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Sterically shielded blue thermally activated

delayed fluorescence emitters with improved
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Cite this: Mater. Horiz., 2016,

3, 145 efficiency and stability†
Received 2nd November 2015,
Accepted 4th January 2016 Dongdong Zhang, Minghan Cai, Yunge Zhang, Deqiang Zhang and Lian Duan*

DOI: 10.1039/c5mh00258c

www.rsc.li/materials-horizons

Blue emitters with thermally activated delayed fluorescence (TADF)

have the potential to achieve 100% internal quantum efficiency, though Conceptual insights
the strategy to design stable blue TADF emitters remains unexplored. Blue emitters with ultimate efficiency and high stability remain the ‘‘Holy
Grail’’ for organic light-emitting diode (OLED) research. Although blue
Here, high efficiency and improved stability are achieved simulta-
phosphorescent OLEDs can achieve extremely high efficiencies, their
neously for blue or sky blue TADF emitters by wise designing of lifetimes are far from satisfactory in scientific literatures. Thermally
molecular structures using tert-butyl units. The tert-butyl substituents activated delayed fluorescence (TADF) emitters, on the other hand, may
act like a shield surrounding the luminance core, not only promoting provide another strategy to develop blue emitters with high efficiency and
the photoluminescence efficiency, but also improving the stability of long lifetime. However, though high efficiencies have been achieved, the
lifetimes of the devices based on blue TADF emitters are far from
the compounds. Consequently, the device with a sterically shielded
satisfactory. Here, high efficiency and long-term stability are achieved
emitter achieves a maximum external quantum efficiency as high as simultaneously in one device based on blue and sky blue TADF emitters
21.2% and a record long T50 (time to 50% of initial luminance) of 770 h for the first time. We demonstrate that sterically shielded TADF emitters
at an initial luminance of 500 cd m2, corresponding to a half lifetime of with tert-butyl units show significantly improved efficiencies and
12 873 h at 100 cd m2. stabilities. The OLED with a sterically shielded sky blue TADF emitter
achieves a maximum EQE as high as 21.2% and a record long T50 of
12 873 h at an initial luminance of 100 cd m2. The strategy proposed
Organic light emitting diodes (OLEDs) are promising for the here may shed light on the design of more efficient and stable blue TADF
next generation displays and lighting due to their low power emitters.
consumption and potentially long operational lifetime.1–5 How-
ever, despite all the efforts devoted, blue OLEDs remain a
bottleneck for further application of OLEDs.6–8 Although a great demand to find new strategies to design blue emitters
organic electrophosphorescent emitters have significantly with high efficiency and excellent stability.
lower the power consumption than fluorescent emitters, blue Recently reported thermally activated delayed fluorescence
phosphorescent OLEDs (PHOLEDs) with long lifetimes are (TADF) emitters may provide an opportunity to solve the
rare.9,10 To improve the operational lifetime of PHOLEDs, problems of blue OLEDs.12–16 TADF emitters are intrinsically
Forrest et al. proposed a graded doped structure to suppress pure organic materials, which can harvest triplet excitons via
the triplet-polaron annihilation, leading to a blue device with reversed intersystem crossing (RISC).16c Therefore, TADF blue
a T80 lifetime (time to 80% of initial luminance) of 213 h at emitters have the potential to combine the advantages of fluores-
1000 cd m2.11 However, the external quantum efficiency (EQE) cence and phosphorescence materials. However, although highly
of the device is about only 9.5%, much lower than the highest efficient devices based on blue TADF emitters have been
values of blue PHOLEDs reported previously. Therefore, there is reported,17,18 the operational lifetimes of the devices are far away
from satisfaction. The OLED based on a blue TADF emitter, 10,100 -
Key Lab of Organic Optoelectronics and Molecular Engineering of Ministry of
(sulfonylbis(4,1-phenylene))bis(9,9-dimethyl-9,10-dihydroacridine)
Education, Department of Chemistry, Tsinghua University, Beijing 100084, (DMAC-DPS), achieved a maximum EQE as high as 19.5%,17a but
P. R. China. E-mail: duanl@mail.tsinghua.edu.cn; Fax: +86-10-62795137; the T50 (time to 50% of initial luminance) was only 1 h at an
Tel: +86-10-62788802 initial luminescence of 500 cd m2. To prolong the lifetime of
† Electronic supplementary information (ESI) available: Experimental details
blue TADF OLEDs, Lee et al. proposed stable blue TADF emitters
including general information, synthesis procedure as well as device fabrication
and characterization, the DSC and TGA thermograms, the CV curves, solvent
based on triazine/dicarbazolylbenzene derivations and a T80 of
dependent PL spectra and the spectra at 77 K, the PL decay curves, the 52 h at 500 cd m2 was achieved.19 Nevertheless, the EQE of the
performances of the devices. See DOI: 10.1039/c5mh00258c stable device is only around 2% although a maximum EQE of

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18.9% can be achieved for devices with different structures. To our

knowledge, blue TADF based devices with high efficiency and long
lifetime simultaneously are not reported until now.
To achieve such a goal, the molecular structure should be
rationally designed. For conventional fluorescent emitters,
besides developing a highly efficient luminance core, the
modification of the peripheral substituents is also important.
The tert-butyl unit has been widely adopted in conventional
fluorophores to reduce the concentration quenching effect and
promote the photoluminescence (PL) efficiency.20 Although tert-
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butyl has been introduced in green TADF emitters to improve Scheme 1 The synthesis process of the emitters.
their solubility,21 no one has ever revealed the influence of
substituents on the efficiencies and stabilities of TADF emitters.
It is anticipated that the efficiencies and stabilities of the blue these emitters was investigated (Fig. S1, ESI†) and these com-
TADF emitters can be improved by attaching bulky substituents pounds show good thermal stability with decomposition tempera-
such as tert-butyl units, which has been demonstrated for tures in the range of 436–454 1C and high glass transition
conventional fluorophores. temperatures (Tg) in the range of 316–325 1C. Such excellent
Herein, we report blue and sky blue TADF emitters incorporating thermal properties readily endow OLEDs based on them with high
cyano and carbazolyl units as the eletron-withdrawing and electron- morphological stability, favorable for the OLED stability during
donating moieties with the luminophores sterically shielded by tert- operation.
butyl units. The cyano and carbazolyl units are adopted since they The geometrical and electronic properties of the compounds
have been demonstrated to be stable moieties.12c,d It is observed that were studied via density functional theory (DFT) and time-
the tert-butyl substituents act like a shield to cover the luminance dependent DFT (TDDFT) calculations using the B3LYP hybrid
core, not only promoting the PL efficiency, but also improving the functional. As can be seen from Fig. 1, for all materials,
stability of the compounds. Consequently, the device with a sterically the highest occupied molecular orbitals (HOMOs) are mainly
shielded emitter achieves a maximum external quantum efficiency delocalized over the carbazolyl moieties while the lowest
as high as 21.2% and a record long T50 (time to 50% of initial unoccupied molecular orbitals (LUMOs) are mainly centered
luminance) of 770 h at an initial luminance of 500 cd m2, on the benzonitrile moieties, indicating that the carbazolyl
corresponding to a half lifetime of 12 873 h at 100 cd m2. moieties act as electron donors and the benzonitrile moieties
A remarkable feature of our system is that high efficiency and high as electron acceptors. The distribution of the frontier orbitals is
stability are achieved simultaneously for the first time in one device barely affected by the introduction of the tert-butyl units.
based on blue and sky blue TADF emitters. Besides, all the compounds show twisted structures with a
All four blue or sky blue TADF emitters, 2,3,5,6-tetra(9H- dihedral angle around 601 between the planes of the carbazolyl
carbazol-9-yl)benzonitrile (4CzBN), 2,3,5,6-tetrakis(3,6-di-tert- and benzonitrile groups, resulting from the large steric
butyl-9H-carbazol-9-yl)benzonitrile (4TCzBN), 2,3,4,5,6-penta- hindrance caused by the carbazolyl and benzonitrile units.
(9H-carbazol-9-yl)benzonitrile (5CzBN) and 2,3,4,5,6-pentakis- Consequently, the HOMO and LUMO of the four compounds
(3,6-di-tert-butyl-9H-carbazol-9-yl)benzonitrile (5TCzBN), were are spatially well separated and small DESTs can be anticipated.
synthesized in a one-step, catalyst free aromatic nucleophilic Besides, rather than completely separated, the HOMO and
substitution reaction as can be seen from Scheme 1 with the LUMO levels were also found to be weakly overlapped in the
reaction yields of all compounds of above 90%. Since no phenyl unit, which is helpful to maintain a high radiative decay
palladium or other rare-earth-metal catalysts were required, rate (kr).12c Therefore, both small DESTs and high krs can be
these compounds are cost effective, showing superiority of anticipated for the four compounds.
competitive advantages over phosphorescent materials. As we The calculated DESTs are 0.19 eV, 0.14 eV, 0.19 eV and
know, the most well-known highly efficient TADF emitter is 0.16 eV for 4CzBN, 4TCzBN, 5CzBN and 5TCzBN, respectively.
1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN),12c The small DESTs indicate the efficient RISC and consequently
which is based on phthalonitrile/carbazole derivations. The efficient TADF emission. As can be seen from Fig. 1, there are
EQE as high as 30% has been achieved13c based on 4CzIPN other adjacent energy levels between the lowest singlet and
and the molecule stability has been systematically studied.12d triplet energy levels, which would act as steps for triplet exciton
However, the strong electron-withdrawing abilities of the up-conversion, resulting in an even more efficient RISC process.22
dicyano units render them difficult to fabricate efficient blue Compared with 4CzBN, the DEST of 4TCzBN is smaller. A similar
emitters. A wise and effective method that can be adopted is using trend is also observed for 5CzBN and 5CzTBN. It is reported
the benzonitrile moiety rather than the phthalonitrile moiety to that the oscillator strength for absorption ( f ) would be expected
fabricate the TADF emitters. The electron-withdrawing abilities of to decrease with decreasing DEST.18 However, the calculated
the benzonitrile moiety are weakened by reducing a cyano unit on f value of 4CzBN is much higher than that of 4TCzBN. It can
the benzene ring, resulting in a relatively large energy gap which is be understood that, on one hand, the HOMO distribution of
favorable to fabricate blue TADF emitters. The thermal stability of 4TCzBN is more delocalized compared to 4CzBN, since the

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Fig. 1 The molecular structures, the distribution of the frontier levels and the calculated energy levels of the emitters.

distribution of HOMO levels is slightly extended to the difference was observed for the oxidation part of the compounds
tert-butyl unit as can be seen from Fig. 1.18 On the other hand, with or without the tert-butyl substituent. For 4CzBN and 5CzBN,
the large steric hindrance introduced by the substituent can the oxidation processes are not reversible with the oxidation
suppress both non-radiative deactivation and changes in potential gradually shifting to lower potentials and the current
the geometries of the singlet and triplet states, leading to a increasing during the repeated CV scans. It was reported that
high f. The same trend is also observed for 5CzBN and 5TCzBN. this irreversible behavior is mainly due to the active sites of
As is reported, large f values are helpful to obtain large krs carbazole (3,6-positions).23 In contrast, after the introduction of
and thus may lead to higher prompt efficiencies for TADF two tert-butyl groups at the 3,6-positions of carbazole, 4TCzBN
emitters.18 and 5TCzBN show reversible oxidation behavior with unchanged
The electrochemical properties of the compounds were curves during repeated CV scans, suggesting that the electro-
probed by cyclic voltammetry (CV) measurement. As can be chemical stabilities of the emitters are greatly improved. The
seen from Fig. S2 (ESI†), all the compounds show reversible HOMO and LUMO values are summarized in Table 1. With the
reduction reactions, attributed to the introduction of electron- increasing number of carbazolyl or the introduction of tert-butyl
withdrawing benzonitrile units. On the contrary, a clear units, the HOMO would be slightly shallower.

Table 1 Summary of the photophysical characteristics of the emitters

Emission HOMO LUMO fPL Stokes shift

(nm) T1 (eV) DEST (eV) f (eV) (eV) Td (ms) kp (s1) (prompta/totalb) (cm1)
4CzBN 442 2.70 0.30 0.0042 5.73 2.87 4.0 1.03  107 0.10/0.49 2695
4TCzBN 456 2.62 0.24 0.1087 5.48 2.73 3.9 2.07  107 0.20/0.68 1720
5CzBN 464 2.68 0.22 0.0339 5.55 2.74 3.7 0.57  107 0.08/0.70 3263
5TCzBN 480 2.60 0.17 0.0427 5.45 2.74 3.4 0.87  107 0.13/0.86 2534
a b
Measured in toluene without degassing oxygen. Measured in toluene after bubbling nitrogen gas.

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Fig. 2 (a) The absorption and the emission spectra of the emitters in toluene at room temperature. (b) The photoluminescence transient decay curves of
the emitters doped in mCBP films (10 wt%). (c) The prompt (o1 ms) and the delayed (41 ms) spectra of 4CzBN and 4TCzBN. (d) The prompt (o 1 ms) and
the delayed (41 ms) spectra of 5CzBN and 5TCzBN.

The photophysical properties of these compounds were suppress the changes in the geometries of the emitters. To
analyzed using ultraviolet-visible (UV-vis) and PL spectro- evaluate the triplet energies of these compounds, the emission
meters. The absorption spectra of these compounds (Fig. 2a) at 77 K was measured, as can be seen from Fig. S4 (ESI†). The
were similar to each other and all exhibit an absorption broad phosphorescence spectra at 77 K are well resolved, indicating
band at around 420 nm, mainly associated with the electron that their T1 states are 3pp* states.13b For the 3pp* state, the
transfer from the carbazolyl units to the benzonitrile units. The highest energy peak of its emission identifies its zero–zero
absorption spectra are slightly red shifted by increasing the energy (E0–0). On the other hand, their singlet states are charge
number of carbazolyl groups or introducing tert-butyl substi- transfer (CT) states without any vibronic structure and thus
tuents. All the compounds show blue emission in toluene with their E0–0s should be calculated from the onset of their broad
peaks at 442 nm, 456 nm, 464 nm and 480 nm for 4CzBN, emission band.13b Therefore, the measured DESTs were 0.30,
4TCzBN, 5CzBN and 5TCzBN, respectively. As can be seen from 0.24, 0.22 and 0.17 eV for 4CzBN, 4TCzBN, 5CzBN and 5TCzBN,
Fig. S3 (ESI†), the PL spectra of the emitters strongly depend on respectively. Similar to the theoretical calculation results, the
the polarity of the solvent, demonstrating that the emission is addition of tert-butyl unit slightly reduces the DESTs of the
originated from the charge transfer (CT) states. The introduced compounds. The PL efficiencies of these compounds were
tert-butyl substituent shows a limited influence on the emission measured in toluene with or without degassing oxygen. As
of the compounds, with only slight red shifts. The stokes shift can be seen from Table 1, after bubbling nitrogen gas, the
can be calculated using the biggest absorption peaks and the efficiencies of all compounds are sharply increased compared
emission peaks of the compounds, as summarized in Table 1. with the one without treatment. The transient and time-
The stokes shifts are small for these compounds since the resolved PL characteristics of these emitters dispersed in
cyano groups have been demonstrated to suppress the changes 3,3-di(9H-carbazol-9-yl)biphenyl (mCBP) with a high-triplet-
in the geometries of the singlet and triplet states of the energy (2.84 eV) were measured. As can be seen from Fig. 2b,
compounds. prompt and delayed components were clearly observed from the
Compared with 4CzBN (5CzBN), the stokes shift of 4TCzBN transient PL decay curves of the four emitters. The PL decay
(5TCzBN) is even smaller, owing to the large steric hindrance curves at different temperatures were also measured (Fig. S5,
introduced by tert-butyl as we discussed above which can also ESI†) and they varied with different temperatures, corresponding

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to the characteristics of the TADF emitters reported previously.12 of RISC (FRISC) were also calculated and are summarized in
The time-resolved PL spectra of these materials (Fig. 2c and d) Table S1 (ESI†). The introduction of tert-butyl units induces
obtained before and after 1 ms were almost the same, indicating higher kps, corresponding to the large f values calculated above.
that the emissions were from the same state. These behaviors Besides, the kRISC and FRISC of 4TCzBN (or 5TCzBN) are also
confirmed that the four emitters were TADF materials. The enhanced compared with 4CzBN (or 5CzBN), owing to the
prompt decay rate (kp), the rate of RISC (kRISC) and the efficiency relatively small DEST when tert-butyl units are introduced. There-
fore, the introduction of the tert-butyl substituent increases the
PL efficiencies of the emitters, thanks to the increased f and
suppressed non-radiative deactivation as well as improved RISC.
To evaluate the electroluminescence properties of the TADF
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emitters, devices were fabricated with device structures of ITO/

HATCN (5 nm)/NPB (30 nm)/TCTA (10 nm)/EML (30 nm)/
DpyPA : Liq (1 : 1, 30 nm)/LiF (0.5 nm)/Al (150 nm). HATCN,
NPB, TCTA, DPyPA and Liq are dipyrazino[2,3-f:2 0 ,3 0 -h]quinoxa-
line-2,3,6,7,10,11-hexacarbonitrile, N,N 0 -bis(1-naphthalenyl)-
0 0 0
N,N -diphenyl-[1,1 -biphenyl]-4,4 -diamine, N,N,N-tris(4-(9-carbazolyl)-
phenyl)amine, 9,10-bis(3-(pyridin-3-yl)phenyl)anthracene and
(8-hydroxyquinolinolato)-lithium, respectively. The doping con-
centrations of the four emitters were optimized to be 40 wt%.
The structures of the devices and the molecules are shown in
Fig. 3. As can be seen from Fig. 4a, the devices show blue to
sky-blue emission with emission peaks at 458 nm, 463 nm,
Fig. 3 The device and the molecular structures. 490 nm and 490 nm for 4CzBN, 4TCzBN, 5CzBN and 5TCzBN,

Fig. 4 (a) The electroluminescence spectra of the devices in a spectral range of 380–780 nm measured under a voltage of 6 V. (b) Current density as a
function of voltage for devices. (c) External quantum efficiency as a function of current density for devices. (d) The lifetimes of the devices measured at an
initial luminance of 500 cd m2.

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Table 2 The summary of the device performances

mCBP
Voltage (V) (10 cd m2) EQEmax (%) EQE (500 cd m2) PEmax (lm W1) CIE Lifetime (h)
4CzBN 3.31 10.6 5.4% 15.7 (0.17, 0.20) 62
4TCzBN 3.30 16.2 6.5% 24.4 (0.16, 0.22) 167
5CzBN 2.96 16.7 9.8% 40.0 (0.22, 0.40) 176
5TCzBN 2.90 21.2 10.7% 56.1 (0.21, 0.41) 770

respectively. The almost same spectra of 5CzBN and 5TCzBN (or Forrest et al. suggested that increasing the intermolecular
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4CzBN and 4TCzBN) facilitate us to compare their lifetimes. separation through the addition of steric bulk to the dopant
The turn-on voltages (at 1 cd m2) of 4CzBN and 4TCzBN are molecules might reduce the exciton–polaron annihilation and
around 3.0 V while they are around 2.5 V for 5CzBN and increase the device lifetime.24 The tert-butyl units introduced in
5TCzBN, which are relatively low among the blue TADF devices our TADF emitters could also efficiently increase the inter-
(Fig. 4b). The maximum EQEs of those devices are 10.6%, molecular distance and reduce the exciton–polaron annihilation
16.2%, 16.7% and 21.2% for 4CzBN, 4TCzBN, 5CzBN and in TADF devices, resulting in a promoted lifetime. What is more,
5TCzBN, respectively (Fig. 4c). These values are among the the reduced lifetime of the excitons, which reduces the chance of
highest efficiencies of the devices based on blue TADF emit- unwanted chemical reactions25,26 and the high Tg as well as the
ters.17–19 The higher efficiencies of the devices with 4TCzBN improved uniformity of the EML film attributed to the introduced
and 5TCzBN are owing to the higher PL efficiencies and the tert-butyl units are all helpful to improve the device stability.
more efficient RISC process resulted from smaller DESTs of the In the search of stable emitters for OLEDs, screening stable
emitters with tert-butyl units, demonstrating that the efficien- moieties and designing a planar molecular structure are regarded
cies of the TADF emitters can be improved by rationally as important parameters.19 Here, we demonstrate that besides
introducing substituents. The device performances are sum- the above factors, the substituent effect is also critical to the
marized in Table 2. device efficiency and lifetime.
The operation lifetimes of the OLEDs were measured at an initial Besides the emitters, hosts would also have considerable
brightness of 500 cd m2 under constant current. As can be seen influence on the performance of OLEDs. For example, when a
from Fig. 4d, the T50s are 62 h, 167 h, 176 h and 770 h for 4CzBN, higher triplet energy host, bis(2-(diphenylphosphino)phenyl)-
4TCzBN, 5CzBN and 5TCzBN, respectively. For display applica- etheroxide (DPEPO), was used, the EQE of the 4TCzBN based
tions, the device lifetime of blue emitters is usually measured at blue device can be promoted to 19.5% (Fig. S7, ESI†). Addition-
an initial luminance of 100 cd m2.11 By adopting a degrada- ally, the efficiency roll-off of those blue emitters can be reduced
tion acceleration factor that relates luminance to lifetime, by using a bipolar host, 2,6-bis(3-(carbazol-9-yl)phenyl)pyridine
 n


500 cd m2 (26DCzPPy), owing to the more balanced charges in the EML
viz. T50 100 cd m2 ¼ T50 500 cd m2  with
100 cd m2 (Fig. S8, ESI†). Therefore, it is believed that the efficiencies and
n = 1.75, the extrapolated blue PHOLED lifetime is 12 873 h at an stabilities of the devices based on these blue TADF emitters can
initial luminance of 100 cd m2. These values are much better be further improved with suitable hosts.
than those of the devices using DMAS-DPS as the emitter with In conclusion, the influence of the substituent on the effici-
an even higher peak device efficiency17a and are approaching encies and stabilities of the blue TADF emitters is thoroughly
the best blue phosphorescent devices using a single-stack studied for the first time. Sterically shielded blue TADF emitters
structure.11 This is the first time that high efficiency and by bulky substituents such as tert-butyl would lead to higher
long-term stability are achieved simultaneously in one device efficiency and better stability. Consequently, the device with a
based on blue or sky blue TADF emitters. sterically shielded emitter achieves a maximum EQE as high as
Compared with 5CzBN (or 4CzBN), the operational lifetime 21.2% and a T50 of 770 h at an initial luminance of 500 cd m2,
of the device based on 5TCzBN (or 4TCzBN) is improved by corresponding to a half lifetime of 12 873 h at 100 cd m2.
4.6 (2.7) folds although their CIE coordinates are almost the This is the first report that ultimate efficiency and long-term
same as can be seen from Table 2. The prolonged lifetimes of stability are achieved simultaneously in one device based on
devices by introducing tert-butyl units can be attributed to a blue or sky blue TADF emitters. The strategy proposed here
combination of several reasons. Firstly, as we discussed above, may shed light on the design of more efficient and stable blue
the electrochemical stabilities of the emitters are improved, TADF emitters.
which is beneficial for improving the lifetimes. Secondly, We would like to thank the National Natural Science
the tert-butyl units surrounding the luminophores of 4TCzBN Foundation of China (Grant No. 51525304 & 51173096) and
and 5TCzBN act as a sterical shield, reducing the interaction the National Key Basic Research and Development Program of
with the adjacent molecules. It is reported that the exciton– China (Grant No. 2015CB655002) for financial support. This
polaron annihilation process may lead to the degradation of work was also supported by CAS Interdisciplinary Innovation
OLEDs during continuous operation. Considering the distance Team. And we’d like to thank Prof. Bing Yang of Jilin Univ. for
dependence of the energy transfer from excitons to polarons, his help in measuring the transient decay curves of the films.

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