at 300 nm.To europium series complexes the band from 220 to 330 nm and maximum peak is at 261 nm.The excitation characteristic peaks are assigned to the ligands-metal energy transfer band through -COO-RE-OOC-.So 300 nm and 261 nm were chosen as excitation wavelength respectively to measure the fluorescence spectra of europium and terbium complexes.We all know that the UV absorption of 18-C-6 is weak
the
5
D
0
energy of Eu
3+
is 17250
but 20430 cm
-1
for the 5D4 energy of Tb
3+
and 25160 cm
-1
for the triplet energy of terephthalic acid.The triplet energy of terephthalic acid is higher a little than the excitation energy of Tb ion
but more higher than Eu
3+
ion's
the lowest excitation energy of Tb
3+
ion matchs well with the triplet state energy of the ligand each other.Thus it is possible that energy transfer from terephthalic acid ligand to Tb
3+
through -COO-RE-OOC- bonds more effectively.Absorbing energy of organic ligands are effectively transfered to the rare earth ion in the luminescence center
and producing a characteristic spectrum.Some non-fluorescence rare earth ions can absorb the energies of triplet organic ligand too
and then transfer them to Eu
3+
or Tb
3+
in this way the fluorescence intensity was enhanced.If the transition energy of non-fluorescence rare earth ions is lower than the
5
D
4
energy of Tb
3+
or
5
D
0
energy of Eu
3+
the luminescence will be quenched.Another way
the high-energy vibration of the OH of H
2
O molecules will heavily quench the luminescence of RE ions
so 18-crown-6 was introduced to replace some coordination H
2
O molecular.These results will provide relatively reliable criteria for the prediction of luminescence properties of rare earth complexes and for seeking excellent luminescent materials.
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