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By Julie Thompson,* Robert I. R.

Blyth, Giuseppe Gigli, and Roberto Cingolani

FULL PAPER

Obtaining Characteristic 4f4f Luminescence from Rare Earth


Organic Chelates

We report a study of a series of heavy rare earth tris-8-hydroxyquinolines (REQ3s), using UV-visible absorption spectroscopy,
infrared absorption spectroscopy, and photoluminescence (PL) measurements. We show that the heavy REQ3s are all chemically similar to each other and to aluminium tris-8-hydroxyquinoline, at least in terms of the ligand behavior. Characteristic rare
earth 4f4f luminescence is only observed for ErQ3 and YbQ3 due to the relatively low energy of the ligand triplet state. We
show that a triplet transfer mechanism cannot be responsible for the observed Yb 4f4f luminescence observed in YbQ3. Instead, an internal chemiluminescent process is shown to be energetically favorable. The thin film PL spectra of all the heavy
REQ3s are dominated by triplet emission, except for that of ErQ3, for which transfer to the Er3+ ion represents an efficient alternative. The PL spectra of powder samples, which would be expected to consist of approximately equal amounts of both isomers, are dominated by singlet emission. This is in contrast to the results from the thin films, and suggests that the isomer which
predominates in the thin films has a much higher intersystem crossing rate than the other isomer.

1. Introduction
Recent years have seen considerable interest in the possibility of using rare earth chelates as the emissive materials in photonic devices, such as light emitting diodes (LEDs)[1] and active
optical waveguides.[2] De-excitation of rare earth ions produces
narrow, well-defined emission lines over a broad wavelength
region in the visible and extending into the infrared. In the visible region of the electromagnetic spectrum the sharp emission
lines obtained from the relaxation of rare earth ions are desirable for full color displays with well defined red, green, or blue
components. In the infrared, the focus changes to telecommunications, as wavelengths corresponding to intra-4f transitions
of erbium (1.5 lm), neodymium (1.3 lm), and ytterbium ions
(0.98 lm) are widely used for fiber optic based systems.
Rare earth chelates consist of a rare earth ion surrounded by
organic ligands, which can act as chromophores. The presence
of an organic chromophore improves the efficiency of the rare
earth light emission. Optically generating rare earth luminescence directly is difficult due to the small absorption coefficients of the lanthanide ions, however the absorption coefficients of organic chromophores is orders of magnitude
higher,[3] and when excited it can transfer its energy to the rare
earth, often called the antenna effect.[4] Numerous rare earth
chelates that have been synthesized have shown photo- and
electroluminescence in the visible and in the infrared.[1]

Rare earth complexes can be split into two main groups, the
light rare earths ranging from La to Eu, and the heavy rare
earths ranging from Tb to Lu, with complexes of gadolinium,
which lies between the two groups, appearing to behave somewhat anomalously.[5]
The rare earth tris-8-hydroxyquinolines (REQ3s), consist of
a trivalent rare earth ion surrounded by three identical hydroxyquinoline ligands, and are analogous in structure to aluminium tris-hydroxyquinoline (AlQ3), the well known green
emitter used in the first organic light-emitting diode, reported
by Tang and van Slyke in 1987.[6] The structures of YbQ3 and
AlQ3 are shown in Figure 1. YbQ3[7] and ErQ3[810] represent
two of the few organic compounds that are known to emit in
the infrared in the solid state, and as such they have received
much attention. The other heavy REQ3s, although potential
emitters of characteristic rare earth visible light, have not thus
far been investigated. In this work, we present a detailed study
of the optical and vibrational properties of a series of heavy
rare earth REQ3s, those of Gd, Dy, Ho, Er, and Yb. We describe the antenna effect in terms of either a triplet guesthost
system or a chemiluminescent redox reaction, to explain why
in some cases rare earth emission is observed and in others
only ligand luminescence is observed. We also discuss the origins of the ligand-related visible luminescence observed in
these molecules.

N
O

[*]

J. Thompson, Dr. R. I. R. Blyth, Dr. G. Gigli, Prof. R. Cingolani


National Nanotechnology Laboratory of INFM
Dipartimento di Ingegneria dell'Innovazione, Universita' di Lecce
Via Arnesano, 73100 Lecce, (Italy)
E-mail: julie.thompson@unile.it

Adv. Funct. Mater. 2004, 14, No. 10, October

3+

Al

(a)

O
N

3+

Yb

(b)

Figure 1. Molecular structures of a) AlQ3 and b) YbQ3.

DOI: 10.1002/adfm.200305169

 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

979

2. Results

2.2. UV-Visible Absorption Spectroscopy

2.1. FTIR

UV-vis absorption spectra of the REQ3s, and that of AlQ3


for comparison, are shown in Figure 3. The AlQ3 spectrum is
in excellent agreement with those in the literature.[13,14] The
REQ3 spectra are dominated by the absorption from the organic ligands, due to the fact that the absorption coefficients of
typical organic molecules are orders of magnitude higher than
those of the rare earth ions.[3]

Figure 2 shows the FTIR spectra of the REQ3s, along with


that of AlQ3. The main peak positions are summarized in
Table 1. The AlQ3 spectrum is in excellent agreement with
those in the literature.[11] It can be seen that the spectra for all
the rare earth molecules are identical, with the exception of a
small peak at 1215 cm1, which is due to (varying amounts of)
residual solvent. As can be seen from Table 1, the vibrations in
Figure 2 include CN, CO, CH, and collective ring vibrations, i.e., vibrations from all parts of the ligand. The similarity
of these vibrations for all the REQ3s indicates that the ligand
environment is the same for all the molecules. In comparison
with AlQ3 the spectra are again very similar, with only small
shifts observed for a few peaks. The main difference between
the REQ3 and AlQ3 spectra is the relative intensity of the ring
stretching peaks at 1575 cm1 and 1600 cm1, but given the similarities in all other peaks, this is unlikely to be significant. The
main systematic variation across the lanthanide series, and the
main difference between AlQ3 and REQ3 would be expected
to be the metaloxygen stretch at ~ 420 cm1 (REO)[12] or
~ 525 cm1 (AlO).[11] However these lie below the range of
the spectrometer used.

AlQ3
Absorbance (arb. units)

FULL PAPER

J. Thompson et al./4f4f Luminescence from Rare Earth Organic Chelates

YbQ3
ErQ3
HoQ3
DyQ3
GdQ3
200

250

300

350

400

450

Wavelength (nm)

Figure 3. UV-vis absorption spectra of evaporated thin films of a series of


REQ3s, with that of AlQ3 for comparison.

GdQ3

Intensity (arb. units)

DyQ3
ErQ3
YbQ3

AlQ3

800

1000

1200

1400

1600

-1

Wavenumber (cm )

Figure 2. FTIR spectra of a series of REQ3s, with that of AlQ3 for comparison.
Table 1. Assignments for the vibrational spectra of Figure 2.

980

YbQ3

AlQ3

Assignment [12]

1603
1573
1498
1466
1379
1317
1275
1231
1108
824
804
788
753

1603
1578
1498
1468
1378
1328
1282
1228
1113
824
804
789
747

Ring stretching
Ring stretching
Ring stretching
Ring stretching
CH bend and ring stretching
CH bend and ring stretching
CH bend
CN stretch, CH bend
CO stretch and CH bend
CH wag
Ring deformation
CH wag
CH wag

 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

As with the FTIR spectra, the UV-vis spectra of the REQ3s


are very similar to each other, with the largest absorption peak
occurring at 263 nm, and the second largest at 380 nm. A third
absorption peak at 320 nm is most readily visible for DyQ3 but
clearly present for all the other REQ3s. The REQ3 spectra correspond well to that of AlQ3, which shows the same two main
features with some structure around 325 nm. These two main
absorption bands have been assigned to the 1Bb (260 nm), and
the 1La (383 nm) excited states,[13] while the smaller absorption peaks around 320 nm have been attributed to a vibronic
progression by analogy with the spectrum of the protonated
form of the ligand.[14] Given the similarity with the AlQ3 spectrum, it seems reasonable to assume that this assignment also
applies to the REQ3s.

2.3. Photoluminescence
The PL spectra, in the visible region, of REQ3 thin films are
shown in Figure 4, together with that of AlQ3 for comparison.
The only characteristic rare earth 4f4f emission lines seen for
these materials are in the infrared, i.e., the 1.5 lm line of ErQ3
(not shown)[810] and the 0.98 lm line of YbQ3, shown in the inset to Figure 4. The expected sharp rare earth luminescence
peaks at 478 nm and 575 nm for Dy[15] and 549 nm and 665 nm
for Ho[15] are absent. The ultraviolet emission at 312 nm for
Gd[15] would not be expected to be seen as the excitation wave-

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Adv. Funct. Mater. 2004, 14, No. 10, October

FULL PAPER

J. Thompson et al./4f4f Luminescence from Rare Earth Organic Chelates

YbQ3

400

600

YbQ3

800 1000
Intensity (arb. units)

Intensity (arb. units)

AlQ3
DyQ3
HoQ3
YbQ3

ErQ3
DyQ3

GdQ3

GdQ3

ErQ3
Er(III)

400

500

600

700

800

Wavelength (nm)

Yb(III)
300

400

500

600

Figure 5. Photoluminescence spectra (k = 325 nm) in the visible region for


powder samples of a series of REQ3s.
700

800

Wavelength (nm)
Figure 4. Photoluminescence spectra (k = 325 nm) in the visible region for
evaporated films of a series of REQ3s, with that of AlQ3 for comparison.
Also shown are the RE3+ absorption spectra of solutions of YbCl3 and ErCl3
in methanol. Inset: the full (visible and IR) PL spectrum of an evaporated
thin film of YbQ3.

length was 325 nm, i.e., of a lower energy. In the thin films,
therefore, there appears to be an efficient energy transfer
mechanism from the ligand to the erbium and ytterbium ions,
which is not present for the other rare earth elements.
All the REQ3 films show luminescence from the ligand. The
emission obtained from these compounds has two distinct regions, centered at 500 nm and 575 nm. The peak maximum for
all the REQ3 films except ErQ3 is at 575 nm, although the
GdQ3 film spectrum contains significant amounts of the
500 nm peak. It is worth noting, however, that the intensity of
the GdQ3 PL was extremely weak, as indicated by the relatively poor statistics. In marked contrast to the other REQ3s, the
ErQ3 visible PL maximum is at 500 nm, and unlike the other
REQ3 spectra somewhat resembles that of AlQ3. Figure 5
shows the photoluminescence spectra of the bulk REQ3 powder samples. In contrast to the thin films, these spectra are
dominated by the peak at ~ 500 nm, again rather resembling
AlQ3.

3. Discussion
Although the only difference between these molecules is the
change in the central metal ion, the REQ3s sublime at a higher
temperature and are also more soluble in common organic solvents, such as methanol, than AlQ3. This would indicate that
metalligand bonds of the REQ3s are stronger and more ionic
than those in AlQ3, which is in agreement with the XPS
data.[16] The UV-vis and FTIR results strongly suggest that the
REQ3 ligands are essentially the same as those of AlQ3, and
Adv. Funct. Mater. 2004, 14, No. 10, October

certainly very similar to each other. Therefore chemical differences are not responsible either for the differences between
the ligand-based visible PL of the REQ3s, or for the difference
between the majority of the REQ3 and AlQ3.
The photoluminescent behavior of the REQ3s reported here
falls into two categories, one where the PL arises solely from
the ligand, with no contribution from the rare earth ions and
one where rare earth luminescence is observed, i.e., ErQ3 and
YbQ3. Considering first the ligand-based luminescence, the
peak at 500 nm can be assigned to emission from singlet states
(fluorescence), analogous to that observed from AlQ3.[17] Conversely the peak at 575 nm can be assigned to emission from
triplet states, i.e., phosphorescence. The production of triplets
from singlets via intersystem crossing is greatly enhanced in
these systems by the presence of a heavy ion, the so called
heavy atom effect.[18] This emission can be distinguished from
singlet fluorescence emission by its longer radiative lifetime.
Peaks at similar wavelengths in PL spectra of heavy transition
metal tris-hydroxyquinolines[17] have been shown to be due to
phosphorescence, exhibiting the characteristic long lifetimes in
comparison to that of the fluorescence peak.
We now consider the 4f4f emission, the mechanism of rare
earth luminescence, when sensitized by organic ligands is
generally accepted as the following: 1) absorption of a photon
produces an excited singlet state on the ligand; 2) intersystem
crossing from the excited singlet to a triplet state; 3) intra-molecular energy transfer from the triplet state of the organic to
one of the excited 4f states of the lanthanide ion, via a Dexter
transfer mechanism;[19] 4) production of lanthanide luminescence by intra-4f transitions within the ion.
Figure 6 shows a schematic energy level diagram of the emissive states of the rare earths[20] compared to the singlet and
triplet states of the hydroxyquinoline ligand. Since the lowest
energy singlet and triplet states cannot be directly identified
from the absorption and luminescence spectra, as an approximation for the ligand singlet and triplet energies we take the

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 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

981

4.0
2

3.5

-*

Q ,Yb3+

2.77 eV

2.5

P0
4

2.0

D2

G5/2

D4

F9/2
5

D0

2.25 eV

F3

G4

S2

Energy

T1

* 2
Q ,Yb3+ ( F5/2)

1.27 eV
4

1.5

F3/2

2
4

1.0
5

0.5

6
7

0.0

F7/2

H4

I9/2

H5/2

F0

S7/2

F5/2

I13/2

Q ,Yb3+

I7

H13/2

Ground state

F5

F6

H15/2

I8

I15/2

H6

F7/2

Figure 7. Schematic energy level diagram for the chemiluminescent redox


process responsible for the Yb3+ luminescence in YbQ3.

Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb
Lanthanide
Figure 6. Schematic energy level diagram showing the emissive levels of
the lanthanides, and the singlet and triplet energies of the quinolate ligands.

values calculated by Martin et al.[21] for AlQ32.77 eV


(447 nm) and 2.13 eV (581 nm) for the singlet and triplet respectively. These values are consistent with our experimental
results, as they place the singlet energy at the point of overlap
of the absorption and (singlet) luminescence spectra, and the
triplet energy at the (triplet-derived) phosphorescence peak.
Figure 6 shows that energy transfer from the triplet level of the
ligand to the emissive states of Er and Yb is energetically
favorable, in agreement with the observed IR luminescence.
However, from Figure 6, it can also be clearly seen that transfer from the triplet level of the organic ligand to the 5S2 or 5F3
states of Ho, the 4F9/2 state of Dy, and the 6P state of Gd is not
energetically favorable, as these states are higher in energy
than the triplet state of the ligand. Figure 6 further suggests
that triplet transfer to the emissive levels of all the rare earths
is likely to be energetically unfavorable, except for the IR
emissions of NdQ3, which have in fact been observed experimentally.[22]
While energy transfer from the triplet level of the ligand to
the emissive states of Er and Yb is energetically favorable, for
efficient transfer other considerations must also be taken in to
account. The efficiency of energy transfer from the ligand triplet to the to rare earth ion is directly proportional to the spectral overlap of the donor emission and the acceptor absorption.
Figure 4 shows the absorption spectra of YbCl3 and ErCl3
showing the RE3+ absorption peaks. For Er3+, states energetically resonant with the ligand triplet state are present, however
no such overlap is present for Yb3+. Therefore the triplet transfer mechanism cannot be responsible for the infrared luminescence seen in YbQ3, as has already been pointed out by Khreis
et al.[7]
A different mechanism for obtaining Yb3+ emission, which
does not require the presence of overlapping energy states, has
been proposed by Horrocks et al.[23] This mechanism, which is
shown in Figure 7, exploits the mixed valence behavior of Yb,
involves a charge transfer from the ligand to the Yb3+, and can
982

Q ,Yb2+

S1

3.0

Energy (eV)

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J. Thompson et al./4f4f Luminescence from Rare Earth Organic Chelates

 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

be described as an internal chemiluminescent redox reaction.


The quinoxy ligand can be optically excited into a singlet state,
from which electron transfer to the rare earth ion can occur,
thereby reducing the Yb3+ to Yb2+, and simultaneously oxidizing the quinoxy ligand, forming a neutral radical (Qrad). As
Yb2+ is a reducing agent and Qrad is an oxidizing agent a back
reaction can occur. If the driving force of this back reaction,
i.e., the change in free energy DG is greater than the energy of
the emissive (2F5/2) state, then the Yb3+ formed may be either
in the ground state, or in the excited state, thereby producing
the characteristic 980 nm luminescence.
The change in free energy DGF for the forward reaction may
be estimated using:[23]
DGF = E(Qrad /Q) E(Q)* E(Yb3+/Yb2+)

(1)

Where E(Qrad/Q) is the reduction potential of the radical


quinolate ligand, E(Qrad)* is the energy of ligand singlet excited state, and E(Yb3+/Yb2+) is reduction potential of the metal ion. For E(Q)* we again take the energy of the ligand
singlet excited state to be 2.77 eV, as discussed earlier. For
E(Yb3+/Yb2+) we take the standard value of 1.05 eV.[24] For
E(Qrad/Q) we take as an approximation the ionization energy
of AlQ3, 5.7 eV,[25] corrected using the standard value of
4.5 eV, in order to have a common reference to the standard
hydrogen electrode, to give a value of 1.2 eV. Using these values we obtain a value of DG = 0.5 eV for the forward reaction.
The driving force of the back reaction can be estimated
using:[23]
DGB = E(Qrad /Q) E(Yb3+/Yb2+)

(2)

from which we obtain a value of DGB = 2.25 eV. Taking the


obtained values of DG for the forward and back reactions, the
energy of the singlet state, and the energy of the 2F5/2 state allows a quantitative consideration of the feasibility of the redox
reaction as shown in Figure 7. It can be seen from Figure 7 that
the electron transfer from the ligand to the rare earth ion is
energetically feasible, and that the resulting Qrad/Yb2+ state is
indeed higher in energy that the 2F5/2 state.

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Adv. Funct. Mater. 2004, 14, No. 10, October

Note that this mechanism cannot proceed via electron transfer from the triplet state of the quinoline ligand, as its energy
(2.13 eV) is below that of the Qrad/Yb2+ state. Therefore, of the
materials studied, only ErQ3 has a competing mechanism to
phosphorescence for the decay of triplet states. As can be seen
from Figure 4, the visible PL spectrum from the evaporated
thin film of ErQ3 differs from those of the other REQ3s in that
its triplet emission seems to be largely absent.
The visible PL spectra of all the powder samples appear to
be dominated by singlet emission, rather than the triplet emission that dominates the majority of the thin-film spectra. It is
well known that AlQ3 can consist of two different isomers, the
fac and the mer. The mer isomer has been calculated as
being the most stable,[21] and is therefore expected to be predominant, especially in thin evaporated films. Klink et al.[19] have
demonstrated that different isomers of the same rare earth chelate can have greatly different intersystem crossing rates, leading to characteristic 4f4f luminescence being observed for
only one of the two isomers. In the case of the REQ3s it has
been shown that two isomers of YbQ3 exist[7] and that one predominates in thin films. Given the chemical similarity of the
REQ3s it seems likely that this is the case for the other REQ3s.
In the powdered samples there is no reason to suspect that one
isomer predominates. If it is indeed the case that one isomer
predominantly fluoresces while the other phosphoresces, then
one would expect the luminescence spectra to both show singlet and triplet emission, as seems to be the case in Figure 5.
In both Figures 4 and 5, the spectral line shape of GdQ3 differs somewhat from all the other REQ3s. However, as the spectral line shape seems to depend upon the relative concentration
of the isomers present, and it is known that gadolinium has different complexing behavior in comparison to the other rare
earths, it is not unreasonable that its spectral line shape is
anomalous.

4. Conclusion
The UV-vis and FTIR spectra indicate that the heavy REQ3s
are all chemically similar to each other and to AlQ3 at least in
terms of the ligand behavior. Characteristic rare earth 4f4f
luminescence is only observed for ErQ3 and YbQ3 among the
heavy REQ3s, due to the relatively low energy of the ligand
triplet state, as shown in Figure 6. The data of Figure 6 also imply that characteristic rare earth 4f4f luminescence will not be
observed for any of the other REQ3s, except for the IR luminescence of NdQ3. The triplet transfer mechanism appears unlikely be responsible for the observed Yb 4f4f luminescence
observed in YbQ3. Instead an internal chemiluminescent process, Figure 7, has been shown to be energetically favorable.
The thin film PL spectra of all the heavy REQ3s are dominated
by triplet emission, except for that of ErQ3 for which transfer
to the Er3+ ion represents an efficient alternative. The PL spectra of the powder samples, which would be expected to consist
of approximately equal amounts of both isomers, are dominated by singlet emission. This is in contrast to the results from
the thin films and suggests that the isomer which predominates
Adv. Funct. Mater. 2004, 14, No. 10, October

in the thin films has a much higher intersystem crossing rate


than the other isomer.
To achieve high efficiency devices utilizing the sharp emission lines from rare earth chelates, this study suggests that a
matching of the triplet state of the organic ligand to the emissive levels of the individual rare earth ion is necessary, except
in the cases where the mechanism of rare earth luminescence
can proceed via a charge transfer process.

FULL PAPER

J. Thompson et al./4f4f Luminescence from Rare Earth Organic Chelates

5. Experimental
5.1. Synthesis
The REQ3s were synthesized largely as described by Khreis et al. for
YbQ3 [7]. Rare earth trichloride-hexahydrate was dissolved in de-ionized water and then added dropwise, whilst stirring, to a solution of 8hydroxyquinoline in 80 % methanol and 20 % deionized water. Upon
addition of the chloride to the quinoline solution, the solution became
an opaque orange color. The mixture was left stirring overnight, after
which the solution color had changed from orange to bright lemon yellow. The resulting solution was filtered using vacuum filtration equipment and the precipitate washed with cold (20 C) methanol. The yellow powder obtained was then re-dissolved in a minimum of hot
methanol and a few drops of hexane were added. The solution was then
placed in a freezer to allow the final product to precipitate out. In some
cases the solvent had to be further evaporated before the product could
be collected. Reaction yields were generally between 20 and 40 %. Calorimetry measurements showed that a small amount of unreacted hydroxyquinoline remained in the complex, but this could be easily removed by heating the product under vacuum to 120 C for a few hours.
Mass spectroscopy [16] confirmed that the product was in fact REQ3
and X-ray photoemission results (XPS) [16] showed that the purity was
sufficient to allow the formation of clean stoichiometric films by evaporation in vacuum. All materials were obtained from Sigma Aldrich, including AlQ3, which was purified in the same manner as the REQ3s.
Thin films (225 25 nm) of each REQ3, and AlQ3 for comparison,
were deposited onto quartz glass substrates, by subliming the purified
powder in vacuum (106 mbar), at an evaporation rate of ~ 0.2 s1,
and a nominal source temperature of 370 C. Interestingly, the evaporation temperatures for the REQ3s were found to be ~ 125 C higher than
that of AlQ3 evaporated at the same rate on the same system. Samples
of the purified powder were also made, by placing some of the material
between two pieces of quartz glass.

5.2. Optical Characterization


Photoluminescence (PL) measurements were carried out by exciting
the samples with a He-Cd laser (325 nm) and collecting the signal with
an Ocean Optics charge coupled detector. UV-visible (UV-vis) absorption spectra measurements were performed using a Varian Cary 100
Scan spectrophotometer. Fourier transform infrared (FTIR) spectra
were taken using a Jasco FT/IR 430 Fourier Infrared spectrometer, by
dissolving the purified powders in a small amount of chloroform and allowing the chloroform to evaporate off, leaving just the REQ3 on the
measurement cell.

[1]
[2]

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Received: December 5, 2003


Final version: February 10, 2004

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983

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J. Thompson et al./4f4f Luminescence from Rare Earth Organic Chelates


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