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1. 内蒙古大学化学与化工学院,内蒙古 呼和浩特,010021
2. 内蒙古农业大学基础部,内蒙古 呼和浩特,010019
收稿日期:2003-07-20,
修回日期:2003-10-29,
纸质出版日期:2004-09-20
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赵永亮, 安晓萍, 赵凤英, 燕来, 宝金荣. 稀土(铕-铽)-18冠6-对苯二甲酸配合物的荧光性能[J]. 发光学报, 2004,(5): 551-555
ZHAO Yong-liang, AN Xiao-ping, ZHAO Feng-ying, YAN Lai, BAO Jin-rong. Fluorescence Property of the Complexes of the RE(Eu-Tb)-18C6-p-Phthalic Acid[J]. Chinese Journal of Luminescence, 2004,(5): 551-555
以对苯二甲酸(L')为桥联配体
18冠6(L)为配体
稀土(Eu-Tb)为中心离子
合成了一系列超分子化合物
对其进行了元素分析
红外光谱及荧光性能测量.确定了配合物的组成为(Eu
1-x
Tb
x
)
2
L
2
L'(ClO
4
)
4
·H
2
O
(6+3x)
;推测出Eu
3+
离子直接与冠醚氧原子配位
而较小半径的Tb
3+
与18冠6则通过H
2
O配位.H
2
O分子与冠醚氧原子以氢键形式连结
对苯二甲酸以双齿形式桥联两个稀土离子冠醚配合物
形成双核结构单元;在此配合物中
Tb
3+
离子对Eu
3+
离子的发光有一定的敏化作用
而Eu
3+
离子对Tb
3+
离子的荧光却有强的猝灭作用.
A series of dinuclear complexes with different Eu
3+
to Tb
3+
ratios with
p
-phthalic acid (L') and ligand of 18 crown 6(L) have been synthesized.Elemental analysis
IR absorption spectra and fluorescence spectra have been studied respectively.The compositions of the complexes were confirmed to be(Eu
1-x
Tb
x
)
2
L
2
L'(ClO
4
)
4
·H
2
O
(6+3x)
.Smaller Tb
3+
coordinated with water molecules
which were hydrogen bonded with crown ether while Eu
3+
coordinated with crown ether directly may be concluded. Shimadzu FR-5301PC fluorescence spectrophotometer was employed to measure the luminescence spectra at room temperature.As results showed the excitation wavelength changed with the molar ratios of Eu
3+
to Tb
3+
.The optimum excited wavelength is at the same position(298 nm) when contents of Tb
3+
is 100% and 90%
respectively.It changes to 254 nm when Tb
3+
content decrease to 70% and Eu
3+
content rise to 30%.The measurement results of the emission spectra of the complexes indicated that the emission peaks of Tb
2
L
2
L'(ClO
4
)
4
·12H
2
O consisted of four groups of emission peaks and Eu
2
L
2
L'(ClO
4
)
4
·6H
2
O has three
while (Eu
1-x
Tb
x
)
2
L
2
L'(ClO
4
)
4
·H
2
O
(6+3x)
has five.The previous are as following:peaks at 490.0
545.8
585.6 and 621.0 nm are as the Tb
3+
ions
5
D
4
→
7
F
J
(
J
=6
5
4
3) transitions correspondingly
among them the emission from
5
D
4
→
7
F
5
is the strongest belonging to hypersensitive transition(Δ
J
=2).The latter are following:first group
578.6 nm belongs to
5
D
0
→
7
F
0
transitions of Eu
3+
the second group
588.2 nm and 592.2 nm
both belong to
5
D
0
→
7
F
1
transitions of Eu
3+
the third group
613.6nm and 618.2 nm both belong to
5
D
0
→
7
F
2
transitions of Eu
3+
.The last one:they appear at about 490
545
579
585 and 620 nm.The first and second fluorescence bands centered around 490 nm and 545 nm corresponding to
5
D
4
→
7
F
6
and
5
D
4
→
7
F
5
transitions of Tb
3+
ions.Overlapped peaks at 585 nm and 620 nm were found caused by interaction between
5
D
0
→
7
F
1
5
D
0
→
7
F
2
transitions of Eu
3+
and
5
D
0
→
7
F
4
5
D
4
→
7
F
3
transitions of Tb
3+
.Variance of fluorescence spectra emission peaks showed that there are interaction between Eu
3+
ions and Tb
3+
ions in (Eu
1-x
Tb
x
)
2
L
2
L'(ClO
4
)
4
·H
2
O
(6+3x)
. The fluorescence emission intensity of Tb
3+
(
5
D
4
→
7
F
5
) in Tb
2
L
2
L'(ClO
4
)
4
·12H
2
O was 1 313.6 comparing with 29.8 of Eu
3+
(
5
D
0
→
7
F
2
) transitions in Eu
2
L
2
L'(ClO
4
)
4
·6H
2
O.Concluded from R=
I
d
/
I
c
(
I
d
=values of the fluorescence emission intensity determined
I
c
=calculated values) is below 1.0 at 490 nm and 545 nm (corresponding to Tb
3+
5
D
4
→
7
F
6
and
5
D
4
→
7
F
5
transitions) even at 585 nm.However when ratio of Eu
3+
and Tb
3+
is 0.9:0.1~0.7:0.3
the R values for peaks at 579 nm and 620 nm are higher than 1.0 collectively
Eu
3+
will quench Tb
3+
fluorescence while Tb
3+
will sensitize Eu
3+
.
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