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Optics and Spectroscopy, Vol. 89, No. 3, 2000, pp. 360–368. Translated from Optika i Spektroskopiya, Vol.

89, No. 3, 2000, pp. 394–403.


Original Russian Text Copyright © 2000 by Sveshnikova, Lanin, Krutineva, Ermolaev.

MOLECULAR
SPECTROSCOPY

A Mechanism of the Influence of Gd(III) and Other Ln(III) Ions


on Sensitized Luminescence of Eu(III) and Tb(III) Ions
in Aqueous and Ethanol Solutions:
The Role of Hydroxyl Bridges
E. B. Sveshnikova, V. E. Lanin, E. V. Krutineva, and V. L. Ermolaev
All-Russian Research Center, Vavilov State Optical Institute, St. Petersburg, 199034 Russia
Received April 14, 2000

Abstract—We studied sensitization of Eu(III) and Tb(III) ions by molecules of 1,10-phenanthroline and
2,2-bipyridil in D2O and d6-ethanol and the influence of Nd(III), Pr(III), Sm(III), Gd(III), and Ho(III) ions on
the luminescence intensity Ilum and lifetime τlum of Eu(III) and Tb(III) in solutions. The stability constants of
complexes of Eu(III) and Gd(III) with 2,2'-bipyridil are measured by spectrophotometric and luminescence
methods. It is shown that luminescence of Eu(III) is quenched by Gd(III) ions at the ion concentration equal to
10–2–10–1 M, which is caused by competing between these ions for a sensitizer. At the concentration of Ln(III)
ions equal to 10–6–10–3 M, the sensitized luminescence of Eu(III) and Tb(III) was quenched and τlum decreased
in the presence of Nd(III) ions, whereas in the presence of Gd(III) the luminescence intensity increased. It is
proved that a bridge that connects the two ions upon energy transfer is formed by hydroxyl groups. The intensity
of luminescence of Eu(III) and Tb(III) in aqueous solutions and its lifetime decreased in the presence of
hydroxyl groups, while upon addition of Gd(III) to these solutions these quantities were restored. We also found
that the addition of Gd(III) to deoxygenated ethanol solutions of 2,2'-bipyridil and Eu(III) slows down photo-
chemical and thermal reactions between bipyridil and Eu(III), resulting in the increase in the luminescence
intensity of Eu(III). © 2000 MAIK “Nauka/Interperiodica”.

INTRODUCTION and organic molecules in aqueous solutions and the


study of the factors that affect the efficiency of the
Sensitization of the Eu(III), Tb(III), Sm(III), and energy transfer is important for the solution of the prob-
Dy(III) ions by various chelates has been often used in lem of the simultaneous immunoassay of several anti-
the fluorescent immunoassay with a lanthanide marker bodies labeled with different lanthanides.
to increase the sensitivity of the method [1]. Studies of
the efficiency of sensitization of Eu(III) ions by dike- The aim of this paper is to study the formation of
tones, as well as of ternary complexes of this ion with complexes of metal ions with 2,2'-bipyridil and 1,10-
diketones and phenanthroline in solutions and suspen- phenanthroline and to investigate the sensitization effi-
sions [1–4] revealed the enhancement of the sensitiza- ciency and the luminescence spectra of Eu(III) and
tion efficiency of Eu(III) upon addition of the Gd(III) Tb(III) ions sensitized by these molecules and p-
and Y(III) ions to solutions, as well as some other ions dimethoxybenzophenone. We also studied the effect of
that are unable to quench both the triplet state of sensi- other lanthanide ions in solution on the luminescence
tizing organic molecules and luminescence of Eu(III) intensity and lifetime of Eu(III) and Tb(III) and deter-
by energy or electron transfer. Thus, the addition of mined the nature of bridge groups responsible for the
ions of some trivalent metals to the solution with a lan- formation of binuclear complexes of lanthanide ions in
thanide marker also increases the intensity of sensitized aqueous and ethanol solutions.
luminescence of the marker.
It was shown in [4] that the addition of 4 × 10–6 M of EXPERIMENTAL
Nd(III) to the aqueous solution of ternary complexes of Salts of Ln(III) were dissolved in the form of chem-
Eu(III) with β-diketones and phenanthroline resulted in ically pure chloride crystal hydrates; 2,2'-biperydil,
a decrease in τlum of Eu(III) caused by the formation of 1,10-phenanthrolone, and p-dimethoxybenzophenone
binuclear β-diketone complexes with Eu(III) and were also chemically pure. At the lanthanide concentra-
Nd(III). It was noted in [5] that upon dissolving of these tions used (10–7–3 × 10–2 M), the salts were virtually
binuclear complexes in hydrocarbon solvents, the completely dissociated in aqueous solutions and only
energy transfer in binuclear complexes was absent. partially dissociated in ethanol. We used doubly dis-
The elucidation of the conditions required for the tilled usual and distilled water and d6-ethanol as sol-
appearance of binuclear complexes of lanthanide ions vents. The deuterated solvents were used to increase the

0030-400X/00/8903-0360$20.00 © 2000 MAIK “Nauka/Interperiodica”


A MECHANISM OF THE INFLUENCE OF Gd(III) AND OTHER Ln(III) IONS 361

quantum yield of luminescence of Tb(III) and Eu(III) bipyridil in complexes of Eu(III) ions deposited from
ions and, hence, to increase the sensitivity of the the ethanol solution to a quartz substrate are identical.
method. Bipyridil solutions in D2O were alkalized by To reliably study the complexing of these ions and mol-
adding NaOD with a subsequent introduction of Ln(III) ecules, we controlled a change in the solution pH upon
ions. The solution pH was controlled with a calibrated the addition of salts, prepared the solutions of mole-
pH meter (pH-673). The luminescence spectra of cules with the same pH, and measured the absorption
Tb(III) and Eu(III) ions were measured with a Hitachi spectra of these solutions. Figure 1 shows that the
650-40 fluorimeter with a minimum spectral slit width 302-nm absorption band of 2,2'-bipyridil appearing in
of 2 nm. The absorption spectra of solutions of 2,2'- the presence of lanthanide ions is mainly determined by
bipirydil, 1,10-phenanthroline, Ln(III) ions, and com- complexing with lanthanide ions rather than by a
plexes of lanthanide ions with 2,2'-bipyridil deposited change in the solution pH. This fact allowed us to deter-
on quartz were measured with a Cary-17 spectropho- mine the first stability constants of these ions in water
tometer with the 0.1–0.5 nm resolution. from the data on the dependence of the concentration of
The decay time τlum of the sensitized luminescence free and bonded molecules of 2,2'-bipyridil on the con-
centration of metal ions in aqueous solution. The stabil-
of Tb(III) and Eu(III) ions was measured with a setup
ity constants found in this way were kst = 8 ± 1 for the
consisting of a 337-nm pulsed LGI-21 nitrogen laser
(pulse length ∆t = 20 ns), a FEU-79 photomultiplier, [Gd(III)-bpy] complex and kst = 6 ± 1 for the [Eu(III)-
and a S8-13 oscilloscope. The luminescence decay of bpy] complex. One can see from Fig. 1 that upon addi-
Tb(III) and Eu(III) in all solutions, in particular, in the tion of aluminum ions into the 2,2'-bipyridil solution at
presence of energy acceptors, was exponential. The rate the concentration an order of magnitude lower than that
constants of energy transfer or the constants of lumi- of lanthanide ions, the spectrum of 2,2'-bipyridil com-
nescence decay of Tb(III) and Eu(III) caused by accep- pletely transforms to the spectrum of another form.
tor ions were measured from the Stern–Volmer formula However, because the solution pH changes very
from the data on the shortening of τlum and on the lumi- strongly due to strong hydrolysis of aluminum salts, the
nescence quenching of these ions at their concentration variation of the spectrum is almost completely deter-
mined by this change in pH, as follows from Fig. 1.
equal to 10–3 M upon direct excitation of Eu(III) ions
into their absorption band and upon sensitization of Our analysis of variations in the absorption spectra
Eu(III) and Tb(III) ions by organic molecules. The rate of aqueous solutions of organic molecules caused by
constants measured by these methods were close to the addition of metal ions showed that the luminescent
each other, which allowed us to determine the rate con- method for measuring relative stability constants of
stants of energy transfer between ions at their lower complexes of metal ions with organic molecular sensi-
concentrations in solutions (10–6–10–4 M) only from the tizers based on the quenching of luminescence of the
data on quenching of the sensitized luminescence of sensitized ion due to the competition between lumi-
Eu(III) and Tb(III) ions neglecting the possibility of nescing and non-luminescing metal ions is valid only
competition between these ions in energy transfer from for the systems where the influence of hydrolysis of
sensitizing organic molecules. metal ions on organic ligands can be neglected.
The quantum yields of luminescence of Eu(III) ions We studied luminescence of Eu(III) sensitized by
sensitized by bipyridil (the sensitization efficiency) in 2,2'-bipyridil and 1,10-phenanthroline and the influ-
water and ethanol were determined by comparing the ence of Gd(III) ions and of variation in the solution pH
quantum yields of luminescence of Eu(III) upon its corresponding to the solution acidification upon addi-
direct excitation into the 7F0–5D3 band and upon its tion of these salts (Fig. 2) on the Eu(III) luminescence
excitation into the absorption band of a sensitizer. intensity by exciting solutions at the isosbestic point of
the absorption spectrum of organic molecules. We
found that at high ion concentrations, the Eu(III) lumi-
STABILITY CONSTANTS OF COMPLEXES OF nescence is quenched by Gd(III) ions (Fig. 2) and the
EU(III) AND GD(III) IONS WITH 2,2'-BIPYRIDIL quenching is mainly caused by the Gd(III) ions them-
IN AQUEOUS SOLUTIONS selves rather than by the solution acidification caused
be these ions.
We studied the effect of addition of Eu(III), Gd(III),
Al(III), and H(I) ions to aqueous solutions of 2,2'-bipy- Thus, at high concentrations of Eu(III) and Gd(III)
ridil and 1,10-phenanthroline on their absorption spec- ions, the Gd(III) ion is a quencher of the Eu(III) lumi-
tra (Fig. 1). Variations in the spectra of these organic nescence sensitized by organic molecules.
molecules after addition of metal salts to the solution Because the values of kst for complexes of Ln(III)
can be caused by two reasons: the formation of com- ions with bipyridil are low for the Eu(III) concentra-
plexes between metal ions and molecules and the tions used, only a part of molecules form complexes
appearance of protonated forms of these molecules due with ions in the ground state, while the majority of
to hydrolysis of the salts added, resulting in the acidifi- europium ions are sensitized in collision complexes
cation of the solution. Note that the absorption spec- with excited bipyridil molecules. For this reason, the
trum of the singly protonated form and the spectrum of slope of straight line of quenching does not reflect the

OPTICS AND SPECTROSCOPY Vol. 89 No. 3 2000


362 SVESHNIKOVA et al.

ε × 104, Òm–1 å–1 ε × 104, Òm–1 å–1


2 2
(a) (b)

1 1

0 0

2 2
(c) (d)

1 1

0 0
260 280 300 320 240 260 280 300 320 340
λ, nm

Fig. 1. Dependence of the absorption spectra of 2,2'-bipyridil (5 × 10–5 M) and 1,10-phenanthroline (4 × 10–5 M) in H2O on the
presence of metal ions at 293 K. (a) 2,2'-bpy in the presence of GdCl3 · 6H2O: (✶) 0 M; (★) 5 × 10–3 M; (m) 5 × 10–2 M; (d) 10–1 M;
(j) 2 × 10–1 M; (✚) 3 × 10−1 M; (✴) 4 × 10–1 M. (b) 2,2'-bpy: (m) pH = 7.2; (d) pH = 5.2; (✶) 4 × 10–1 M of Gd(III) (pH = 5.3).
1,10-phen: (✡) pH = 7.0; (s) pH = 5.2; (n) 10–1 M of Gd(III) (pH = 5.2). (c) 2,2'-bpy in the presence of EuCl3 · 6H2O: (✶) 0 M; (m)
8 × 10–3 M; (d) 2.5 × 10–3 M; (✴) 5 × 10–2 M; (r) 10–1 M; (✚) 5 × 10−1 M. (d) 2,2'-bpy in the presence of AlCl3· 6H2O: (r) 0 M;
(j) 5 × 10–5 M; (d) 2.5 × 10–4 M; (m) 10–3 M; (★) 5 × 10–3 M; (✶) 2.5 × 10−2 M; (✴) 5 × 10–2 M (absorption spectra were measured
using a reference channel in which a cell with the solution of metal ions at the appropriate concentration was placed).

OPTICS AND SPECTROSCOPY Vol. 89 No. 3 2000


A MECHANISM OF THE INFLUENCE OF Gd(III) AND OTHER Ln(III) IONS 363

relation between the stability constants of europium 0 /I


Ilum lum
and gadolinium ions. 2.8

EFFECT OF GD(III) IONS ON SENSITIZED


LUMINESCENCE OF EU(III) AT ITS LOW 2.4
CONCENTRATIONS
We studied the influence of Gd(III) ions of the inten- 2.0
sity of sensitized luminescence of Eu(III) in solutions
of 2,2'-bipyridil and 1,10-phenanthroline (3 × 10–3 M)
in D2O at the concentrations of Eu(III) between 10–5 1.6
and 10–4 M. We found that the addition of Gd(III) ions
at concentrations exceeding by 2–3 orders of magni-
tude that of the Eu(III) ions, resulted in the increase in 1.2
the sensitized luminescence of europium ions and in
the redistribution of the intensity ratio of the 5D0–7F1
0 0.02 0.04 0.06 0.08 0.10
and 5D0–7F2 transitions in the luminescence spectrum [Gd(III)], M
of Eu(III). In these experiments, we excited organic
molecules into the long-wavelength wing of their Fig. 2. Quenching of luminescence of 2 × 10–2 M Eu(III) by
absorption band. The influence of Gd(III) depended on Gd(III) ions in H2O for the pH values corresponding to the
the excitation wavelength and could be explained by a solution acidification produced by Gd(III) ions. (m) sensi-
trivial increase in the solution absorption caused by tizer: 2,2'-bipyridil, quencher: Gd(III); (n) quenching of the
complexing of organic molecules with Gd(III) (Fig. 1) Eu(III) luminescence by varying pH; (d) sensitizer: 1,10-
and additional energy transfer from the excited mole- phenanthroline, quencher: Gd(III); (s) quenching of the
Eu(III) luminescence by varying pH. Luminescence was
cules to Eu(III) ions. excited at the isosbestic point of the absorption spectrum at
We managed to observe luminescence of Eu(III) 290 nm (T = 293 K).
sensitized by 2,2'-bipyridil and 1,10-phananthroline in
the D2O solution down to the Eu(III) concentration of We obtained an unexpected result by studying the
2.0 × 10–8 M (Fig. 3). effect of Gd(III) (10–4 M) on the sensitized lumines-
To neglect the influence of lanthanide ions on the cence of Eu(III) in bubbled and nonbubbled solutions
absorption spectra of 2,2'-bipyridil, we studied the of 3 × 10–3 M 2,2'-bipyridil + 10–5 Eu(III) in d6-ethanol.
effect of Gd(III) of the sensitized luminescence of The removal of O2 from this solvent did not enhance the
Eu(III) in D2O solutions at concentrations of Eu(III), sensitized luminescence of Eu(III), but on the contrary
Gd(III), and bipyridil equal to 10–6, 10–4, and 3.5 × (Table 1) resulted in a strong luminescence quenching,
10−3 M, respectively. The solutions were bubbled, this quenching being an order of magnitude weaker in
which enhanced the intensity of sensitized lumines- the presence of Gd(III) ions in the solution. We found
cence of Eu(III) approximately by an order of magni- that upon irradiation of ethanol solutions of Eu(III) that
tude (Table 1). Both bubbled and nonbubbled D2O
did not contain any other ions, the sensitized lumines-
solutions exhibited the same enhancement of sensitized cence of Eu(III) decreased (while τlum did not change).
luminescence of Eu(III) in the presence of Gd(III). The
magnitude of this effect was different for the two lumi- This suggests that the photochemical reaction between
nescence bands of Eu(III) (Table 1), the effect being excited bipyridil molecules and Eu(III) ions proceeded.
independent of the exciting wavelength in the region The addition of the Gd(III) and La(III) ions to the solu-
from 310 to 325 nm. The variations in the absorption tion retarded the reaction. We assume that removal of
spectrum of bipyridil caused by the addition of 10–4 M O2 from the solution favors the dark reaction of reduc-
Gd(III) were very small at the bipyridil concentrations tion of Eu(III) ions, which is retarded by the Gd(III)
used. ions.

Table 1. Effect of removing of O2 and addition of 10–4 M of Gd(III) on the intensity of two bands of Eu(III) luminescence
sensitized by bipyridil (3 × 10–3 M) in D2O and C2D5OD solutions at 293 K

Ibubbl/Inbubbl, Ibubbl/Inbubbl, IEu + Gd/IEu IEu + Gd/IEu


Solution composition
Eu(III) solution Eu(III) + Gd(III) solution The 5D0–7F1 transition The 5D0–7F2 transition
D2O, 10–6M Eu(III) 9±1 7±1 3.5 ± 0.5 1.7 ± 0.2
C2D5OD, 10–5 M Eu(III) 0.03 ± 0.003 0.3 ± 0.03 2.6 ± 1 2.6 ± 1

OPTICS AND SPECTROSCOPY Vol. 89 No. 3 2000


364 SVESHNIKOVA et al.

qsen. lum qsen. lum


0.6 0.04

0.4

0.02

0.2

0 0.01 0.02 0.03 0.04 0 0.1 0.2 0.3 0.4


[Eu(III)], å [Eu(III)], mM
qsen. lum × 103 qsen. lum × 103
2 1.0

1 0.5

0 2 4 6 8 0 0.1 0.2 0.3 0.4 0.5


[Eu(III)], µM [Eu(III)], µM

Fig. 3. Dependences of the quantum yield of Eu(III) luminescence sensitized by 2,2'-bipyridil on the ion concentration in the 3.5 ×
10–3 M 2,2'-bipyridil solution in D2O measured for two luminescence bands of Eu(III) at 293 K: (d) the 5D0–7F1 band; (✶) the 5D0–
7F band (pH = 6.5 for 3 × 10–4 M of Eu(III)).
2

Thus, we found that the addition of Gd(III) to aque- hence, the additional sensitization channel of Eu(III)
ous solutions changes the relative intensities of lumi- did not appear in the presence of Gd(III). The presence
nescence bands of Eu(III) ions. We also found that, as of bpy–Eu(III) complexes in these frozen solutions is
in the studies of diketone complexes of Eu(III) [1–4], confirmed by the observation of sensitized lumines-
the Gd(III) ions affect the sensitized luminescence of cence of Eu(III).
europium ions. This influence is observed in the solu-
The quantum yield of luminescence of many che-
tions where the concentration of sensitizing ligands is lates of Eu(III) is lower than unity because of the exist-
more than an order of magnitude higher than the con- ence of a reversible photochemical reaction [6, 7].
centration of the added lanthanide ions, so that the Therefore, we can assume that along with energy trans-
addition of Gd(III) in the solution cannot affect com- fer from the excited sensitizer to the Eu(III) ion in solu-
plexing of Eu(III) ions and sensitizers. At the same tions, a reversible photochemical reaction takes place,
time, the explanation of the influence of Gd(III) on the which reduces the efficiency of Eu(III) sensitization,
intensity of sensitized luminescence of Eu(III) by the while the formation of the ion pair with Gd(III)
additional sensitization due to energy transfer from decreases the rate of this reaction. However, the study
complexes of Gd(III) to the Eu(III) complexes sug- of the quantum yield of luminescence of Eu(III) sensi-
gested in papers [1, 3] is not satisfactory. Because the tized by pyridil as a function of the Eu(III) concentra-
concentration of bipyridil in our experiments was tion showed that, in ethanol and water under the condi-
invariable, the phosphorescence spectra of free bipyri- tions close to complete energy transfer, the quantum
dil and bipyridil bonded with ions coincided in ethanol yield is close to unity. Therefore, upon formation of the
and water–glycerol solutions at 77 K (Fig. 4) and, complexes of bipyridil molecules with Eu(III) ions, the

OPTICS AND SPECTROSCOPY Vol. 89 No. 3 2000


A MECHANISM OF THE INFLUENCE OF Gd(III) AND OTHER Ln(III) IONS 365

predominant channel of their interaction is the energy Ilum, rel. units


transfer, and the increase in the luminescence intensity
of Eu(III) by a factor of two in the presence of Gd(III)
cannot be explained by the suppression of the photo-
chemical process accompanying energy transfer from
bipyridil to Eu(III) or Tb(III). We can assume that
Gd(III) affects the luminescence of Eu(III) itself rather
than the rate of energy transfer.

HYDROXYL COMPLEXES OF LN(III) IONS


It was assumed in [4] that Gd(III) ions affect lumi-
nescence of Eu(III) ions in bridge complexes of these
ions. However, the nature of the bridge that can bind
these ions and the mechanism of the effect of Gd(III) on
the luminescence intensity and lifetime of Eu(III) and 350 400 450 500 550
Tb(III) remain open. λ, nm
To answer to this question, we will analyze the data
Fig. 4. Effect of lanthanide ions on phosphorescence spectra
on the sensitized luminescence spectra of Eu(III) and
will study energy transfer from Eu(III) and Tb(III) ions of 2,2'-bipyridil (10–4 M) in ethanol at 77 K (λex = 310 nm):
to other lanthanide ions in aqueous and ethanol solu- (d) 0 M of Ln(III); (m) 10–2 M of Gd(III); (✶) 10–2 M of
tions. One can see from Fig. 3 that as the concentration Eu(III); (r) 10–2 M of La(III).
of Eu(III) ions sensitized by bipyridil in water
decreases, the luminescence intensity at the 5D0–7F2
transition increases compared to that of the allowed Gd(III) affects the degree of complexing of Eu(III) ions
magnetic dipole 5D0–7F1 transition, which does not in water.
change upon variation in the symmetry of the environ-
ment of Eu(III). Similar variations in the luminescence
spectrum of Eu(III) were obtained upon its sensitiza- ENERGY TRANSFER IN HYDROXYL BRIDGE
tion by phenanthroline. This fact shows that the number COMPLEXES OF LN(III) IONS AND EFFECT
of Eu(III) complexes increases as the concentration of OF GD(III) ON THIS PROCESS
these ions decreases. A decrease in the concentration of We studied the influence of lanthanide ions on the
bipyridil by 35 times does not affect the intensity ratio lifetime and intensity of sensitized luminescence of
for these two bands in the studied range of concentra- Eu(III) and Tb(III) at the concentration of the interac-
tions of Eu(III) in D2O. The independence of the sym- tion ions equal to 10–3 M. We also studied the effect of
metry of the Eu(III) environment on the bipyridil con- acceptor ions on the intensity of intrinsic luminescence
centration suggests that the change in the relative inten- of Eu(III) upon direct excitation in the concentration
sities of the luminescence bands with decreasing range between 10–4 and 10–3 M, as well as the influence
concentration of bipyridil cannot be explained by an of lanthanide ions on the intensity of sensitized lumi-
increase in the number of complexes of Eu(III) with nescence of Eu(III) and Tb(III) in the concentration
bipyridil. This conclusion is confirmed by the observa- range between 10–6 and 10–3 M. We found that the pres-
tion of the same variations in the luminescence spec-
ence of Gd(III) ions (10–3 M) in aqueous solutions
trum of europium chloride in D2O upon its direct exci-
(pH = 6) of Eu(III) ions (10–3 M) does not affect the
tation into the 7F0–5D3 band in the range of concentra- intensity and lifetime of the Eu(III) luminescence. At
tions of Eu(III) from 10–4 to 10–3 M. Lanthanide salts the same time, in the presence of lanthanide ions at the
were added to solutions in the form of chlorides. How- same concentration, whose absorption spectra are over-
ever, the increase in complexing of Eu(III) ions as their lapped with the luminescence spectra of Eu(III) or
concentration and that of Cl– anions introduced with Tb(III), the luminescence intensity of the latter ions
Eu(III) decreased indicates unambiguously that Cl– decreases and its lifetime shortens, the luminescence
cannot serve as a bridge that provides the interaction decay being exponential.
between lanthanide ions in aqueous solutions in the
range of ion concentrations under study. Comparison of the quenching of sensitized lumines-
cence with the luminescence lifetime of sensitized ions
Therefore, we can assume that the spectrum of shows that for the concentration of quenching ions
Eu(III) reflects complexing of europium ions with OH– equal to 10–3 M the competition between sensitizing
or OD– groups of water, which increases when concen- ions and ion acceptors in the energy transfer from 2,2'-
trations of Eu(III) ions and hydroxyl groups in water bipyridil to these ions only slightly contributes to the
become closer to each other, while the addition of quenching of sensitized luminescence of Tb(III) and

OPTICS AND SPECTROSCOPY Vol. 89 No. 3 2000


366 SVESHNIKOVA et al.

Table 2. Quenching of luminescence of Eu(III) and Tb(III) Using the data on quenching of luminescence of Eu(III)
sensitized by 2,2'-bipyridil and p-dimethoxybenzophenone and Tb(III) ions by Nd(III) ions, we calculated the rate
and shortening of τlum of these ions in the presense of Ln(III) constants kt of energy transfer by the Stern–Volmer for-
ions for Cion = 10–3 M, Cbpy = 10–3 M in D2O (pD = 6) at 293 K mula at different ion concentrations. The results are
0 0 presented in Table 3.
Compounds τ lum /τlum I lum /Ilum
One can see from Table 3 that, upon sensitization by
Eu(III) + Nd(III), p-CH3O 1.3 ± 0.05 1.7 ± 0.1 phenanthroline or bipyridil, kt increases more than two
benzoph. orders of magnitude for both pairs of ions as the total
Eu(III) + Nd(III), bpy 1.3 ± 0.05 1.8 ± 0.1, 1.3 ± 0.1*
concentration of ion donors and acceptors decreases
from 10–3 to 10–6 M. This result can be explained by the
Eu(III) + Er(III), bpy 1.3 ± 0.05 1.3 ± 0.1* influence of hydroxyl bridges on energy transfer
Eu(III) + Pr(III), bpy 1.3 ± 0.05 1.6 ± 0.1 because the concentration of hydroxyl groups in solu-
Eu(III) + Gd(III), bpy 1.0 ± 0.05 1.0 ± 0.05 tion is lower than that of the ions under study, the
Eu(III) + Ho(III), bpy 1.6 ± 0.1 hydrolysis constants of lanthanide ions are of the order
of 10–9 [8], the stability constants of complexes of
Tb(III) + Nd(III), bpy 1.2 ± 0.05 1.2 ± 0.1
Ln(III) ions with OH– are of the order of 105 [9], and the
Tb(III) + Sm(III), bpy 1.3 ± 0.05 1.3 ± 0.1 relative concentration of lanthanide ions in complexes
*Quenching of luminescence of Eu(III) ions by Ln(III) ions upon with hydroxyl groups increases with decreasing con-
direct excitation into the 395-nm absorption band of Eu(III). centration of lanthanide ions in solution, while kt
should increase with an increasing amount of binuclear
complexes Ln1–OD–Ln2. When [OD–] ! [Ln(III)], kt
Eu(III) ions by Pr(III), Nd(III), Sm(III), Ho(III), and should increase linearly with the concentration of
Er(III) ions (Table 2). bridge groups in solution [10]. Here, we observed an
approximately linear increase in kt with decreasing con-
This fact allowed us to study energy transfer centration of lanthanide ions in solution; and we can
between these ions at low concentrations in solutions assume that kt changes in accordance with variation in
from the quenching of their sensitized luminescence in the ratio of concentrations of lanthanide ions and
the presence of ion acceptors. We performed this study hydroxyls in solution.
at concentrations of donors and acceptors from 10–6 to Because water–ethanol solutions are also used in
10–3 M. We observed the quenching of luminescence of fluorescent immunoassay [1], we studied the influence
Tb(III) and Eu(III) ions by lanthanide ion acceptors. of the Pr(III), Gd(III), and La(III) ions on luminescence
The quenching of luminescence of Eu(III) and Tb(III) of Eu(III) in d6-ethanol sensitized by 2,2'-bipyridil. As
by Nd(III) ions at the ion concentration in D2O equal to in aqueous solutions, we observed quenching of the
10–6–10–5 M strongly supports the bridge mechanism of sensitized luminescence of Eu(III) by Ln(III) ions,
energy transfer between ions. We found that the which were not involved in energy transfer, in ethanol
replacement of bidentate sensitizers, 2,2'-bipyridil and at high concentrations of lanthanide ions and low con-
1,10-phenanthroline, by monodentate p-dimethoxy- centrations of bipyridil. This study showed the ability
benzophenone reduced the efficiency of Eu(III) sensiti- of the added lanthanide ions to compete with Eu(III)
zation, but did not change the efficiency of quenching ions in complexing and allowed us to measure the rela-
of Eu(III) luminescence by Nd(III) ions. This result tive stability constants of these ions.
confirms our assumption that the ions in water are The study in the region of high concentrations of
bonded by hydroxyl groups rather than by bipyridil or bipyridil (10−3 M) and low concentrations of foreign
phenanthroline. We will discuss in detail the depen- ions (10–4–10–5 M) added to the 10–5 M Eu(III) solution
dence of energy transfer between lanthanide ions on the is also of interest. In this case, luminescence of Eu(III)
concentration of hydroxyl groups in our next paper. was quenched only in solutions containing Pr(III) ions

Table 3. Rate constants of energy transfer from Eu(III) and Tb(III) ions sensitized by 2,2'-bipyridil (10–3 M) and 1,10-
phenanthroline (5 × 10–3 M) to Nd(III) ions in D2O (pD = 6) at 293 K
Eu Eu Tb
Ion concentration, M k t × 105, k t × 105, k t × 105,
M–1 s–1 sensitized by bpy M–1 s–1 sensitized by phen M–1 s–1 sensitized by bpy
10–3 2 3.5 2.2
10–4 5.2 19.0 16.5
10–5 72.0 125.0 200.0
10–6 360.0 1000.0

OPTICS AND SPECTROSCOPY Vol. 89 No. 3 2000


A MECHANISM OF THE INFLUENCE OF Gd(III) AND OTHER Ln(III) IONS 367

that were able to accept the electronic excitation energy (a) (b) (c)
of Eu(III). The addition of Gd(III) and La(III) salts into Ilum, rel. units
solution did not affect the lifetime of Eu(III) lumines- 1
cence.
We studied quenching of sensitized luminescence of
Eu(III) by Pr(III) ions by decreasing the concentration
of lanthanide ions in solution keeping the concentration
of 2,2'-bipyridil constant in the region of lanthanide ion
concentrations from 10–6 to 10–3 M. At concentrations
of Pr(III) and Eu(III) between 10–6 and 10–5 M, the sen-
sitized luminescence of Eu(III) is quenched by Pr(III)
ions. At such low ion concentrations, this is possible
only if ion pairs were formed. We added crystal
hydrates of lanthanide salts in ethanol, and it is possible
that hydroxyl groups serve as bridges between ions in
this solvent. The rate constants of energy transfer cal-
culated from the Stern–Volmer formula were equal to 0
580 620 580 620 580 620
3 × 107 and 6 × 106 for concentrations of Pr(III) in solu- λ, nm
tion equal to 10–6 and 10–5, respectively; i.e., they are of
the same order of magnitude as the rate constants of
Fig. 5. Effect of the OD– anions and addition of Gd(III) to
energy transfer between lanthanide ions in water. the alkalized D2O solution on the luminescence spectrum of
Earlier, we observed the inhibition of quenching of Eu(III) at 293 K: (a) 10–3 M of EuCl3 in D2O; (b) 10–3 M of
sensitized luminescence of Eu(III) induced by Gd(III) EuCl3 in D2O + 10–3 M of NaOD; (c) 10–3 M of EuCl3 in
ions in bubbled ethanol solutions. This was possibly D2O + 10−3 M of NaOD + 10–2 M of GdCl3.
caused by a dark reaction of reduction of europium ions
in the absence of O2. The presence of the dark reaction
between Ln(III) ions and bipyridil is confirmed by the 10–2 M) on these quantities. The solution was alkalized
increase in the intensity of sensitized luminescence of
the 10–4 M bpy + 10–3 M Eu(III) solution by one and a by adding 10–4–2 × 10–3 M of NaOD. We found that at
half times after it has been kept in the dark for 30 min. the OD– concentration equal to 2 × 10–3 M, i.e., at the
After illumination of the solution, this additional lumi- concentration of hydroxyl groups comparable to that of
nescence of Eu(III) rapidly disappeared. This result Tb(III) and Eu(III) ions, luminescence of these ions
reflects the existence of two processes: the gradual was quenched and the its lifetime decreased in the pres-
increase in the fraction of complexes of lanthanide ions
and bipyridil in the ethanol solution and efficient pho- ence of hydroxyl groups. The addition of 10–3 M of
tochemical quenching of sensitization of Eu(III) in Gd(III) resulted in a weak increase in the luminescence
these complexes. intensity, while after the addition of 10–2 M of Gd(III)
Our study showed that as the concentration of the initial luminescence intensity and lifetime were
Eu(III) and Tb(III) ions in solutions decreased, their almost completely restored (Fig. 5). The alkalization of
luminescence was more efficiently quenched by for- the solution resulted in the change in the luminescence
eign ions that were present in solution at low concentra- spectrum of Eu(III): The 5D0–7F0 band appeared in the
tions; i.e., upon formation of bridge hydroxyl com-
plexes, any impurity ions in solution, which can play spectrum and relative intensities of the 5D0–7F1 and
the role of acceptors in energy transfer from lanthanide 5D –7F bands were changed. After the addition of
0 2
ions, can quench luminescence of lanthanide markers. Gd(III), the symmetry of the Eu(III) environment
If such deactivation channel of lanthanide markers increased and the luminescence spectrum of Eu(III)
exists or lanthanide ions are deactivated in hydroxyl returned to the spectrum of a solvated ion (Fig. 5). The
complexes, we can assume the existence of another influence of Gd(III) on the luminescence spectrum of
mechanism of the influence of Gd(III) on sensitized
luminescence of lanthanide ions, which consists in Eu(III) (10–6 M) sensitized by bipyridil in neutral solu-
drawing off hydroxyl groups from Eu(III) and Tb(III) tions was the same (Table 1).
ions, resulting in a weaker quenching of luminescence
of the se ions in hydroxyl complexes. To verify the Therefore, such a channel of the influence of Gd(III)
existence of this mechanism, we studied the depen- on luminescence of lanthanide markers exists, and
dences of the luminescence intensity and lifetime for luminescence of Ln(III) ions at low concentrations can
Eu(III) (10–3 M) and Tb(III) (10–3 M) on the OD– con- be quenched by hydroxyl groups and enhanced by
centration in D2O and the influence of Gd(III) (10−3 and Gd(III) in neutral solutions.

OPTICS AND SPECTROSCOPY Vol. 89 No. 3 2000


368 SVESHNIKOVA et al.

CONCLUSIONS ACKNOWLEDGMENTS
We can make the following conclusions from our This work was supported by the Russian Foundation
study: for Basic Research (project nos. 97-03-32398 and 00-
(1) Complexing of lanthanide ions at low concentra- 03-32208) and the Ministry of Science and Technology
tions with organic molecules in aqueous solutions is of the Russian Federation. The authors thank T. A. Sha-
accompanied by the formation of complexes of these khverdov for useful discussion of the results and for
ions with hydroxyl groups of water. The number of providing the possibility for bubbling solutions.
hydroxyl complexes of lanthanide ions increases as the
ion concentration approaches that of hydroxyl groups
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OPTICS AND SPECTROSCOPY Vol. 89 No. 3 2000