Kris
Driesen
,
Sofie
Fourier
,
Christiane
Görller-Walrand
and
Koen
Binnemans
*
Katholieke Universiteit Leuven, Department of Chemistry, Celestijnenlaan 200F, B-3001, Leuven, Belgium. E-mail: Koen.Binnemans@chem.kuleuven.ac.be
First published on 14th November 2002
Lanthanide complexes of 1,10-phenanthroline (phen), 2,2′-bipyridine (bipyridyl, bpy) and dipicolinate (dpa), together with uncomplexed lanthanide ions (Ln=
Nd, Sm, Dy, Ho, Er) were doped into silica–polyethylene glycol (SiO2–PEG) inorganic–organic hybrid materials. The samples were prepared via a sol–gel process. The intensities of the f–f transitions in the absorption spectrum were analysed by application of the Judd–Ofelt theory. Sets of phenomenological Ωλ intensity parameters have been extracted. The hypersensitive transitions are strongly influenced by the drying time of the sol–gel glass. The PEG molecules compete with the organic ligand for complex formation to the lanthanide ions complex. 1,10-Phenanthroline and bipyridyl complexes are not stable in the presence of PEG, but the dipicolinate complexes are.
The closed 5s- and 5p-shells efficiently shield the 4f-shell of lanthanides from the environment and this results in unique optical features. Lanthanide f–f-transitions show narrow lines in the near-infrared, visible and ultraviolet part of the spectrum, but the magnetic dipole (MD) and induced electric dipole (ED) transitions are weak.5 There is a lot of interest in the trivalent lanthanide ions because of their strong luminescence with high coloric purity and the antenna effect.6 When a lanthanide ion is surrounded by a ligand that contains a light-absorbing group, the excitation energy absorbed by the ligand can be transferred to the lanthanide ion (=antenna effect). The strong light absorption capacity by the ligand improves the luminescence yield. Complexes of Eu3+ and Tb3+ with 1,10 phenanthroline (phen) and 2,2′-bipyridine (bpy) have been studied in silica–PEG sol–gels.7 The absorption spectra of different lanthanide complexes doped in silica–PEG sol–gels are the subject of this paper. The lanthanide complexes [Ln(bpy)2]Cl3, [Ln(phen)2]Cl3, Na3[Ln(dpa)3] and LnCl3
(bpy=
bipyridyl, 2,2′-bipyridine, phen
=
1,10-phenanthroline, dpa
=
dipicolinate, Ln
=
Nd, Sm, Dy, Ho, Er) are incorporated. The induced ED-transitions can be characterised by the three phenomenological intensity parameters Ωλ(λ
=
2, 4, 6). These Ωλ-intensity parameters derived from the Judd–Ofelt theory represent the square of the charge displacement due to induced electric dipole transitions.8,9 The parameters can be determined by a least-squares fit to the experimental dipole strengths extracted from the absorption spectra and can be used to rationalize the spectroscopic and structural properties of the complexes and the hybrid materials.10 The Ω2-parameter, gives information on the intensities of the so-called hypersensitive transitions, i.e. transitions which are strongly influenced by small changes in the coordination sphere. Comparisons are made between the different ligands, the different lanthanides and the sol–gel materials. The influence of PEG and water will be discussed.
The preparation of lanthanide(III) phenanthroline and bipyridyl complexes [Ln(phen)2]Cl3·2H2O and [Ln(bpy)2]Cl3·2H2O (phen=
1,10-phenanthroline; bpy
=
2,2′-bipyridine; Ln
=
Nd, Sm, Dy, Ho and Er) is described elsewhere.10 For the Na3[Ln(dpa)3] complexes, pyridine-2,6-dicarboxylic acid (dipicolinic acid) is dissolved in a warm 0.2 M NaOH solution. The pH must be around pH
=
7 or 8. The resulting solution is further concentrated by evaporation of the water and the pH is measured again. Before cooling down, an equivalent quantity (Ln∶dpa 1∶3) of the lanthanide salt is added. Small crystals appear after a few minutes. The precipitate was filtered, then washed several times with cold water and dried in a vacuum oven. The dried complexes were characterised by IR spectrometry and CHN elemental analysis.
A different approach was used for the glasses containing LnCl3
(Ln=
Nd, Sm, Dy, Ho, Er). An exact quantity of Ln2O3 was dissolved in a concentrated solution of HCl. Repetitive evaporation of the solution and redissolving in water removed the excess of hydrogen chloride. Finally a neutral water solution with a known quantity of Ln3+ was obtained. This solution was added to the water fraction in solution B.
The buffered silica–PEG sol–gel method was used for the dipicolinate, bipyridyl and phenanthroline complexes. When LnCl3 was added to a neutralised sol–gel lanthanide phosphates precipitated, therefore pH=
2 was used for these samples. Samples with different concentrations were prepared.
Another experiment was done with different equivalents (1–20) of phenanthroline or bipyridyl added to a fixed lanthanide concentration. Exact amounts of ligand were added to a solution B containing a fixed concentration of Ln3+.
Absorption spectra were recorded at room temperature using a Shimadzu UV-3100 spectrophotometer. Three absorption spectra of each sample were recorded: one before gelling, one after 24 h of drying at 50°C and a third one after a month of drying at 50
°C. During this month of heat treatment the volume of the glasses shrunk further to between 85% and 95% of the starting volume. Also spectra of [Ln(phen)2]Cl3·2H2O and [Ln(bipy)2]Cl3·2H2O were recorded in solution B and in pure PEG.
![]() | ||
Fig. 1 Dipole strength of three transitions: (a)
4F5/2![]() ![]() ![]() ![]() ![]() ![]() |
The relationships between experimental dipole strengths Dexp, the theoretical calculated dipole strengths Dth and the Judd–Ofelt parameters are given in eqn. (1)–(3).
![]() | (1) |
![]() | (2) |
Dexp![]() ![]() | (3) |
Phenanthroline and bipyridyl dissolve very well in these hybrid sol–gel materials. The influence of high concentrations of the ligands on the dipole strength, while Nd3+ concentration was kept constant, was investigated (Fig. 2). Extra amounts of 1,10-phenanthroline influence the dipole strength of the hypersensitive transition 4G5/2←
4I9/2, with a plateau when the ligand concentration is twelve times the lanthanide concentration. The intensity of the non-hypersensitive transitions does not change as a function of the phenanthroline content. Other lanthanides show similar behaviour. Little or no influence on the transition intensities is observed when the bipyridyl concentration is increased.
![]() | ||
Fig. 2 Dipole strength of three transitions: 4F5/2![]() ![]() ![]() ![]() ![]() ![]() |
There was no difference between the Judd–Ofelt parameters of the final solution C and the gelled samples that stayed in the oven for 24 h. The values of the Ω2-parameters do not change when the starting solution was transformed into a gel. During a longer drying period, these parameters do change. In contrast, the Ω4- and Ω6-values vary little upon heating and no general trend can be observed. The Ω4- and Ω6-parameters both decrease when going from Nd3+ to Sm3+ and from Dy3+ to Er3+. When the Ωλ-values for the different ligands are compared, we distinguish two groups. Between the parameters of [Ln(bpy)2]Cl3, [Ln(phen)2]Cl3, LnCl3 little variation is found. The parameters for Na3[Ln(dpa)3] are quite different. In Fig. 3, the absorption spectrum of the hypersensitive transition of Nd3+ and two other transitions are compared for two ligands. There is crystal-field fine structure in the spectrum of Na3[Nd(dpa)3]. Spectra of the other complexes are similar and do not show fine structure.
![]() | ||
Fig. 3 Comparison of the fine structure in the room temperature absorption spectrum of the hypersensitive transition 4G5/2![]() ![]() |
For comparison the calculated Judd–Ofelt parameter of Ln3+ in pure PEG or in 80% PEG with 20% water are also summarised in Table 2 (see later). It is clear that the 20% water added affects the spectrum. No values are given for Dy3+ because the faults were too big. They are in the order of 1 for the Ω4-parameter and 1.5 for the Ω6-parameter.
The Ω2-parameter is associated with short-range coordination effects and its value increases with increasing coordination number, higher basic character of the ligand and higher covalence of the bonding.5 The intensity of the hypersensitive transition and the value of the Ω2-parameter depends on the ligand type: oxygen donor>
nitrogen–oxygen donor
>
sulfur donor
>
aqua ion. There is an inverse relationship between the length of the ligand–lanthanide bond and the Ω2-parameter. The Ω4- and Ω6-parameters that are related to the other transitions depend on long-range effects. More rigid matrices have lower Ω4- and Ω6-values. Rigidity increases in the following order: coordination complexes
<
halide vapours
<
hydrated ions
<
viscous solutions
<
glasses
<
crystalline mixed oxides.5
No difference in parameter values is observed during the 24 h of drying. In this period the silica backbone was formed and the samples gelled. The long range-effects that influence Ω4- and Ω6-values are not changed. This is interesting because it indicates that the other components (water, PEG, ligand) are responsible for the transition intensities and not the silica. Results of the complexes in pure PEG and 80% PEG (+20% water) confirm this statement because silica is absent in this case. The Ω4- and Ω6-parameters of the 80% PEG are similar to those for solution C and the gels dried for a short period. The Ω4- and Ω6-parameters of the pure PEG are similar to those of the long dried gels.
The influence of the different ligands was studied. The spectra of [Ln(bpy)2]Cl3, [Ln(phen)2]Cl3 and LnCl3 are very similar. On the other hand the spectrum and therefore the Ωλ-parameters are totally different for Na3[Ln(dpa)3]. This is evident from Table 1. Luminescence of phenanthroline and bipyridyl complexes of Tb3+ and Eu3+ in silica–PEG sol–gels was previously studied.7 These organic ligands are used to improve luminescence yield via the antenna effect. This means that a part of the ligands has to be close enough to the lanthanide to transfer the excitation energy.16 Bipyridyl dissolves very well in PEG. But at high concentration (C>
0.08 M) the phenanthroline complex crystallises and there is no homogenous distribution of the lanthanide. In Table 1, little effect of complex formation is observed; the values are not much higher than those for LnCl3 where the only interactions are ionic. This means that the ligands are close enough to the lanthanide to transfer energy at high concentration (C
>
0.1 M bipy) but still do not bond strongly and are not able to influence the lanthanide ion much. Water and PEG dominate all the parameters. Only at higher concentrations does 1,10-phenanthroline influence the hypersensitive transition of Nd3+
(Fig. 2). Beyond a metal-to-ligand ratio (Ln3+∶ligand) 1∶12, further addition of the ligand gives little change in dipole strength and a plateau is reached. Therefore samples with ratio 1∶12 were prepared. For bipyridyl, which is a more flexible molecule than 1,10-phenanthroline and which is better soluble in PEG, little or no change was observed. It appears that the cation complexing capacity of PEG is too high in comparison to that of bipyridyl so that the bipyridyl ligand cannot efficiently compete with the PEG molecules for the lanthanide ion.
Ion | Matrix | Ligandb | Ω 2 | Ω 4 | Ω 6 | |
---|---|---|---|---|---|---|
a All parameters are expressed in 10−20 cm2. b Phen 1∶12 means that the lanthanide to 1,10-phenanthroline ratio was 1 to 12. | ||||||
Nd3+ | Si–PEG | dpa | (1) | 4.2![]() ![]() |
6.9![]() ![]() |
11.1![]() ![]() |
(2) | 3.9![]() ![]() |
6.8![]() ![]() |
11.5![]() ![]() |
|||
phen 1∶12 | (1) | 4.1![]() ![]() |
5.9![]() ![]() |
7.8![]() ![]() |
||
(2) | 4.4![]() ![]() |
6.1![]() ![]() |
8.1![]() ![]() |
|||
phen 1∶2 | (1) | 2.2![]() ![]() |
6.6![]() ![]() |
8.3![]() ![]() |
||
(2) | 2.8![]() ![]() |
6.2![]() ![]() |
7.9![]() ![]() |
|||
bipy 1∶12 | (1) | 1.6![]() ![]() |
5.8![]() ![]() |
7.7![]() ![]() |
||
(2) | 2.4![]() ![]() |
6.9![]() ![]() |
7.8![]() ![]() |
|||
bipy 1∶2 | (1) | 1.2![]() ![]() |
5.9![]() ![]() |
7.8![]() ![]() |
||
(2) | 2.7![]() ![]() |
5.1![]() ![]() |
6.5![]() ![]() |
|||
chloride | (1) | 0.7![]() ![]() |
6.5![]() ![]() |
7.7![]() ![]() |
||
(2) | 2.3![]() ![]() |
6.5![]() ![]() |
7.3![]() ![]() |
|||
PEG | chloride | (1) | 0.9![]() ![]() |
6.5![]() ![]() |
7.8![]() ![]() |
|
(2) | 2.7![]() ![]() |
5.8![]() ![]() |
6.3![]() ![]() |
|||
Ho3+ | Si–PEG | dpa | (1) | 6.4![]() ![]() |
4.6![]() ![]() |
5.0![]() ![]() |
(2) | 6.6![]() ![]() |
4.8![]() ![]() |
5.4![]() ![]() |
|||
phen 1∶12 | (1) | 5.1![]() ![]() |
5.5![]() ![]() |
2.4![]() ![]() |
||
(2) | 5.7![]() ![]() |
4.9![]() ![]() |
3.2![]() ![]() |
|||
phen 1∶2 | (1) | 3.4![]() ![]() |
3.2![]() ![]() |
3.2![]() ![]() |
||
(2) | 3.9![]() ![]() |
3.5![]() ![]() |
3.8![]() ![]() |
|||
bipy 1∶12 | (1) | 2.8![]() ![]() |
3.5![]() ![]() |
3.7![]() ![]() |
||
(2) | 3.7![]() ![]() |
4.6![]() ![]() |
4.1![]() ![]() |
|||
bipy 1∶2 | (1) | 1.6![]() ![]() |
4.2![]() ![]() |
2.7![]() ![]() |
||
(2) | 3.3![]() ![]() |
4.0![]() ![]() |
2.3![]() ![]() |
|||
chloride | (1) | 1.4![]() ![]() |
3.3![]() ![]() |
3.4![]() ![]() |
||
(2) | 4.1![]() ![]() |
3.3![]() ![]() |
3.6![]() ![]() |
|||
PEG | chloride | (1) | 1.5![]() ![]() |
3.3![]() ![]() |
3.6![]() ![]() |
|
(2) | 3.9![]() ![]() |
3.3![]() ![]() |
3.4![]() ![]() |
|||
Er3+ | Si–PEG | dpa | (1) | 6.5![]() ![]() |
1.9![]() ![]() |
3.2![]() ![]() |
(2) | 6.7![]() ![]() |
1.7![]() ![]() |
4.0![]() ![]() |
|||
phen 1∶12 | (1) | 6.2![]() ![]() |
1.7![]() ![]() |
2.2![]() ![]() |
||
(2) | 7.0![]() ![]() |
1.8![]() ![]() |
2.6![]() ![]() |
|||
phen 1∶2 | (1) | 3.3![]() ![]() |
2.5![]() ![]() |
1.4![]() ![]() |
||
(2) | 5.2![]() ![]() |
2.5![]() ![]() |
1.4![]() ![]() |
|||
bipy 1∶12 | (1) | 4.2![]() ![]() |
2.5![]() ![]() |
2.1![]() ![]() |
||
(2) | 4.7![]() ![]() |
2.9![]() ![]() |
2.5![]() ![]() |
|||
bipy 1∶2 | (1) | 3.2![]() ![]() |
2.3![]() ![]() |
1.6![]() ![]() |
||
(2) | 5.1![]() ![]() |
2.1![]() ![]() |
1.5![]() ![]() |
|||
chloride | (1) | 2.3![]() ![]() |
1.9![]() ![]() |
1.5![]() ![]() |
||
(2) | 5.5![]() ![]() |
2.8![]() ![]() |
2.1![]() ![]() |
|||
PEG | chloride | (1) | 2.9![]() ![]() |
1.5![]() ![]() |
1.6![]() ![]() |
|
(2) | 4.8![]() ![]() |
1.5![]() ![]() |
1.3![]() ![]() |
Ω 2 | Ω 4 | Ω 6 | ||
---|---|---|---|---|
a All parameters are expressed in 10−20 cm2. b These parameters could not be determined (see text). | ||||
Nd3+ | A | 0.9![]() ![]() |
6.5![]() ![]() |
7.8![]() ![]() |
B | 2.7![]() ![]() |
5.8![]() ![]() |
6.3![]() ![]() |
|
Sm3+ | A | b | 4.6![]() ![]() |
1.9![]() ![]() |
B | b | 5.9![]() ![]() |
2.1![]() ![]() |
|
Ho3+ | A | 1.5![]() ![]() |
3.3![]() ![]() |
3.6![]() ![]() |
B | 3.9![]() ![]() |
3.3![]() ![]() |
3.4![]() ![]() |
|
Er3+ | A | 2.9![]() ![]() |
1.5![]() ![]() |
1.6![]() ![]() |
B | 4.8![]() ![]() |
1.5![]() ![]() |
1.3![]() ![]() |
The parameters for the bipy, phen and chloride complexes in pure silica sol–gels have been published.17 Because PMMA cuvettes were used in this study, the samples could not be heated to 100°C as in ref. 17. It is therefore difficult to compare the final results. As the long-range parameters of the PEG–silica sol–gels are more determined by PEG than by the silica one can expect that the final parameters will be different. But in both cases the Ω2-parameter value increases when water is removed.
As can be deduced from the parameter values and from Fig. 3, the dipicolinate complex molecule gives a totally different spectrum. The dipicolinate ligand crystallises with lanthanides in a complex of D3-symmetry.18 According to model calculations of Na3[Ln(dpa)3]
(Ln=
Nd, Ho or Er), or complexes with similar tridentate ligands like oxydiacetate in aqueous solution, the most important contribution to the intensities of hypersensitive transitions in these ions can be correlated with the ligand polarizability.19 Absorption and IR-luminescence of Na3[Nd(dpa)3] has been studied in pure silica sol–gels.11 No antenna effect was observed because the gap between energy levels of the ligand and the lanthanide ion is too large. The luminescence of Na3[Eu(dpa)3] has also been studied in the past.20 In the present study other lanthanide complexes are doped in a silica–PEG sol–gel and Judd–Ofelt analysis has been done. The spectra of the Na3[Ln(dpa)3] complexes (Ln
=
Nd, Sm, Dy, Ho, Er) in silica–PEG sol–gels still show some crystal-field fine structure and the Ωλ-parameters differ from the other complexes. This clearly shows that dipicolinate is a better ligand than phenanthroline or bipyridine. The Ω2-parameters are higher than in the other systems. The tridentate dipicolinate ligand is also strong enough to shield the lanthanide from water. The Ω4- and Ω6-parameters are higher than those of the other ligands. The parameters are more determined by the low rigidity of the surrounding complex than by the rigidity of the silica–PEG matrix. This can be explained by efficient shielding over a long range.
Some general statements can be made for both the Ω4- and Ω6-parameters. The values for the lighter lanthanides are larger than those for the heavy lanthanides, with a minimum between Sm3+ and Dy3+. The radial integrals in the expressions of the Judd–Ofelt parameters decrease from over the lanthanide series (no reliable Ωλ-parameter can be determined for Eu3+, Gd3+ and Tb3+).
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