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: [email protected] (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 pounds, in the powder form and displaying
ions. In addition, such an ideal material should not unusually high emission quantum efficiencies
only be water soluble but also display adequate (70–80%), have resulted from this concept [2,4].
mechanical properties, allowing its preparation These compounds may be used as powdered
either as bulk monoliths or thin films that could be phosphors or dispersed in semiconducting con-
easily deposited on different substrates by casting jugated polymers. In the last case light emitting
from solutions. diodes with narrow emission line bandwidth have
Among various organic molecules considered been proposed [5].
in this framework, it is undoubtedly that the In parallel to these works, a considerable
b-diketones are extremely promising. Since the amount of research has been devoted to the
early 1960s the lanthanides b-diketonate chelates materials synthesis through the combination of
have been known to be very stable, easily the sol–gel route with the principles of the host–
synthesised and highly light emissive under UV guest chemistry. These efforts have led to the
excitation. The UV excitation is followed by production of a significant number of innovative
efficient intramolecular energy transfer from organic–inorganic frameworks with tunable design
ligand excited states to the lanthanide emissive and suitable features. The major interest of this
levels, yielding characteristic and intensely lumi- approach is the possibility of preparing multi-
nescent narrow band f–f electronic transitions functional nanoscale organic–inorganic systems
[1,2]. In fact some of lanthanide b-diketone whose fields of application range from electro-
complexes exhibit laser action in solution [3], and chemistry, biology, mechanics, ceramics, electro-
have been also considered to be serious candidates nics to photonics [6].
as luminescent dopants for the fabrication of Among the sol–gel derived structures proposed
hybrid phosphors and other optical devices. so far, a family of outstanding lanthanide-based
The main drawback that derives from the use of hybrid compounds have been reported [7]. The
the lanthanide b-diketonates lies in the difficulty in host matrix, termed as di-ureasil, comprises poly-
obtaining them in the anhydrous form. In general, ether-based chains of variable length grafted to
the b-diketones chelates are obtained as hydrates, both ends to a siliceous backbone through urea
in which two or three water molecules are attached cross linkages. These xerogels, which are easily
to a central lanthanide ion. Concerning trivalent produced as thin, elastomeric and highly trans-
europium (Eu) ions emitting a orange–red light parent monoliths, may withstand a large amount
the general formula of the complexes may be of guest dopants. When doped with trivalent
written as [EuL3(H2O)n ], where L holds for the lanthanide ions like Nd3+, Eu3+ and Tb3+ the
b-diketonate ligands and n ¼ 2; 3: The water di-ureasils display remarkable emission properties.
molecules in the first coordination shell of the Besides a broad long-lived emission covering the
lanthanide ion bring deleterious effects to the light whole visible range of the electromagnetic spec-
emission properties. Quenching of the 5D0 excited trum, the di-ureasils exhibit the typical intra-4f
state of Eu3+ ions through non-radiative decay narrow line emission in the green (Tb3+) [8], red
paths provided by OH oscillators of coordinated (Eu3+) and even in the near infrared (Nd3+) [9–
water molecules is a phenomenon known for many 12], thus opening new prospects for their applica-
years. One of the possible strategies to improve the tions. In addition, the colour emitted by the Eu3+-
light emission properties of lanthanide b-diketo- doped di-ureasils may be readily tuned across the
nate chelates has involved the substitution of the !
Commission Internationale d’ Eclairage (CIE)
water molecules in the coordination shell with chromaticity diagram by varying either the salt
other chemical species. Heterocyclic ligands like concentration or the excitation wavelength [13]. In
2,20 -bipyridine and 1,10-phenanthroline, substi- spite of the above-mentioned properties, high
tuted sulphoxides and phosphine oxides, aromatic multiphonon decay rates are observed for Eu3+
carboxylic acids among many others, have been excited states. Typical calculated quantum effi-
extensively employed [2]. Crystalline mixed com- ciencies of around 8% are obtained for emission
 C. Molina et al. / Journal of Luminescence 104 (2003) 93–101 95

from the 5D0 excited state within the entire range and O,O-bis(2-aminopropyl)poly(propyleneglycol)-
of compositions studied up to now. Hydrated poly(ethyleneglycol)-poly(propyleneglycol) com-
precursor salts like perchlorate and triflate have mercially Jeffamine-ED600s, average molecular
been used and at least 3 water molecules are weight 600 mol/g) were mixed in the molar ratio
suggested to occupy the Eu3+ first coordination 1:2 and stirred in tetrahydrofuran (THF) under
shell [9,10]. reflux for 24 h. THF was evaporated and a urea
In this work we bring together the most cross-linked organic–inorganic precursor (EtO)3
attractive characteristics of the three concepts, Si(CH2)3-NH(C=O)NH-[poly(propyleneglycol)]a
(1) the organic–inorganic hybrid, (2) the host– [poly(ethyleneglycol)]b(poly(propyleneglycol)]c-NH
guest approaches and (3) the possible optimisation (C=O)NH-(CH2)3Si(OEt)3 (with a þ c ¼ 2:5 and
of the light output provided by the utilisation of b ¼ 8:5) was thus obtained.
lanthanide b-diketonate compounds, by means The Eu3+ b-diketonate complex [Eu(TTA)3
of the incorporation of highly emissive Eu3+ (H2O)2] (where TTA stands for thenoyltrifluoroa-
b-diketonates into a di-ureasil with a short cetone) was one of the Eu3+ b-diketonate salts
polyether chain. On the basis of previous studies firstly synthesised and already proposed as active
[9–13], we have concluded that this host frame- specie in polymeric laser hosts [14]. In this work it
work protects the Eu3+ ions from the effect of was prepared according to the method proposed
water molecules due to coordination ability of in Ref. [15] (these salts are tentatively represented
di-ureasil to the lanthanide ion. The absence of in Scheme 1). The hydrated complexes were then
water molecules in the lanthanide coordination incorporated in the di-ureasil. [Eu(TTA)3(H2O)2]
shell can be expected and therefore reduced non- was first dissolved in the organic–inorganic pre-
radiative decay rates of Eu3+ excited states. cursor. Ammonium fluoride, NH4F, dissolved in
ethanol, was used as a nucleophilic catalyst for the
hydrolysis reaction ([NH4F]/[Si]=0.02) and water
2. Experimental (molar ratio [H2O]/[Si]=6) was added under
stirring, allowing the formation of a wet gel.
The synthesis of the di-ureasil hybrid structure, Finally, ethanol and water were slowly removed at
designated as U(600) (where 600 stands for the 501C to give a transparent monolith of a rubbery
average molecular weight of the starting organic material. The complex concentration in the hy-
precursor) has been described in detail elsewhere brids prepared ranges from 0.5 to 25 mol% of
[10]. All chemical reagents were commercially Eu3+ [(Eu3+/Eu3++Si)  100]. As usual in poly-
available and were purchased from Fluka mer science, these concentrations could be also
and Aldrich. 3-(isocyanatopropyl)triethoxysilane expressed by n=[O]/[Eu], where n is the number of

H H

R2 R1
H H
O O
HC CH
O O
Eu
H 2C CH2
O O
HC O O CH R1 = R 2 = CF3
S

R1 R2
CH CH

R2 CH 2 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 97

[Eu(TTA)3(H2O)2]. Hence, all weak bands of f–f Table 1

Judd–Ofelt’s O2;4 intensity parameters (10
20 cm2), experimen-
transitions of Eu3+ bands are hidden by the strong
tal (texp ) and calculated radiative (tcalc ) decay times (ms), and
band except the 7F0-5D2 band appearing as a quantum efficiencies (f ¼ texp =tcalc ) (%) obtained for the
weak band at 463.6 nm. The relative intensity of the hydrated b-diketone complex and the compound resulting
broad UV band to the intrinsic Eu3+ lines in fact from the incorporation of the complex into the organic–
shows the so-called ‘‘antenna’’ role played by the b- inorganic host
diketone molecules [2]. The spectrum obtained for Compound O2 O4 tcalc (ms) texp (ms) f (%)
the compound resulting from the incorporation
[Eu(TTA)3(H2O)2] 33.0 4.6 1.24 0.34 27
process also display the broad UV band. On the
[Eu(TTA)3-HOST] 40.0 5.0 0.77 0.57 74
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 Table 1 also gathers the results obtained for the
incorporation process. More quantitative informa- Judd–Ofelt’s O2;4 intensity parameters readily
tion concerning to the quantum efficiency may be obtained from the emission spectra considering
obtained from emission spectra shown in Fig. 1(b). as usual the magnetic dipolar transition 5D0-7F1
Assignments are done in the figure. Concerning the as a Refs. [10,18]. It is observed that the
hydrated complex, the Eu3+ point symmetry is incorporation of the b-diketone salts into the
described by a distorted Archimedean anti-prism hybrid host resulted in compounds displaying
[17] and the emission spectrum is dominated by the transition intensities even stronger (higher O2
induced electric dipole 5D0-7F2 transition peaking values) than those observed in the initial hydrated
at 611.5, 615.1 and 620.2 nm. Malta et al. have salts. In fact the values obtained for the O2
considered theoretically the different contributions parameter are among the highest reported in the
to electric dipole transitions [2,4,18]. They were able literature [2]. Another interesting feature is asso-
to distinguish contributions from the well-known ciated with the non-radiative loss of the 5D0
forced electric dipole and dynamic coupling me- excited state. The non-radiative rates may be
chanisms. They found that in the case of b- evaluated comparing the experimental decay times
diketonates the last mechanism largely dominates (texp ) and calculated radiative lifetimes (tcalc ),
indicating that Eu3+ ions are embedded in highly which was also easily obtained from emission
polarizable chemical environment. Moreover, the spectra [10]. Emission quantum efficiencies (f) are
energy transfer process from the b-diketone ligand evaluated by the ratio between experimental and
to the Eu3+ excited state levels were found to be calculated decay times (f ¼ texp =tcalc ). Table 1
very efficient. In this case the emission quantum also shows these results. The quantum efficiency is
yields can be determined mainly by the decay rather low for the hydrated initial salts (23% in
process from the Eu3+ emitting levels [18]. A agreement with Ref. [18]). It is still lower (8%) for
pronounced inhomogeneous broadening of the the Eu3+ containing hybrid host as shown in a
corresponding emission lines occurs upon incor- previous study [9,10] where the low values were
poration of the complex into the hybrid framework, mainly governed by non-radiative loss through
suggesting that a distribution of sites should be OH oscillators in the Eu3+ first coordination
available for the Eu3+ ions (Fig. 1(b)). 5D0 decay shell. An important enhancement is observed
times values are shown in Table 1. 0.34 ms is the for the quantum efficiencies of the new compounds
value obtained for the hydrated compound and an prepared in this investigation (74%), suggesting
increase to 0.57 ms is observed upon the incorpora- that the coordination ability of the hybrid
tion, with no variation for the different composi- host was strong enough to displace the two water
tions. It should be noted that a single exponential molecules from the coordination shell of the
decay could fit the experimental data. The sites Eu3+ ions. No difference was found for the
accounting for the inhomogeneously broadened different concentrations of Eu3+ complex in
bands should be in fact very similar. 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 -0.5
scattering approximation [20]: 2 4 6 8
-1
(c) k (Å )
X Ni 2 2
kwðkÞ ¼ S02 e
2si k e
2Ri=lðkÞ fij ðp; kÞ ( Fourier transform
Fig. 2. (a) kwðkÞ EXAFS curves; (b) F(A)
i
R2i curves and (c) fit of the filtered EXAFS spectrum (line-filtered
 
 sin 2kRi þ Fij ðkÞ ; ð1Þ spectrum; circles—Fit (Eq. (1)). Upper curves—[Eu(TTA)3
(H2O)2] and lower curves—[Eu(TTA)3-HOST].
where Ni is the number of atoms i in the
coordination shell at average interatomic distance free path through the relation GðkÞ ¼ k=l: In this
Ri from the absorbing atom, si is the Debye– case the spectrum obtained for the compound
Waller factor, which takes into account the static [Eu(TTA)3(H2O)2] was used with the crystallo-
and thermal structural disorder, lðkÞ is the graphic data from Ref. [17]. A mean distance of
photoelectron mean free path and S02 is an ( for the 6 oxygen atoms from the 3 TTA
2.42 A
amplitude reduction factor reflecting multielectron ligand molecules and 2.53 A ( for the 2 oxygen
effects. fij ðp; kÞ and fij ðkÞ are the amplitude and atoms from the 2 water molecules were employed
phase functions for this coordination shell which for that procedure.
were obtained from the McKale’s tables [21]. The The Fourier-filtered signal obtained for the new
use of theoretical phase and amplitude functions Eu3+-complex doped hybrid were then simulated
requires a test of these functions on a structurally by a least-square fitting procedure, leading to the
well known reference compound, and in particular determination of the structural parameters R; N
to determine the threshold energy (E0 þ DE) and and Ds (Ds ¼ s
s0 where s0 stands for the
the G parameter related to the photoelectron mean reference compound) for the coordination shell
 C. Molina et al. / Journal of Luminescence 104 (2003) 93–101 99

around the absorbing Eu3+ atom. The reliably of Therefore the spectroscopic results give confidence
the fit is given by the value of the residual function to the fact that the urea cross-linkages are not
r defined as involved in the first coordination shell of the Eu3+
X  2 X ion, in agreement with results reported recently for
r¼ ki wexp ðki Þ
wth ðki Þ = kwexp ðki Þ2 : ð2Þ
analogous nanocomposites involving the U(600)
i i
hybrid host and Eu perchlorate salts [24].
Fig. 2(c) shows the good fit attained and the The room temperature FT–IR absorption spec-
results point to 8 neighbour atoms for the Eu3+ tra of the [Eu(TTA)3(H2O)2] complex and the
central ion. 6 of these atoms are located at a mean doped [Eu(TTA)3(U600)n ] were also obtained and
distance of 2.44 A( (Ds ¼ 0:10 A
( 2) and 2 atoms are
are reproduced in Fig. 3. The skeleton CO
found at a mean distance of 2.30 A ( (Ds ¼ 0:06 A
( 2).
stretching region (nCO, between 1200 and
The picture that can be drawn from these results 1000 cm
1) is one of the most powerful diagnostic
together with the luminescence data suggests that tools to monitor complexation effects involving
the 2 water molecules were withdrawn from the the ether oxygen atoms of polymer-type chains
Eu3+ first shell being substituted by 2 other ligand and cations [25–29]. Bonding of cations to the
atoms. This suggestion could be further confirmed heteroatoms of the polyether chains result in a
by the results presented hereafter. shift of the usually very intense nCO band to lower
Coming back to emission spectra, the red shift wave numbers.
observed for the 5D0-7F0 transition with respect Fig. 3 demonstrates that the infrared spectrum
to 17374 cm
1 calculated [22] for gaseous Eu3+ of U(600) exhibits a band at approximately
seems to confirm this suggestion. This red shift was 1110 cm
1 and a shoulder around 1143 cm
1
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 ; (e)
ð3Þ
where the CN coefficient is a nephelauxetic
parameter adjustment associated with the total (d)
Absorbance (arb.units)

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 (c)
with the Eu3+ ion [23].
According to the coordination revealed by the
EXAFS data which comprises 6 oxygen atoms (b)
from the TTA groups and 2 ether-type oxygen
atoms from the polymer chains, the predicted
energy shift calculated from Eq. (3), (a)
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 800 1200 1600
Eq. (3) could alternatively be obtained considering Wavenumber (cm-1)
the Eu3+ coordination to two carbonyl oxygen
atoms from the urea bridges—instead of the two 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)
ether-type oxygen atoms. By considering the latter [Eu(TTA)3(H2O)2]. The spectra of the di-ureasils have been
possibility a value of 121.473 cm
1 is obtained scaled so that the height of the nCH2 band is approximately the
which is far enough from the experimental value. same.
100 C. Molina et al. / Journal of Luminescence 104 (2003) 93–101

which are ascribed, respectively, to the CO a band at approximately the same frequency.
stretching vibration mode and to the coupled However, this event is considerably weaker than
vibration of the CO stretching and CH2 rocking the 1080 cm
1 peak produced by the U(600)-based
modes [25–31]. In the spectra obtained for the new materials (Fig. 4). Since the bonding of Eu3+ ions
compounds described here the position of the to polyether chains gives rise to a characteristic
1113 cm
1 feature, associated with non-coordi- nCO band located near 1078–1073 cm
1 [25,26],
nated (OCH2CH2) moieties, remains practically these data provide unequivocal evidence that there
unchanged, although its intensity is considerably is coordination of the ether-type oxygen atoms of
reduced in the sample with n ¼ 17: The results of the polymer chains to the Eu3+ ions much
the curve-fitting performed between 1220 and probably substituting for water molecules. The
977 cm
1 on the spectra of the b-diketonate- downshift of the nCO band found in the present
containing hybrids and of the pure hydrated salt case is practically the same as in the literature,
are reproduced in Fig. 4. In the low-frequency side indicating that the interaction between the lantha-
of the nCO envelope, the growth of a shoulder nide ion and the ether-type oxygen atoms of the
near 1080 cm
1 is distinctly discerned in the polymer segments is of the same order of
spectra. It is noteworthy that the new component magnitude in the POE-based polymer electrolytes
observed around 1080 cm
1 in the spectra of all studied by Bernson et al. [25,26] and in our
the doped samples can not be ascribed to the b-diketonate system. This result is quite extra-
salt though curiously [Eu(TTA)3(H2O)2] displays 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
(e)
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-
(d) 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)-
Absorbance (arb.units)

based xerogels doped with Eu perchlorate [24]. In

fact both bands are essentially unaffected by the
(c)
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.
(b) 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.
(a)

4. Conclusions

1000 1100 1200 Enhanced quantum efficiency for he photoemis-

Wavenumber (cm-1) sion of Eu3+ ions was obtained from the new
materials composed of a Eu3+ b-diketonate
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)
complex in the hybrid host of di-ureasil. The
[Eu(TTA)3(H2O)2]. Dot lines show Gaussian components studied materials were b-diketone hydrated salt
obtained in the deconvolution process. comprising the thenoyltrifluoroacetone (TTA)
 C. Molina et al. / Journal of Luminescence 104 (2003) 93–101 101

ligand and the organic–inorganic framework [7] L.D. Carlos, V. de Zea Bermudez, M.C. Duarte, M.M.
described by a siliceous backbone to which short Silva, C.J. Silva, M.J. Smith, M. Assunc-a* o, L. Alc!acer,
In: C. Ronda, T. Welker (Eds.), Physics and Chemistry
polyether-based segments were covalently bond
of Luminescent Materials VI, Vol. 97–29, Electro-
through urea bridges. X-ray absorption and IR chemical Society Proceedings, San Francisco, 1997,
absorption results considered together with lumi- p. 352.
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