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

Sensitization of the Eu(III), Tb(III), Sm(III), and
Dy(III) ions by various chelates has been often used in
the fluorescent immunoassay with a lanthanide marker
to increase the sensitivity of the method [1]. Studies of
the efficiency of sensitization of Eu(III) ions by dike-
tones, as well as of ternary complexes of this ion with
diketones and phenanthroline in solutions and suspen-
sions [1–4] revealed the enhancement of the sensitiza-
tion efficiency of Eu(III) upon addition of the Gd(III)
and Y(III) ions to solutions, as well as some other ions
that are unable to quench both the triplet state of sensi-
tizing organic molecules and luminescence of Eu(III)
by energy or electron transfer. Thus, the addition of
ions of some trivalent metals to the solution with a lan-
thanide marker also increases the intensity of sensitized
luminescence of the marker.
It was shown in [4] that the addition of 4 × 10–6 M of
Nd(III) to the aqueous solution of ternary complexes of
Eu(III) with β-diketones and phenanthroline resulted in
a decrease in τlum of Eu(III) caused by the formation of
binuclear β-diketone complexes with Eu(III) and
Nd(III). It was noted in [5] that upon dissolving of these
binuclear complexes in hydrocarbon solvents, the
energy transfer in binuclear complexes was absent.
The elucidation of the conditions required for the
appearance of binuclear complexes of lanthanide ions
study of the factors that affect the efficiency of the
energy transfer is important for the solution of the prob-
lem of the simultaneous immunoassay of several anti-
bodies labeled with different lanthanides.
The aim of this paper is to study the formation of
complexes of metal ions with 2,2'-bipyridil and 1,10-
phenanthroline and to investigate the sensitization effi-
ciency and the luminescence spectra of Eu(III) and
Tb(III) ions sensitized by these molecules and p-
dimethoxybenzophenone. We also studied the effect of
other lanthanide ions in solution on the luminescence
intensity and lifetime of Eu(III) and Tb(III) and deter-
mined the nature of bridge groups responsible for the
formation of binuclear complexes of lanthanide ions in
aqueous and ethanol solutions.
EXPERIMENTAL
Salts of Ln(III) were dissolved in the form of chem-
ically pure chloride crystal hydrates; 2,2'-biperydil,
1,10-phenanthrolone, and p-dimethoxybenzophenone
were also chemically pure. At the lanthanide concentra-
tions used (10–7–3 × 10–2 M), the salts were virtually
completely dissociated in aqueous solutions and only
partially dissociated in ethanol. We used doubly dis-
tilled usual and distilled water and d6-ethanol as sol-
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
quantum yield of luminescence of Tb(III) and Eu(III)
ions and, hence, to increase the sensitivity of the
method. Bipyridil solutions in D2O were alkalized by
adding NaOD with a subsequent introduction of Ln(III)
ions. The solution pH was controlled with a calibrated
pH meter (pH-673). The luminescence spectra of
Tb(III) and Eu(III) ions were measured with a Hitachi
650-40 fluorimeter with a minimum spectral slit width
of 2 nm. The absorption spectra of solutions of 2,2'-
bipirydil, 1,10-phenanthroline, Ln(III) ions, and com-
plexes of lanthanide ions with 2,2'-bipyridil deposited
on quartz were measured with a Cary-17 spectropho-
tometer with the 0.1–0.5 nm resolution.
The decay time τlum of the sensitized luminescence
of Tb(III) and Eu(III) ions was measured with a setup
consisting of a 337-nm pulsed LGI-21 nitrogen laser
(pulse length ∆t = 20 ns), a FEU-79 photomultiplier,
and a S8-13 oscilloscope. The luminescence decay of
Tb(III) and Eu(III) in all solutions, in particular, in the
presence of energy acceptors, was exponential. The rate
constants of energy transfer or the constants of lumi-
nescence decay of Tb(III) and Eu(III) caused by accep-
tor ions were measured from the Stern–Volmer formula
from the data on the shortening of τlum and on the lumi-
nescence quenching of these ions at their concentration
equal to 10–3 M upon direct excitation of Eu(III) ions
into their absorption band and upon sensitization of
Eu(III) and Tb(III) ions by organic molecules. The rate
constants measured by these methods were close to
each other, which allowed us to determine the rate con-
stants of energy transfer between ions at their lower
concentrations in solutions (10–6–10–4 M) only from the
data on quenching of the sensitized luminescence of
Eu(III) and Tb(III) ions neglecting the possibility of
competition between these ions in energy transfer from
sensitizing organic molecules.
The quantum yields of luminescence of Eu(III) ions
sensitized by bipyridil (the sensitization efficiency) in
water and ethanol were determined by comparing the
quantum yields of luminescence of Eu(III) upon its
direct excitation into the 7F0–5D3 band and upon its
excitation into the absorption band of a sensitizer.
STABILITY CONSTANTS OF COMPLEXES OF
EU(III) AND GD(III) IONS WITH 2,2'-BIPYRIDIL
IN AQUEOUS SOLUTIONS
We studied the effect of addition of Eu(III), Gd(III),
Al(III), and H(I) ions to aqueous solutions of 2,2'-bipy-
ridil and 1,10-phenanthroline on their absorption spec-
tra (Fig. 1). Variations in the spectra of these organic
molecules after addition of metal salts to the solution
can be caused by two reasons: the formation of com-
plexes between metal ions and molecules and the
appearance of protonated forms of these molecules due
to hydrolysis of the salts added, resulting in the acidifi-
cation of the solution. Note that the absorption spec-
trum of the singly protonated form and the spectrum of
OPTICS AND SPECTROSCOPY Vol. 89 No. 3 2000
361
bipyridil in complexes of Eu(III) ions deposited from
the ethanol solution to a quartz substrate are identical.
To reliably study the complexing of these ions and mol-
ecules, we controlled a change in the solution pH upon
the addition of salts, prepared the solutions of mole-
cules with the same pH, and measured the absorption
spectra of these solutions. Figure 1 shows that the
302-nm absorption band of 2,2'-bipyridil appearing in
the presence of lanthanide ions is mainly determined by
complexing with lanthanide ions rather than by a
change in the solution pH. This fact allowed us to deter-
mine the first stability constants of these ions in water
from the data on the dependence of the concentration of
free and bonded molecules of 2,2'-bipyridil on the con-
centration of metal ions in aqueous solution. The stabil-
ity constants found in this way were kst = 8 ± 1 for the
[Gd(III)-bpy] complex and kst = 6 ± 1 for the [Eu(III)-
bpy] complex. One can see from Fig. 1 that upon addi-
tion of aluminum ions into the 2,2'-bipyridil solution at
the concentration an order of magnitude lower than that
of lanthanide ions, the spectrum of 2,2'-bipyridil com-
pletely transforms to the spectrum of another form.
However, because the solution pH changes very
strongly due to strong hydrolysis of aluminum salts, the
variation of the spectrum is almost completely deter-
mined by this change in pH, as follows from Fig. 1.
Our analysis of variations in the absorption spectra
of aqueous solutions of organic molecules caused by
the addition of metal ions showed that the luminescent
method for measuring relative stability constants of
complexes of metal ions with organic molecular sensi-
tizers based on the quenching of luminescence of the
sensitized ion due to the competition between lumi-
nescing and non-luminescing metal ions is valid only
for the systems where the influence of hydrolysis of
metal ions on organic ligands can be neglected.
We studied luminescence of Eu(III) sensitized by
2,2'-bipyridil and 1,10-phenanthroline and the influ-
ence of Gd(III) ions and of variation in the solution pH
corresponding to the solution acidification upon addi-
tion of these salts (Fig. 2) on the Eu(III) luminescence
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-
nescence is quenched by Gd(III) ions (Fig. 2) and the
quenching is mainly caused by the Gd(III) ions them-
selves rather than by the solution acidification caused
be these ions.
Thus, at high concentrations of Eu(III) and Gd(III)
ions, the Gd(III) ion is a quencher of the Eu(III) lumi-
nescence sensitized by organic molecules.
Because the values of kst for complexes of Ln(III)
ions with bipyridil are low for the Eu(III) concentra-
tions used, only a part of molecules form complexes
with ions in the ground state, while the majority of
europium ions are sensitized in collision complexes
with excited bipyridil molecules. For this reason, the
slope of straight line of quenching does not reflect the
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
CONCENTRATIONS
We studied the influence of Gd(III) ions of the inten-
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
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
the sensitized luminescence of europium ions and in
the redistribution of the intensity ratio of the 5D0–7F1
and 5D0–7F2 transitions in the luminescence spectrum
of Eu(III). In these experiments, we excited organic
molecules into the long-wavelength wing of their
absorption band. The influence of Gd(III) depended on
the excitation wavelength and could be explained by a
trivial increase in the solution absorption caused by
complexing of organic molecules with Gd(III) (Fig. 1)
and additional energy transfer from the excited mole-
cules to Eu(III) ions.
We managed to observe luminescence of Eu(III)
sensitized by 2,2'-bipyridil and 1,10-phananthroline in
the D2O solution down to the Eu(III) concentration of
2.0 × 10–8 M (Fig. 3).
To neglect the influence of lanthanide ions on the
absorption spectra of 2,2'-bipyridil, we studied the
effect of Gd(III) of the sensitized luminescence of
Eu(III) in D2O solutions at concentrations of Eu(III),
Gd(III), and bipyridil equal to 10–6, 10–4, and 3.5 ×
10−3 M, respectively. The solutions were bubbled,
which enhanced the intensity of sensitized lumines-
cence of Eu(III) approximately by an order of magni-
tude (Table 1). Both bubbled and nonbubbled D2O
solutions exhibited the same enhancement of sensitized
luminescence of Eu(III) in the presence of Gd(III). The
magnitude of this effect was different for the two lumi-
nescence bands of Eu(III) (Table 1), the effect being
independent of the exciting wavelength in the region
from 310 to 325 nm. The variations in the absorption
spectrum of bipyridil caused by the addition of 10–4 M
Gd(III) were very small at the bipyridil concentrations
used.
2.4
2.0
1.6
1.2
0 0.02 0.04 0.06 0.08 0.10
[Gd(III)], M
Fig. 2. Quenching of luminescence of 2 × 10–2 M Eu(III) by
Gd(III) ions in H2O for the pH values corresponding to the
solution acidification produced by Gd(III) ions. (m) sensi-
tizer: 2,2'-bipyridil, quencher: Gd(III); (n) quenching of the
Eu(III) luminescence by varying pH; (d) sensitizer: 1,10-
phenanthroline, quencher: Gd(III); (s) quenching of the
Eu(III) luminescence by varying pH. Luminescence was
excited at the isosbestic point of the absorption spectrum at
290 nm (T = 293 K).
We obtained an unexpected result by studying the
effect of Gd(III) (10–4 M) on the sensitized lumines-
cence of Eu(III) in bubbled and nonbubbled solutions
of 3 × 10–3 M 2,2'-bipyridil + 10–5 Eu(III) in d6-ethanol.
The removal of O2 from this solvent did not enhance the
sensitized luminescence of Eu(III), but on the contrary
(Table 1) resulted in a strong luminescence quenching,
this quenching being an order of magnitude weaker in
the presence of Gd(III) ions in the solution. We found
that upon irradiation of ethanol solutions of Eu(III) that
did not contain any other ions, the sensitized lumines-
cence of Eu(III) decreased (while τlum did not change).
This suggests that the photochemical reaction between
excited bipyridil molecules and Eu(III) ions proceeded.
The addition of the Gd(III) and La(III) ions to the solu-
tion retarded the reaction. We assume that removal of
O2 from the solution favors the dark reaction of reduc-
tion of Eu(III) ions, which is retarded by the Gd(III)
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-
ous solutions changes the relative intensities of lumi-
nescence bands of Eu(III) ions. We also found that, as
in the studies of diketone complexes of Eu(III) [1–4],
the Gd(III) ions affect the sensitized luminescence of
europium ions. This influence is observed in the solu-
tions where the concentration of sensitizing ligands is
more than an order of magnitude higher than the con-
centration of the added lanthanide ions, so that the
addition of Gd(III) in the solution cannot affect com-
plexing of Eu(III) ions and sensitizers. At the same
time, the explanation of the influence of Gd(III) on the
intensity of sensitized luminescence of Eu(III) by the
additional sensitization due to energy transfer from
complexes of Gd(III) to the Eu(III) complexes sug-
gested in papers [1, 3] is not satisfactory. Because the
concentration of bipyridil in our experiments was
invariable, the phosphorescence spectra of free bipyri-
dil and bipyridil bonded with ions coincided in ethanol
and water–glycerol solutions at 77 K (Fig. 4) and,
hence, the additional sensitization channel of Eu(III)
did not appear in the presence of Gd(III). The presence
of bpy–Eu(III) complexes in these frozen solutions is
confirmed by the observation of sensitized lumines-
cence of Eu(III).
The quantum yield of luminescence of many che-
lates of Eu(III) is lower than unity because of the exist-
ence of a reversible photochemical reaction [6, 7].
Therefore, we can assume that along with energy trans-
fer from the excited sensitizer to the Eu(III) ion in solu-
tions, a reversible photochemical reaction takes place,
which reduces the efficiency of Eu(III) sensitization,
while the formation of the ion pair with Gd(III)
decreases the rate of this reaction. However, the study
of the quantum yield of luminescence of Eu(III) sensi-
tized by pyridil as a function of the Eu(III) concentra-
tion showed that, in ethanol and water under the condi-
tions close to complete energy transfer, the quantum
yield is close to unity. Therefore, upon formation of the
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
predominant channel of their interaction is the energy
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
Tb(III) remain open.
To answer to this question, we will analyze the data
on the sensitized luminescence spectra of Eu(III) and
will study energy transfer from Eu(III) and Tb(III) ions
to other lanthanide ions in aqueous and ethanol solu-
tions. One can see from Fig. 3 that as the concentration
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
magnetic dipole 5D0–7F1 transition, which does not
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-
tion by phenanthroline. This fact shows that the number
of Eu(III) complexes increases as the concentration of
these ions decreases. A decrease in the concentration of
bipyridil by 35 times does not affect the intensity ratio
for these two bands in the studied range of concentra-
tions of Eu(III) in D2O. The independence of the sym-
metry of the Eu(III) environment on the bipyridil con-
centration suggests that the change in the relative inten-
sities of the luminescence bands with decreasing
concentration of bipyridil cannot be explained by an
increase in the number of complexes of Eu(III) with
bipyridil. This conclusion is confirmed by the observa-
tion of the same variations in the luminescence spec-
trum of europium chloride in D2O upon its direct exci-
tation into the 7F0–5D3 band in the range of concentra-
tions of Eu(III) from 10–4 to 10–3 M. Lanthanide salts
were added to solutions in the form of chlorides. How-
ever, the increase in complexing of Eu(III) ions as their
concentration and that of Cl– anions introduced with
Eu(III) decreased indicates unambiguously that Cl–
cannot serve as a bridge that provides the interaction
between lanthanide ions in aqueous solutions in the
range of ion concentrations under study.
Therefore, we can assume that the spectrum of
Eu(III) reflects complexing of europium ions with OH–
or OD– groups of water, which increases when concen-
trations of Eu(III) ions and hydroxyl groups in water
become closer to each other, while the addition of
OPTICS AND SPECTROSCOPY Vol. 89 No. 3 2000
365
Ilum, rel. units
350 400 450 500 550
λ, nm
Fig. 4. Effect of lanthanide ions on phosphorescence spectra
of 2,2'-bipyridil (10–4 M) in ethanol at 77 K (λex = 310 nm):
(d) 0 M of Ln(III); (m) 10–2 M of Gd(III); (✶) 10–2 M of
Eu(III); (r) 10–2 M of La(III).
Gd(III) affects the degree of complexing of Eu(III) ions
in water.
ENERGY TRANSFER IN HYDROXYL BRIDGE
COMPLEXES OF LN(III) IONS AND EFFECT
OF GD(III) ON THIS PROCESS
We studied the influence of lanthanide ions on the
lifetime and intensity of sensitized luminescence of
Eu(III) and Tb(III) at the concentration of the interac-
tion ions equal to 10–3 M. We also studied the effect of
acceptor ions on the intensity of intrinsic luminescence
of Eu(III) upon direct excitation in the concentration
range between 10–4 and 10–3 M, as well as the influence
of lanthanide ions on the intensity of sensitized lumi-
nescence of Eu(III) and Tb(III) in the concentration
range between 10–6 and 10–3 M. We found that the pres-
ence of Gd(III) ions (10–3 M) in aqueous solutions
(pH = 6) of Eu(III) ions (10–3 M) does not affect the
intensity and lifetime of the Eu(III) luminescence. At
the same time, in the presence of lanthanide ions at the
same concentration, whose absorption spectra are over-
lapped with the luminescence spectra of Eu(III) or
Tb(III), the luminescence intensity of the latter ions
decreases and its lifetime shortens, the luminescence
decay being exponential.
Comparison of the quenching of sensitized lumines-
cence with the luminescence lifetime of sensitized ions
shows that for the concentration of quenching ions
equal to 10–3 M the competition between sensitizing
ions and ion acceptors in the energy transfer from 2,2'-
bipyridil to these ions only slightly contributes to the
quenching of sensitized luminescence of Tb(III) and
366 SVESHNIKOVA et al.

Table 2. Quenching of luminescence of Eu(III) and Tb(III)
sensitized by 2,2'-bipyridil and p-dimethoxybenzophenone
and shortening of τlum of these ions in the presense of Ln(III)
ions for Cion = 10–3 M, Cbpy = 10–3 M in D2O (pD = 6) at 293 K
0 0
Compounds τ lum /τlum I lum /Ilum
Eu(III) + Nd(III), p-CH3O 1.3 ± 0.05 1.7 ± 0.1
benzoph.
Eu(III) + Nd(III), bpy 1.3 ± 0.05 1.8 ± 0.1, 1.3 ± 0.1*
Eu(III) + Er(III), bpy 1.3 ± 0.05 1.3 ± 0.1*
Eu(III) + Pr(III), bpy 1.3 ± 0.05 1.6 ± 0.1
Eu(III) + Gd(III), bpy 1.0 ± 0.05 1.0 ± 0.05
Eu(III) + Ho(III), bpy 1.6 ± 0.1
Tb(III) + Nd(III), bpy 1.2 ± 0.05 1.2 ± 0.1
Tb(III) + Sm(III), bpy 1.3 ± 0.05 1.3 ± 0.1
*Quenching of luminescence of Eu(III) ions by Ln(III) ions upon
direct excitation into the 395-nm absorption band of Eu(III).
Eu(III) ions by Pr(III), Nd(III), Sm(III), Ho(III), and
Er(III) ions (Table 2).
This fact allowed us to study energy transfer
between these ions at low concentrations in solutions
from the quenching of their sensitized luminescence in
the presence of ion acceptors. We performed this study
at concentrations of donors and acceptors from 10–6 to
10–3 M. We observed the quenching of luminescence of
Tb(III) and Eu(III) ions by lanthanide ion acceptors.
The quenching of luminescence of Eu(III) and Tb(III)
by Nd(III) ions at the ion concentration in D2O equal to
10–6–10–5 M strongly supports the bridge mechanism of
energy transfer between ions. We found that the
replacement of bidentate sensitizers, 2,2'-bipyridil and
1,10-phenanthroline, by monodentate p-dimethoxy-
benzophenone reduced the efficiency of Eu(III) sensiti-
zation, but did not change the efficiency of quenching
of Eu(III) luminescence by Nd(III) ions. This result
confirms our assumption that the ions in water are
bonded by hydroxyl groups rather than by bipyridil or
phenanthroline. We will discuss in detail the depen-
dence of energy transfer between lanthanide ions on the
concentration of hydroxyl groups in our next paper.
Using the data on quenching of luminescence of Eu(III)
and Tb(III) ions by Nd(III) ions, we calculated the rate
constants kt of energy transfer by the Stern–Volmer for-
mula at different ion concentrations. The results are
presented in Table 3.
One can see from Table 3 that, upon sensitization by
phenanthroline or bipyridil, kt increases more than two
orders of magnitude for both pairs of ions as the total
concentration of ion donors and acceptors decreases
from 10–3 to 10–6 M. This result can be explained by the
influence of hydroxyl bridges on energy transfer
because the concentration of hydroxyl groups in solu-
tion is lower than that of the ions under study, the
hydrolysis constants of lanthanide ions are of the order
of 10–9 [8], the stability constants of complexes of
Ln(III) ions with OH– are of the order of 105 [9], and the
relative concentration of lanthanide ions in complexes
with hydroxyl groups increases with decreasing con-
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
should increase linearly with the concentration of
bridge groups in solution [10]. Here, we observed an
approximately linear increase in kt with decreasing con-
centration of lanthanide ions in solution; and we can
assume that kt changes in accordance with variation in
the ratio of concentrations of lanthanide ions and
hydroxyls in solution.
Because water–ethanol solutions are also used in
fluorescent immunoassay [1], we studied the influence
of the Pr(III), Gd(III), and La(III) ions on luminescence
of Eu(III) in d6-ethanol sensitized by 2,2'-bipyridil. As
in aqueous solutions, we observed quenching of the
sensitized luminescence of Eu(III) by Ln(III) ions,
which were not involved in energy transfer, in ethanol
at high concentrations of lanthanide ions and low con-
centrations of bipyridil. This study showed the ability
of the added lanthanide ions to compete with Eu(III)
ions in complexing and allowed us to measure the rela-
tive stability constants of these ions.
The study in the region of high concentrations of
bipyridil (10−3 M) and low concentrations of foreign
ions (10–4–10–5 M) added to the 10–5 M Eu(III) solution
is also of interest. In this case, luminescence of Eu(III)
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
that were able to accept the electronic excitation energy
of Eu(III). The addition of Gd(III) and La(III) salts into
solution did not affect the lifetime of Eu(III) lumines-
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
3 × 107 and 6 × 106 for concentrations of Pr(III) in solu-
tion equal to 10–6 and 10–5, respectively; i.e., they are of
the same order of magnitude as the rate constants of
energy transfer between lanthanide ions in water.
Earlier, we observed the inhibition of quenching of
sensitized luminescence of Eu(III) induced by Gd(III)
ions in bubbled ethanol solutions. This was possibly
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
increase in the intensity of sensitized luminescence of
the 10–4 M bpy + 10–3 M Eu(III) solution by one and a
half times after it has been kept in the dark for 30 min.
After illumination of the solution, this additional lumi-
nescence of Eu(III) rapidly disappeared. This result
reflects the existence of two processes: the gradual
increase in the fraction of complexes of lanthanide ions
and bipyridil in the ethanol solution and efficient pho-
tochemical quenching of sensitization of Eu(III) in
these complexes.
Our study showed that as the concentration of
Eu(III) and Tb(III) ions in solutions decreased, their
luminescence was more efficiently quenched by for-
eign ions that were present in solution at low concentra-
tions; i.e., upon formation of bridge hydroxyl com-
plexes, any impurity ions in solution, which can play
the role of acceptors in energy transfer from lanthanide
ions, can quench luminescence of lanthanide markers.
If such deactivation channel of lanthanide markers
exists or lanthanide ions are deactivated in hydroxyl
complexes, we can assume the existence of another
mechanism of the influence of Gd(III) on sensitized
luminescence of lanthanide ions, which consists in
drawing off hydroxyl groups from Eu(III) and Tb(III)
ions, resulting in a weaker quenching of luminescence
of the se ions in hydroxyl complexes. To verify the
existence of this mechanism, we studied the depen-
dences of the luminescence intensity and lifetime for
Eu(III) (10–3 M) and Tb(III) (10–3 M) on the OD– con-
centration in D2O and the influence of Gd(III) (10−3 and
OPTICS AND SPECTROSCOPY Vol. 89 No. 3 2000
367
(a) (b) (c)
Ilum, rel. units
1
0
580 620 580 620 580 620
λ, nm
Fig. 5. Effect of the OD– anions and addition of Gd(III) to
the alkalized D2O solution on the luminescence spectrum of
Eu(III) at 293 K: (a) 10–3 M of EuCl3 in D2O; (b) 10–3 M of
EuCl3 in D2O + 10–3 M of NaOD; (c) 10–3 M of EuCl3 in
D2O + 10−3 M of NaOD + 10–2 M of GdCl3.
10–2 M) on these quantities. The solution was alkalized
by adding 10–4–2 × 10–3 M of NaOD. We found that at
the OD– concentration equal to 2 × 10–3 M, i.e., at the
concentration of hydroxyl groups comparable to that of
Tb(III) and Eu(III) ions, luminescence of these ions
was quenched and the its lifetime decreased in the pres-
ence of hydroxyl groups. The addition of 10–3 M of
Gd(III) resulted in a weak increase in the luminescence
intensity, while after the addition of 10–2 M of Gd(III)
the initial luminescence intensity and lifetime were
almost completely restored (Fig. 5). The alkalization of
the solution resulted in the change in the luminescence
spectrum of Eu(III): The 5D0–7F0 band appeared in the
spectrum and relative intensities of the 5D0–7F1 and
5D –7F bands were changed. After the addition of
0 2
Gd(III), the symmetry of the Eu(III) environment
increased and the luminescence spectrum of Eu(III)
returned to the spectrum of a solvated ion (Fig. 5). The
influence of Gd(III) on the luminescence spectrum of
Eu(III) (10–6 M) sensitized by bipyridil in neutral solu-
tions was the same (Table 1).
Therefore, such a channel of the influence of Gd(III)
on luminescence of lanthanide markers exists, and
luminescence of Ln(III) ions at low concentrations can
be quenched by hydroxyl groups and enhanced by
Gd(III) in neutral solutions.
368 SVESHNIKOVA et al.
CONCLUSIONS
We can make the following conclusions from our
study:
(1) Complexing of lanthanide ions at low concentra-
tions with organic molecules in aqueous solutions is
accompanied by the formation of complexes of these
ions with hydroxyl groups of water. The number of
hydroxyl complexes of lanthanide ions increases as the
ion concentration approaches that of hydroxyl groups
in aqueous solution.
(2) In aqueous solutions, along with the interaction
between organic molecular sensitizers and lanthanide
ions, binuclear complexes of lanthanide ions are
formed via the OH bridges, the distance between lan-
thanide ions in such complexes being larger than
0.5 nm. This fact explains the results obtained in [4],
where it was found that the experimental rates of the
intracomplex energy transfer between lanthanide ions
in diketone complexes of these ions with 1,10-phenan-
throline could agree with the inductive-resonance cal-
culations if only one assumed that the distance between
the ions was less than 0.7 nm. This contradicted the
assumption about the diketone bridge. The formation of
binuclear complexes via the OH– group is confirmed by
the fact that binuclear complexes of these diketones are
absent in nonpolar solvents [5].
(3) In ethanol nondried solutions of 2,2'-bipyridil,
binuclear complexes of lanthanide ions also exist and
the irreversible photochemical reaction of reduction of
Eu(III) ions takes place. The formation of binuclear
complexes with Gd(III) or La(III) inhibits this reaction.
(4) The enhancement of luminescence of Eu(III)
and Tb(III) in the presence of Gd(III) in the D2O solu-
tion is explained by the removing of hydroxyl groups
from Eu(III) and Tb(III) ions, which quench lumines-
cence of these ions.
ACKNOWLEDGMENTS
This work was supported by the Russian Foundation
for Basic Research (project nos. 97-03-32398 and 00-
03-32208) and the Ministry of Science and Technology
of the Russian Federation. The authors thank T. A. Sha-
khverdov for useful discussion of the results and for
providing the possibility for bubbling solutions.
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Translated by M. Sapozhnikov
OPTICS AND SPECTROSCOPY Vol. 89 No. 3 2000