ISSN 0030400X, Optics and Spectroscopy, 2010, Vol. 109, No. 6, pp. 917920. Pleiades Publishing, Ltd., 2010.

Original Russian Text N.V. Petrochenkova, I.A. Tkachenko, A.G. Mirochnik, V.E. Karasev, V.Ya. Kavun, 2010, published in Optika i Spektroskopiya, 2010, Vol. 109, No. 6,
pp. 11581161.

CONDENSEDMATTER
SPECTROSCOPY

Luminescence and Magnetic Properties of Europium(III)

Carboxylatodibenzoylmethanates
N. V. Petrochenkovaa, I. A. Tkachenkob, A. G. Mirochnikb, *,
V. E. Karasevb, and V. Ya. Kavunb
a

Nevelskoy Maritime State University, ul. Verkhneportovaya 50a, Vladivostok, 690059 Russia
b
Institute of Chemistry, FarEastern Branch of the Russian Academy of Sciences,
pr. Stoletiya Vladivostoka 159, Vladivostok, 690022 Russia
* email: mirochnik@ich.dvo.ru
Received April 22, 2010

AbstractThis paper reports on the results of an investigation of the luminescence and magnetic properties
of europium(III) carboxylates, which are determined by the structure of the Stark and Zeeman sublevels. It
has been established that the energy splittings lum between the 7F0 ground level and the 7F1 term in the lumi
nescence spectra of these compounds well correlate with the energy splittings magn obtained from magne
tochemical measurements.
DOI: 10.1134/S0030400X10120167

INTRODUCTION
The luminescence and magnetic properties of
europium compounds are determined by the structure
of the Stark and Zeeman sublevels [13]. The
europium compounds based on carboxylic acids can
be separated into two groups: (i) europium com
pounds with a conventional Stark structure of the
luminescence spectra and (ii) europium compounds
with an anomalous Stark structure of the lumines
cence spectra, which is characterized by an unusually
high relative intensity of the line of the 5D07F0 singlet
transition and in which the energy splitting between
the 7F0 ground level and the nearest level of the 7F1
multiplet is unusually small (~175 cm1) [46].
The anomalous Stark structure of the lumines
cence spectra of europium carboxylatodibenzoyl
methanates and the temperature behavior of their
luminescence [46] have stimulated an active search
for correlations between the luminescence and mag
netic characteristics of the above compounds. In this
paper, we report on a comparative study of the lumi
nescence
and
magnetic
characteristics
of
europium(III) compounds with conventional and
anomalous Stark structures of the luminescence spec
tra.
SAMPLE PREPARATION
AND EXPERIMENTAL TECHNIQUE
Europium(III) acrylate Eu(Acr)3 3H2O and
europium(III) methacrylate Eu(Macr)3 were synthe
sized by dissolving asprepared europium(III) hydrox
ide in the corresponding acids according to the proce

dure described in [7] with the subsequent evaporation

of the resulting solutions on a water bath.
Europium(III) (carboxylato)bis(dibenzoylmetha
nates) Eu(Dbm)2Acid, where Dbm is dibenzoyl
methane, methacrylic acid (Macr), propionic acid
(Prop), acetic acid (Ac), and EuDbm(Acr)2 were syn
thesized according to the procedure described in [6] by
the reaction of equimolecular amounts of Eu(NO3)3
6H2O, dibenzoylmethane (HDbm), and the corre
sponding acid in ethanol with the subsequent neutral
ization of the reaction mixture by adding a solution of
ammonia.
The luminescence spectra of samples in the form of
powders were recorded on an SDL1 spectrometer.
The excitation source was a DRSh250 mercury lamp
(exc = 365 nm, UFS6 filter). The measurements
were performed at temperatures of 77 and 300 K.
The molar magnetic susceptibility of the com
pounds under investigation was measured on a
SQUID MPMS 7 magnetometer in the temperature
range of 2300 K.
RESULTS AND DISCUSSION
The compounds of Eu3+ (4f 6) and Sm3+ (4f 5) ions,
unlike the other lanthanide ions, are characterized by
a small value of the energy splitting between the lower
and first excited multiplets [1, 8]. The Eu3+ ion has the
7F level, which is closely located to the 7F ground
1
0
(nonmagnetic) level and populated in part already at
room temperature.
The compounds under investigation can be sepa
rated into two groups. The first group includes

917

918

PETROCHENKOVA et al.

Spectralluminescent and magnetochemical characteristics of europium(III) compounds

Transition, , cm1

Compound
I
II
III
IV
V
VI

D07F0

Eu(Acr)3 3H2O
Eu(Macr)3
EuDbm(Acr)2
*Eu(Dbm)2Ac
*Eu(Dbm)2Prop
*Eu(Dbm)2Macr

17382
17379
17251
17333
17323
17371

F1

D07F1

17024
17053
16962
17161
17147
17165

16998
16995
16869
16926
16910
16932

europium(III) compounds with a conventional Stark

structure of the luminescence spectra (compounds I
III) (table, Fig. 1). The second group contains
europium(III) compounds with an anomalous Stark
structure of the luminescence spectra (compounds
IVVI) (table, Fig. 2). The luminescence spectra of
compounds IIII do not substantially differ in the
character of the energy splitting and the intensity of
the ff transitions from the luminescence spectra of
wellknown mononuclear compounds. For these
compounds, the maximum intensity is observed in the
5D 7F electric dipole transition (Fig. 1).
0
2

16943
16762
16769
16641
16641
16642

lum , cm1 magn, cm1

81
291
193
520
506
523

358
326
289
172
176
206

361
326
234
175
223
206

nents) of the 7F1 multiplet is anomalously small

(~175 cm1) (Fig. 2) compared to the corresponding
energy splitting for the majority of the wellknown
europium compounds (~350 cm1) [9].
Figures 3 and 4 show the temperature dependences
of the molar magnetic susceptibility m of the
europium compounds under investigation. In contrast
to the other lanthanides, for which the temperature
dependence of the molar magnetic susceptibility m
obeys the CutieWeiss law, the temperature depen
dence of m for the europium complexes is determined
by the thermal population of the 7F1 level nearest to the
ground level. By using the wellknown CaroPorcher
formula [8]

The luminescence spectra of compounds IVVI

are characterized by an unusually high relative inten
sity of the line of the 5D07F0 singlet transition, and
the energy splitting between the 7F0 ground level and
the nearest component (among the three compo

( m) LT = 8 N 2/ = 2 .0 86/ ,

Ilum, arb. units

5D
0

7F

5D
0

2
5D
0

7F

7F
1

2
1

1
0

570

600
, nm

630

Fig. 1. Luminescence spectra of europium(III) acrylate at temperatures of (1) 77 and (2) 300 K.
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LUMINESCENCE AND MAGNETIC PROPERTIES

Ilum, arb. units
3

D0

919

7F
2

2
5

D0

7F
0
5D
0

7F
1

1
2

570

600
, nm

630

Fig. 2. Luminescence spectra of the [Eu(Dbm)23] 22 complex at temperatures of (1) 77 and (2) 300 K.

m 103, mol/m3

12

1
2

3
0

100

200

300

T, K
Fig. 3. Temperature dependences of the molar magnetic susceptibility m of complexes (1) VI, (2) V, and (3) III.

where (m)LT is the limiting lowtemperature value of

m, we obtain the energy splitting between the 7F0 and
7F levels. It should be noted that the observed increase
1
in the molar magnetic susceptibility m for the
europium complexes (Figs. 3, 4) in the vicinity of liq
uidhelium temperature is associated with the pres
ence of impurities of other rareearth paramagnetic
ions in the compound [8].
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CONCLUSIONS
Thus, it has been established that the energy split
tings lum in the luminescence spectra of all the com
pounds studied in this work and the energy splittings
magn obtained from magnetochemical measurements
are well correlated with each other (table). However, in
contrast to the works by Legendziewicz et al. [2, 3],
who compared the values of magn with the energy

920

PETROCHENKOVA et al.
m 103, mol/m3
10

1
2

6
3

100

200

300

T, K
Fig. 4. Temperature dependences of the molar magnetic susceptibility m of complexes (1) IV, (2) II, and (3) I.

splittings lum between the ground level and the center

of gravity of the 7F1 multiplet, we obtained a better
correlation between the values of magn and lum in the
case where lum was taken as the splitting between the
7F ground level and the nearest level of the 7F multip
0
1
let. It should be noted that the energy splittings lum
and magn for compounds IVVI are 1.52.0 times
smaller than those for compounds IIII (table). This
circumstance is most likely responsible for the
observed increase in the molar magnetic susceptibility
m for compounds IVVI as compared to compounds
IIII (Figs. 3, 4) and indicates that the dominant con
tribution to thermal population of the energy level is
introduced by the nearest component of the 7F1 term.
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25 (8), 1037 (2001).

3. J. Legendziewicz and M. Borzechowska, J. Alloys

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Translated by O. BorovikRomanova

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2010