Journal of Luminescence 104 (2003) 93–101

Enhanced emission from Eu(III) b-diketone complex

combined with ether-type oxygen atoms of
di-ureasil organic–inorganic hybrids
C. Molinaa, K. Dahmouchea, Y. Messaddeqa, S.J.L. Ribeiroa,*, M.A.P. Silvab,
V. de Zea Bermudezc, L.D. Carlosd
a
Institute of Chemistry, UNESP, P.O. Box 355, Zip 14801-970, Araraquara-SP, Brazil
b
Laboratoire POMA, UMR CNRS 6136, Universite d’Angers, 49045 Angers, France
c
!
Departamento de Qu!ımica, Universidade de Tras-os-Montes e Alto Douro, 5001-911 Vila Real Codex, Portugal
d
Departamento de F!ısica, Universidade de Aveiro, 3810 Aveiro, Portugal

Received 17 June 2002; received in revised form 2 December 2002; accepted 2 December 2002

Abstract

Organic–inorganic hybrids, named di-ureasils and described by polyether-based chains grafted to both ends to a
siliceous backbone through urea cross linkages, were used as hosts for incorporation of the well-known coordination
complex of trivalent europium (Eu3+) ions described by the formula [Eu(TTA)3(H2O)2] (where TTA stands for
thenoyltrifluoroacetone). By comparing with Eu3+-doped di-ureasil without complex form the new materials prepared
here enhanced the quantum efficiency for photoemission of Eu3+ ions. The enhancement can be explained by the
coordination ability of the organic counterpart of the host structure which is strong enough to displace water molecules
in [Eu(TTA)3(H2O)2] from the rare earth neighbourhood after the incorporation process. High intensity of Eu3+
emission was observed with a low non-radiative decay rate under ultraviolet excitation. The quantum efficiency
calculated from the decay of 5D0 emission was 74%, which in the same range of values previously obtained for the most
efficient Eu3+ coordination compounds reported in literature. Luminescence, X-ray absorption and infrared absorption
results considered together leads to a picture where the first coordination shell of Eu3+ is composed of the 6 oxygen
atoms of the 3 b-diketonate ligands and 2 ether-like oxygen atoms of the host.
r 2003 Elsevier Science B.V. All rights reserved.

PACS: 81.07.Pr; 32.70.Cs; 78.55.
m; 71.55.Jv

Keywords: Organic–inorganic hybrids; Europium (III)

1. Introduction different fields, ranging from phosphors to photo/

electroluminescent devices and fluoroimunoessay
In the search for new lanthanide light emissive reagents, new organic ligands have been proposed
compounds with potential application in several in the last decades. In terms of photoexcitation,
one looks for high ultraviolet (UV) absorption
*Corresponding author. Fax: +52-16-2227932. coefficients, high-energy transfer rate from ligand
E-mail address: sidney@iq.unesp.br (S.J.L. Ribeiro). to lanthanide ion and consequently high quantum
0022-2313/03/$ - see front matter r 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0022-2313(02)00684-1
94 C. Molina et al. / Journal of Luminescence 104 (2003) 93–101
efficiency for visible light emission of lanthanide
ions. In addition, such an ideal material should not
only be water soluble but also display adequate
mechanical properties, allowing its preparation
either as bulk monoliths or thin films that could be
easily deposited on different substrates by casting
from solutions.
Among various organic molecules considered
in this framework, it is undoubtedly that the
b-diketones are extremely promising. Since the
early 1960s the lanthanides b-diketonate chelates
have been known to be very stable, easily
synthesised and highly light emissive under UV
excitation. The UV excitation is followed by
efficient intramolecular energy transfer from
ligand excited states to the lanthanide emissive
levels, yielding characteristic and intensely lumi-
nescent narrow band f–f electronic transitions
[1,2]. In fact some of lanthanide b-diketone
complexes exhibit laser action in solution [3], and
have been also considered to be serious candidates
as luminescent dopants for the fabrication of
hybrid phosphors and other optical devices.
The main drawback that derives from the use of
the lanthanide b-diketonates lies in the difficulty in
obtaining them in the anhydrous form. In general,
the b-diketones chelates are obtained as hydrates,
in which two or three water molecules are attached
to a central lanthanide ion. Concerning trivalent
europium (Eu) ions emitting a orange–red light
the general formula of the complexes may be
written as [EuL3(H2O)n ], where L holds for the
b-diketonate ligands and n ¼ 2; 3: The water
molecules in the first coordination shell of the
lanthanide ion bring deleterious effects to the light
emission properties. Quenching of the 5D0 excited
state of Eu3+ ions through non-radiative decay
paths provided by OH oscillators of coordinated
water molecules is a phenomenon known for many
years. One of the possible strategies to improve the
light emission properties of lanthanide b-diketo-
nate chelates has involved the substitution of the
water molecules in the coordination shell with
other chemical species. Heterocyclic ligands like
2,20 -bipyridine and 1,10-phenanthroline, substi-
tuted sulphoxides and phosphine oxides, aromatic
carboxylic acids among many others, have been
extensively employed [2]. Crystalline mixed com-
pounds, in the powder form and displaying
unusually high emission quantum efficiencies
(70–80%), have resulted from this concept [2,4].
These compounds may be used as powdered
phosphors or dispersed in semiconducting con-
jugated polymers. In the last case light emitting
diodes with narrow emission line bandwidth have
been proposed [5].
In parallel to these works, a considerable
amount of research has been devoted to the
materials synthesis through the combination of
the sol–gel route with the principles of the host–
guest chemistry. These efforts have led to the
production of a significant number of innovative
organic–inorganic frameworks with tunable design
and suitable features. The major interest of this
approach is the possibility of preparing multi-
functional nanoscale organic–inorganic systems
whose fields of application range from electro-
chemistry, biology, mechanics, ceramics, electro-
nics to photonics [6].
Among the sol–gel derived structures proposed
so far, a family of outstanding lanthanide-based
hybrid compounds have been reported [7]. The
host matrix, termed as di-ureasil, comprises poly-
ether-based chains of variable length grafted to
both ends to a siliceous backbone through urea
cross linkages. These xerogels, which are easily
produced as thin, elastomeric and highly trans-
parent monoliths, may withstand a large amount
of guest dopants. When doped with trivalent
lanthanide ions like Nd3+, Eu3+ and Tb3+ the
di-ureasils display remarkable emission properties.
Besides a broad long-lived emission covering the
whole visible range of the electromagnetic spec-
trum, the di-ureasils exhibit the typical intra-4f
narrow line emission in the green (Tb3+) [8], red
(Eu3+) and even in the near infrared (Nd3+) [9–
12], thus opening new prospects for their applica-
tions. In addition, the colour emitted by the Eu3+-
doped di-ureasils may be readily tuned across the
!
Commission Internationale d’ Eclairage (CIE)
chromaticity diagram by varying either the salt
concentration or the excitation wavelength [13]. In
spite of the above-mentioned properties, high
multiphonon decay rates are observed for Eu3+
excited states. Typical calculated quantum effi-
ciencies of around 8% are obtained for emission
 C. Molina et al. / Journal of Luminescence 104 (2003) 93–101
from the 5D0 excited state within the entire range
of compositions studied up to now. Hydrated
precursor salts like perchlorate and triflate have
been used and at least 3 water molecules are
suggested to occupy the Eu3+ first coordination
shell [9,10].
In this work we bring together the most
attractive characteristics of the three concepts,
(1) the organic–inorganic hybrid, (2) the host–
guest approaches and (3) the possible optimisation
of the light output provided by the utilisation of
lanthanide b-diketonate compounds, by means
of the incorporation of highly emissive Eu3+
b-diketonates into a di-ureasil with a short
polyether chain. On the basis of previous studies
[9–13], we have concluded that this host frame-
work protects the Eu3+ ions from the effect of
water molecules due to coordination ability of
di-ureasil to the lanthanide ion. The absence of
water molecules in the lanthanide coordination
shell can be expected and therefore reduced non-
radiative decay rates of Eu3+ excited states.
2. Experimental
The synthesis of the di-ureasil hybrid structure,
designated as U(600) (where 600 stands for the
average molecular weight of the starting organic
precursor) has been described in detail elsewhere
[10]. All chemical reagents were commercially
available and were purchased from Fluka
and Aldrich. 3-(isocyanatopropyl)triethoxysilane
H H
R2
H H
O O
HC
O O
Eu
H 2C
O O
HC O O
R1
CH
R2 CH 2
95
and O,O-bis(2-aminopropyl)poly(propyleneglycol)-
poly(ethyleneglycol)-poly(propyleneglycol) com-
mercially Jeffamine-ED600s, average molecular
weight 600 mol/g) were mixed in the molar ratio
1:2 and stirred in tetrahydrofuran (THF) under
reflux for 24 h. THF was evaporated and a urea
cross-linked organic–inorganic precursor (EtO)3
Si(CH2)3-NH(C=O)NH-[poly(propyleneglycol)]a
[poly(ethyleneglycol)]b(poly(propyleneglycol)]c-NH
(C=O)NH-(CH2)3Si(OEt)3 (with a þ c ¼ 2:5 and
b ¼ 8:5) was thus obtained.
The Eu3+ b-diketonate complex [Eu(TTA)3
(H2O)2] (where TTA stands for thenoyltrifluoroa-
cetone) was one of the Eu3+ b-diketonate salts
firstly synthesised and already proposed as active
specie in polymeric laser hosts [14]. In this work it
was prepared according to the method proposed
in Ref. [15] (these salts are tentatively represented
in Scheme 1). The hydrated complexes were then
incorporated in the di-ureasil. [Eu(TTA)3(H2O)2]
was first dissolved in the organic–inorganic pre-
cursor. Ammonium fluoride, NH4F, dissolved in
ethanol, was used as a nucleophilic catalyst for the
hydrolysis reaction ([NH4F]/[Si]=0.02) and water
(molar ratio [H2O]/[Si]=6) was added under
stirring, allowing the formation of a wet gel.
Finally, ethanol and water were slowly removed at
501C to give a transparent monolith of a rubbery
material. The complex concentration in the hy-
brids prepared ranges from 0.5 to 25 mol% of
Eu3+ [(Eu3+/Eu3++Si)  100]. As usual in poly-
mer science, these concentrations could be also
expressed by n=[O]/[Eu], where n is the number of
R1
CH
CH2
CH R1 = R 2 = CF3
S
R2
CH
R1
Scheme 1.
96 C. Molina et al. / Journal of Luminescence 104 (2003) 93–101

ether-type oxygen atoms in the polymer chains per EXAFS data analysis was performed on a
Eu3+ cation. In that case 0.5, 5 and 25 mol% Macintosh microcomputer [16].
corresponds to n ¼ 800; 170 and 17, respectively.
Excitation and emission spectra were obtained
under both continuous (450 W) and pulsed Xe 3. Results and discussion
lamps excitation with a SPEX Fluorolog F2121
spectrofluorimeter. In all measurements the front A high intensity of the orange–red emission due
face acquisition mode was employed at room to Eu3+ ions is observed when the [Eu(TTA)3
temperature. Decay curves were processed with the (H2O)2] and the organic–inorganic hybrid pre-
SPEX 1934 phosphorimeter. pared are illuminated with UV light. Fig. 1(a)
Infrared (IR) absorption spectra were acquired shows excitation spectra obtained for the b-
using a Fourier transform (FT)-IR Perkin Elmer diketonate complex and the doped hybrid by
Spectrometer Spectrum 2000 system. The spectra monitoring the visible emission at 615 nm. Within
were collected over the range 4000–400 cm
1 by the compositions range studied here no variation
averaging 32 scans at a maximum resolution of could be observed in the spectra. A broad strong
4 cm
1. Solid samples (2 mg) were finely ground UV absorption band is observed in the ex-
and dispersed in approximately 175 mg of dried citation spectrum of the hydrated compound
spectroscopic grade potassium bromide (KBr,
Merck). The mixed powder was pressed to form
a disc. Prior to recording the spectra under (a)
ambient conditions the discs were introduced in a
dessicator over phosphorous pentoxide for at least
12 h at room temperature in order to reduce the
levels of adsorbed water. A linear baseline was
assumed in all cases in the frequency ranges where
no significant absorption was detected. In order to
evaluate absorption bands envelopes and to
identify underlying components, iterative least-
Intensity (arb.units)

squares curve-fitting procedure in the Peakfit [24]1

software was used. The best fit of the experimental
240 320 400 480
data were obtained by varying the frequency,
bandwidth and intensity of Gaussian bands. (b)
The X-ray absorption experiments (EXAFS)
have been conducted using the XAFS beamline of 2
the Brazilian Synchrotron Light Laboratory
(LNLS, Campinas, SP, Brazil-www.lnls.br). The 0 1 3 4
LNLS storage ring works with beam energy of
1.85 GeV and during data collection the average
current was 140 mA A Si(1 1 1) two-crystal mono-
chromator was used and spectra were recorded
close to the Eu LIII edge (6977 eV) in the
fluorescence mode. Air filled chamber was used
in the detection of the ‘‘I0 ’’ signal and a NaI 600 650 700
detector was used to detect the fluorescence signal. Wavelength (nm)
Fig. 1. Excitation (a) and emission (b) spectra obtained for the
complex [Eu(TTA)3(H2O)2]—upper curves and the new com-
1
Peakfit is a product of Jandel Corporation, 2591 Rerner pound [Eu(TTA)3-HOST]—lower curves. Numbers denote J
Boulevard, San Rafael, CA 94901, USA. levels for the Eu3+ 5D0-7FJ transitions.
 C. Molina et al. / Journal of Luminescence 104 (2003) 93–101
[Eu(TTA)3(H2O)2]. Hence, all weak bands of f–f
transitions of Eu3+ bands are hidden by the strong
band except the 7F0-5D2 band appearing as a
weak band at 463.6 nm. The relative intensity of the
broad UV band to the intrinsic Eu3+ lines in fact
shows the so-called ‘‘antenna’’ role played by the b-
diketone molecules [2]. The spectrum obtained for
the compound resulting from the incorporation
process also display the broad UV band. On the
other hand the 463.6 nm band appears even weaker
by comparison with the strongest one. This
qualitative observation points toward an increase
in the efficiency of the UV excitation upon the
incorporation process. More quantitative informa-
tion concerning to the quantum efficiency may be
obtained from emission spectra shown in Fig. 1(b).
Assignments are done in the figure. Concerning the
hydrated complex, the Eu3+ point symmetry is
described by a distorted Archimedean anti-prism
[17] and the emission spectrum is dominated by the
induced electric dipole 5D0-7F2 transition peaking
at 611.5, 615.1 and 620.2 nm. Malta et al. have
considered theoretically the different contributions
to electric dipole transitions [2,4,18]. They were able
to distinguish contributions from the well-known
forced electric dipole and dynamic coupling me-
chanisms. They found that in the case of b-
diketonates the last mechanism largely dominates
indicating that Eu3+ ions are embedded in highly
polarizable chemical environment. Moreover, the
energy transfer process from the b-diketone ligand
to the Eu3+ excited state levels were found to be
very efficient. In this case the emission quantum
yields can be determined mainly by the decay
process from the Eu3+ emitting levels [18]. A
pronounced inhomogeneous broadening of the
corresponding emission lines occurs upon incor-
poration of the complex into the hybrid framework,
suggesting that a distribution of sites should be
available for the Eu3+ ions (Fig. 1(b)). 5D0 decay
times values are shown in Table 1. 0.34 ms is the
value obtained for the hydrated compound and an
increase to 0.57 ms is observed upon the incorpora-
tion, with no variation for the different composi-
tions. It should be noted that a single exponential
decay could fit the experimental data. The sites
accounting for the inhomogeneously broadened
bands should be in fact very similar.
97
Table 1
Judd–Ofelt’s O2;4 intensity parameters (10
20 cm2), experimen-
tal (texp ) and calculated radiative (tcalc ) decay times (ms), and
quantum efficiencies (f ¼ texp =tcalc ) (%) obtained for the
hydrated b-diketone complex and the compound resulting
from the incorporation of the complex into the organic–
inorganic host
Compound O2 O4 tcalc (ms) texp (ms) f (%)
[Eu(TTA)3(H2O)2] 33.0 4.6 1.24 0.34 27
[Eu(TTA)3-HOST] 40.0 5.0 0.77 0.57 74
Table 1 also gathers the results obtained for the
Judd–Ofelt’s O2;4 intensity parameters readily
obtained from the emission spectra considering
as usual the magnetic dipolar transition 5D0-7F1
as a Refs. [10,18]. It is observed that the
incorporation of the b-diketone salts into the
hybrid host resulted in compounds displaying
transition intensities even stronger (higher O2
values) than those observed in the initial hydrated
salts. In fact the values obtained for the O2
parameter are among the highest reported in the
literature [2]. Another interesting feature is asso-
ciated with the non-radiative loss of the 5D0
excited state. The non-radiative rates may be
evaluated comparing the experimental decay times
(texp ) and calculated radiative lifetimes (tcalc ),
which was also easily obtained from emission
spectra [10]. Emission quantum efficiencies (f) are
evaluated by the ratio between experimental and
calculated decay times (f ¼ texp =tcalc ). Table 1
also shows these results. The quantum efficiency is
rather low for the hydrated initial salts (23% in
agreement with Ref. [18]). It is still lower (8%) for
the Eu3+ containing hybrid host as shown in a
previous study [9,10] where the low values were
mainly governed by non-radiative loss through
OH oscillators in the Eu3+ first coordination
shell. An important enhancement is observed
for the quantum efficiencies of the new compounds
prepared in this investigation (74%), suggesting
that the coordination ability of the hybrid
host was strong enough to displace the two water
molecules from the coordination shell of the
Eu3+ ions. No difference was found for the
different concentrations of Eu3+ complex in
the hybrid host.
98 C. Molina et al. / Journal of Luminescence 104 (2003) 93–101

Apart from exhibiting quantum efficiency values 1.5

comparable to the most efficient compounds
1.0
known up to now [2], these new highly emissive

k*khi (k)
materials may be easily obtained as thin films by 0.5
casting from solutions. The use of the dip/spin
coating process has allowed us to produce 100 nm 0.0
to 10 mm-thick films and therefore potential
-0.5
application in photo and electroluminescent de-
0 4 8 12
vices is suggested. -1
(a) k (Å )
Since the new compounds were amorphous in
X-ray diffraction measurements, further charac- 12
terisation of the coordination site of the metallic

F (R) (arb.units)
ions can only be done by spectroscopic techniques. 8
We have been using X-ray absorption (EXAFS) at
the Eu3+ LIII-edge and infrared absorption. 4
The EXAFS signals kwðk) displayed in Fig. 2(a)
were extracted from the raw data using the 0
Lengeler–Eisenberger method [19]. The kwðkÞ 0 2 4 6
spectrum was Fourier-transformed using k2 pon- (b) R (Å)
deration and a Kaiser window (t ¼ 2:5), leading to
the spectra scaled in distances R(A) ( and not 0.5
corrected for phase shifts, as displayed in Fig. 2(b).
One peak around 2 A ( is clearly observed, related to
k*khi (k)

the first coordination shell of Eu3+ ions. It was 0.0

filtered and back-transformed to k-space. The
resulting EXAFS-filtered signals have been treated
as a sum of sinusoidal wave functions using single
scattering approximation [20]:
X Ni 2 2
kwðkÞ ¼ S02 e
2si k e
2Ri=lðkÞ fij ðp; kÞ
i
R2i
 
 sin 2kRi þ Fij ðkÞ ;
where Ni is the number of atoms i in the
coordination shell at average interatomic distance
Ri from the absorbing atom, si is the Debye–
Waller factor, which takes into account the static
and thermal structural disorder, lðkÞ is the
photoelectron mean free path and S02 is an
amplitude reduction factor reflecting multielectron
effects. fij ðp; kÞ and fij ðkÞ are the amplitude and
phase functions for this coordination shell which
were obtained from the McKale’s tables [21]. The
use of theoretical phase and amplitude functions
requires a test of these functions on a structurally
well known reference compound, and in particular
to determine the threshold energy (E0 þ DE) and
the G parameter related to the photoelectron mean
-0.5
2 4 6 8
-1
(c) k (Å )
( Fourier transform
Fig. 2. (a) kwðkÞ EXAFS curves; (b) F(A)
curves and (c) fit of the filtered EXAFS spectrum (line-filtered
ð1Þ spectrum; circles—Fit (Eq. (1)). Upper curves—[Eu(TTA)3
(H2O)2] and lower curves—[Eu(TTA)3-HOST].
free path through the relation GðkÞ ¼ k=l: In this
case the spectrum obtained for the compound
[Eu(TTA)3(H2O)2] was used with the crystallo-
graphic data from Ref. [17]. A mean distance of
( for the 6 oxygen atoms from the 3 TTA
2.42 A
ligand molecules and 2.53 A ( for the 2 oxygen
atoms from the 2 water molecules were employed
for that procedure.
The Fourier-filtered signal obtained for the new
Eu3+-complex doped hybrid were then simulated
by a least-square fitting procedure, leading to the
determination of the structural parameters R; N
and Ds (Ds ¼ s
s0 where s0 stands for the
reference compound) for the coordination shell
 C. Molina et al. / Journal of Luminescence 104 (2003) 93–101
around the absorbing Eu3+ atom. The reliably of
the fit is given by the value of the residual function
r defined as
X  2 X
r¼ ki wexp ðki Þ
wth ðki Þ = kwexp ðki Þ2 : ð2Þ
i i
Fig. 2(c) shows the good fit attained and the
results point to 8 neighbour atoms for the Eu3+
central ion. 6 of these atoms are located at a mean
distance of 2.44 A( (Ds ¼ 0:10 A
( 2) and 2 atoms are
found at a mean distance of 2.30 A ( (Ds ¼ 0:06 A
( 2).
The picture that can be drawn from these results
together with the luminescence data suggests that
the 2 water molecules were withdrawn from the
Eu3+ first shell being substituted by 2 other ligand
atoms. This suggestion could be further confirmed
by the results presented hereafter.
Coming back to emission spectra, the red shift
observed for the 5D0-7F0 transition with respect
to 17374 cm
1 calculated [22] for gaseous Eu3+
seems to confirm this suggestion. This red shift was
related with the nature of the Eu3+-first coordina-
tion shell by means of a phenomenological
equation [23]
DE ¼ Ecomplex
Egaseous ¼ CN ½n1 d1 þ ? þ ni di ;
ð3Þ
where the CN coefficient is a nephelauxetic
parameter adjustment associated with the total
number of Eu3+-first ligands, nj is the number of
atoms of type j in the first coordination shell and dj
is an adjusted parameter, which measures the
tendency of a particular atom to bond covalently
with the Eu3+ ion [23].
According to the coordination revealed by the
EXAFS data which comprises 6 oxygen atoms
from the TTA groups and 2 ether-type oxygen
atoms from the polymer chains, the predicted
energy shift calculated from Eq. (3),
111.873 cm
1, agrees very well with the experi-
mental value extratec from Fig. 1, 112.473 cm
1.
We should stress that the red shift predicted from
Eq. (3) could alternatively be obtained considering
the Eu3+ coordination to two carbonyl oxygen
atoms from the urea bridges—instead of the two
ether-type oxygen atoms. By considering the latter
possibility a value of 121.473 cm
1 is obtained
which is far enough from the experimental value.
99
Therefore the spectroscopic results give confidence
to the fact that the urea cross-linkages are not
involved in the first coordination shell of the Eu3+
ion, in agreement with results reported recently for
analogous nanocomposites involving the U(600)
hybrid host and Eu perchlorate salts [24].
The room temperature FT–IR absorption spec-
tra of the [Eu(TTA)3(H2O)2] complex and the
doped [Eu(TTA)3(U600)n ] were also obtained and
are reproduced in Fig. 3. The skeleton CO
stretching region (nCO, between 1200 and
1000 cm
1) is one of the most powerful diagnostic
tools to monitor complexation effects involving
the ether oxygen atoms of polymer-type chains
and cations [25–29]. Bonding of cations to the
heteroatoms of the polyether chains result in a
shift of the usually very intense nCO band to lower
wave numbers.
Fig. 3 demonstrates that the infrared spectrum
of U(600) exhibits a band at approximately
1110 cm
1 and a shoulder around 1143 cm
1
(e)
(d)
Absorbance (arb.units)
(c)
(b)
(a)
800 1200 1600
Wavenumber (cm-1)
Fig. 3. Room temperature FT–IR spectra: (a) n ¼ N (non-
doped sample), (b) n ¼ 850; (c) n ¼ 170; (d) n ¼ 17; (e)
[Eu(TTA)3(H2O)2]. The spectra of the di-ureasils have been
scaled so that the height of the nCH2 band is approximately the
same.
100 C. Molina et al. / Journal of Luminescence 104 (2003) 93–101
which are ascribed, respectively, to the CO
stretching vibration mode and to the coupled
vibration of the CO stretching and CH2 rocking
modes [25–31]. In the spectra obtained for the new
compounds described here the position of the
1113 cm
1 feature, associated with non-coordi-
nated (OCH2CH2) moieties, remains practically
unchanged, although its intensity is considerably
reduced in the sample with n ¼ 17: The results of
the curve-fitting performed between 1220 and
977 cm
1 on the spectra of the b-diketonate-
containing hybrids and of the pure hydrated salt
are reproduced in Fig. 4. In the low-frequency side
of the nCO envelope, the growth of a shoulder
near 1080 cm
1 is distinctly discerned in the
spectra. It is noteworthy that the new component
observed around 1080 cm
1 in the spectra of all
the doped samples can not be ascribed to the
salt though curiously [Eu(TTA)3(H2O)2] displays
(e)
(d)
Absorbance (arb.units)
(c)
(b)
(a)
1000 1100
Wavenumber (cm-1)
Fig. 4. Curve-fitting results of the nCO region: (a) n ¼ N (non-
doped sample), (b) n ¼ 850; (c) n ¼ 170; (d) n ¼ 17; (e)
[Eu(TTA)3(H2O)2]. Dot lines show Gaussian components
obtained in the deconvolution process.
a band at approximately the same frequency.
However, this event is considerably weaker than
the 1080 cm
1 peak produced by the U(600)-based
materials (Fig. 4). Since the bonding of Eu3+ ions
to polyether chains gives rise to a characteristic
nCO band located near 1078–1073 cm
1 [25,26],
these data provide unequivocal evidence that there
is coordination of the ether-type oxygen atoms of
the polymer chains to the Eu3+ ions much
probably substituting for water molecules. The
downshift of the nCO band found in the present
case is practically the same as in the literature,
indicating that the interaction between the lantha-
nide ion and the ether-type oxygen atoms of the
polymer segments is of the same order of
magnitude in the POE-based polymer electrolytes
studied by Bernson et al. [25,26] and in our
b-diketonate system. This result is quite extra-
ordinary, as it means that, in spite of the bulkiness
of the TTA ligands, no steric effects influence
the approach of the polyether chains to the central
ion.
The analysis of the amide I and amide II regions
(between 1500 and 1800 cm
1) leads us to state
that the carbonyl oxygen atoms of the urea cross-
links do not play any active role in samples with
n > 17; a conclusion that is in perfect agreement
with the situation recently observed in U(600)-
based xerogels doped with Eu perchlorate [24]. In
fact both bands are essentially unaffected by the
presence of the b-diketonate chelate (Fig. 3). This
observation may be interpreted as an indication
that the urea carbonyl oxygen atoms do not
belong to the lanthanide ion coordination shell.
At n ¼ 17; any conclusions regarding the amide I
and amide II range of frequencies are subject to
much uncertainty due to extensive overlapping of
the b-diketonate ligands and polymer bands.
4. Conclusions
1200 Enhanced quantum efficiency for he photoemis-
sion of Eu3+ ions was obtained from the new
materials composed of a Eu3+ b-diketonate
complex in the hybrid host of di-ureasil. The
studied materials were b-diketone hydrated salt
comprising the thenoyltrifluoroacetone (TTA)
 C. Molina et al. / Journal of Luminescence 104 (2003) 93–101
ligand and the organic–inorganic framework
described by a siliceous backbone to which short
polyether-based segments were covalently bond
through urea bridges. X-ray absorption and IR
absorption results considered together with lumi-
nescence data led to a picture where the Eu3+ first
coordination shell was composed of the oxygen
atoms of the b-ketonate ligands and the ether-type
oxygen atoms of the host. The high light output of
the Eu3+ emission was observed with low non-
radiative decays under UV excitation showing the
replacement of the water molecules by the host
ether oxygen atoms in the Eu3+ coordination
shell. The calculated quantum efficiency equals to
74%, and is in the same range of values previously
obtained for the most efficient Eu3+ coordination
compounds reported in literature. This approach
makes the compounds introduced potentially
interesting for application in luminescent devices.
Acknowledgements
This research was partially supported by LNLS-
National Synchrotron Light Laboratory, Brazil.
The financial support from FCT (PRAXIS/P/
CTM/13175/98) CAPES-ICCTI (Contract 61/00),
FAPESP, PRONEX and CNPq (Portuguese and
Brazilian agencies) is gratefully acknowledged.
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