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de

FULL PAPER
Versatile, Benzimidazole/Amine-Based Ambipolar
Compounds for Electroluminescent Applications:
Single-Layer, Blue, Fluorescent OLEDs, Hosts for
Single-Layer, Phosphorescent OLEDs
By Chih-Hsin Chen, Wei-Sheng Huang, Mei-Yi Lai, Wen-Cheng Tsao, Jiann T. Lin,*
Ying-Hsien Wu, Tung-Huei Ke, Li-Yin Chen, and Chung-Chih Wu*

A series of compounds containing arylamine and 1,2-diphenyl-1H-
benz[d]imidazole moieties are developed as ambipolar, blue-emitting
materials with tunable blue-emitting wavelengths, tunable ambipolar carrier-
transport properties and tunable triplet energy gaps. These compounds
possess several novel properties: (1) they emit in the blue region with high
quantum yields; (2) they have high morphological stability and thermal
stability; (3) they are capable of ambipolar carrier transport; (4) they possess
tunable triplet energy gaps, suitable as hosts for yellow-orange to green
phosphors. The electron and hole mobilities of these compounds lie in the
range of 0.68–144 T 10
6 and 0.34–147 T 10
6 cm2 V
1 s
1, respectively.
High-performance, single-layer, blue-emitting, fluorescent organic light-
emitting diodes (OLEDs) are achieved with these ambipolar materials. High-
performance, single-layer, phosphorescent OLEDs with yellow-orange to
green emission are also been demonstrated using these ambipolar materials,
which have different triplet energy gaps as the host for yellow-orange-emitting
to green-emitting iridium complexes. When these ambipolar, blue-emitting
materials are lightly doped with a yellow-orange-emitting iridium complex,
white organic light-emitting diodes (WOLEDs) can be achieved, as well by the
use of the incomplete energy transfer between the host and the dopant.
[*] Dr. J. T. Lin, Dr. C.-H. Chen, W.-S. Huang, M.-Y. Lai, Dr. W.-C. Tsao
Institute of Chemistry, Academia Sinica
Taipei, Taiwan 115 (Republic of China)
E-mail: jtlin@chem.sinica.edu.tw
Prof. J. T. Lin
Department of Chemistry, National Central University
Chungli, Taiwan 320 (Republic of China)
Prof. C.-C. Wu, Y.-H. Wu, T.-H. Ke, L.-Y. Chen
Department of Electrical Engineering
Graduate Institute of Electro-optical Engineering and
Graduate Institute of Electronics Engineering
National Taiwan University
Taipei, Taiwan 106 (Republic of China)
E-mail: chungwu@cc.ee.ntu.edu.tw
DOI: 10.1002/adfm.200900561
1. Introduction
Organic light-emitting diodes (OLEDs)
have drawn great attention because of their
applications in full-color, flat-panel displays
and solid-state lighting.[1] Considerable
progress has been made in small-molecule-,
dendrimer-, and polymer-based OLEDs in
recent years. Within the past decade,
organo-transition metal complexes have
emerged as promising phosphorescent
emitters for OLEDs since these complexes
are able to harvest both triplet and
singlet excitons and greatly improve device
efficiency;[2] however, metal complexes
normally have to be doped in an appropriate
host to avoid self-quenching. Moreover, the
materials used for the host, carrier transport
or carrier blocking need to have a suffi-
ciently large triplet (T1) energy to effectively
confine triplet excitons on phosphorescent
dopants and to prevent the back transfer
of triplet excitons from the metal complexes
to the host and adjacent functional layers.[3]
It becomes generally more difficult to
find appropriate hosts and functional
materials for blue-emitting phosphorescent materials, which have
relatively large triplet energies.[4] As such, there are only a small
number of blue-emitting phosphorescent devices that show
Commission Internationale de l0 Eclairage (CIE) y values below 0.2
(true blue), yet still with a respectable electroluminescence (EL)
efficiency.[4c,4e,4f ] Therefore, blue-emitting fluorescent materials
and devices will still play a major role in the foreseeable future of
OLED applications. Blue-emitting fluorescent materials can be
used, not only for blue-emitting OLEDs as is, but also as the host for
guest emitters to facilitate white emission and other colors.
The multilayer configuration is commonly adopted for OLEDs
because it is relatively convenient to tune the carrier transport or to
control the exciton distribution by choosing appropriate materials.
Nevertheless, for commercially viable OLED applications, it is
desirable to greatly simplify the OLED structures and fabrication.
Such a goal may be achieved if molecules possessing dual/multiple
functions are used. For example, a two-layer device structure is

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possible by use of compounds with dual functions of emission and
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hole-transport, or of emission and electron-transport. Even an
ultimate, single-layer device should be plausible if a compound
can be made highly emissive and simultaneously capable of
electron and hole transporting with balanced carriers mobilities
(i.e., ambipolar). Several criteria need to be fulfilled for developing
the materials used in single-layer OLEDs: (1) high emission
quantum yield; (2) good and balanced electron and hole mobilities;
(3) high glass-transition temperature; (4) matched highest
occupied molecular orbital (HOMO) and lowest unoccupied
molecular orbital (LUMO) energy levels with the energy levels of
the anodes and cathodes. The first three criteria have to be tackled
by appropriate molecular design and the fourth criterion can
be assisted by surface/interface modification/engineering of
the electrodes.
A viable strategy for ambipolar transport materials is to
appropriately incorporate both hole- and electron-transport units
in the same molecules. In recent years, we have successfully
developed green-emitting compounds capable of ambipolar
transport, and single-layered OLEDs using these compounds as
the sole organic component exhibited very-promising perfor-
mances.[5] After our successful attempts with single-layered,
green-emitting OLEDs, we further extended the strategy to the
development of even-more-challenging, ambipolar, blue-emitting
materials for single-layered blue OLEDs[6] and obtained an initial
success. Impressive performances were achieved with a non-
optimized, single-layer, blue-emitting device: 2.4%; 1.2 lm W
1;
2.4 cd A
1; 2378 cd m
2; (0.15, 0.12) at 100 mA cm
2. Moreover, a
high-performance, single-layer device using these compounds as
the host for a yellow-orange phosphorescent dopant was
also demonstrated: 6.9%; 4.4 lm W
1; 20 cd A
1; 19 637 cd m
2;
(0.53, 0.47) at 100 mA cm
2.
High-performance, single-component, single-layered, blue-
emitting OLEDs should be cost effective because of their
simplified device fabrication. Moreover, with the implementation
of effective, single-layer, blue OLEDs, phosphorescent OLEDs with
Figure 1. The structures of the ambipolar compounds.
2662 ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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simple device structures may be further realized if phosphorescent
metal complexes can be doped into single-layered, blue-emitting
OLEDs to generate efficient electrophosphorescence. In this paper,
we report the synthesis and characterization of highly emissive
blue fluorophores capable of ambipolar carrier transport. To
make such a vision closer to reality, in this work, we have
substantially extended our previous work on the molecular designs
of ambipolar blue-emitting materials. For instance, we carried out:
(1) exploration of the structure-property relationships for physical/
photophysical properties (fluorescence, triplet energy, thermal
properties etc.); (2) exploration of the bridging effects of different
types of linking spacers between amine and benzimidazole on
various physical/photophysical/carrier-transport properties; (3)
exploration of the effects of various linking topologies (e.g., para,
meta, etc.) on various physical/photophysical/carrier-transport
properties. With systematic variation of the molecular structures
and studies of their properties, we have developed a series of
ambipolar, blue-emitting materials with tunable blue-emitting
wavelengths, tunable ambipolar carrier-transport properties and
tunable triplet energy gaps. These materials can be used for high-
performance, single-component, single-layered, blue-emitting,
fluorescent OLEDs and as the hosts for orange and green
phosphorescent emitters to produce efficient, phosphorescent
OLEDs with simple device structures.
2. Results and Discussions
2.1. Synthesis
The compounds synthesized (1–11) in this study are shown
in Figure 1 and their synthetic sequences are illustrated in
Scheme S1 (Supporting Information). Selective replacement
of one bromo substituent in the aromatic dibromides,
2,7-dibromo-9,9-diethyl-9H-fluorene, 4,40 -dibromobiphenyl and
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2,7-dibromo-20 ,70 -di-tert-butyl-9,90 -spirobi-[fluorene], by the appear to have a lower Tg value than their congeners with a para-

diphenylamino or the carbazolyl moiety was achieved via
the Buchward–Hartwig C-N bond-formation reaction[7] or the
Ullmann C-N coupling reaction.[8] Compounds 1a–5a, 10a and
11a were obtained in moderate to good yields. The boronic acids
(1b–5b, 10b and 11b) derived from the corresponding bromide
precursors were then allowed to react with 2-(4-bromophenyl)-1-
phenyl-1H-benz[d]imidazole and 2-(3-bromophenyl)-1-phenyl-
1H-benz[d]imidazole via palladium-catalyzed Suzuki coupling
reactions[9] to yield compounds 1–11 in good yields (54–70%).
The compounds were soluble in dichloromethane, tetrahydro-
furan (THF) and toluene.
2.2. Thermal Properties
The thermal properties of the compounds were determined by
thermogravimetric analysis (TGA) and differential scanning
calorimetry (DSC) measurements (Table 1). These compounds
possess high thermal-decomposition temperatures (Td) ranging
from 373 to 467 8C. They were all amorphous once made, or readily
formed a glass from their melts upon fast cooling, and the glassy
state persisted in the subsequent heating cycles. The glass-
transition temperatures (Tg) of the compounds range from 99 to
170 8C. In accordance with previous reports, incorporation of a
9-carbazolyl unit[10] or a spirobifluorene moiety[11] significantly
raises the Td and Tg values of the compounds. For example, the Td
and Tg values increase by >40 8C and 20 8C, respectively, when
the diphenylamino unit is replaced by a 9-carbazolyl unit (2 vs. 1; 4
vs. 3; 7 vs. 6; 9 vs. 8). Replacement of the 9,9-diethylfluorene unit or
biphenyl moiety with spirobifluorene results in an increment of Td
and Tg values by >45 and >50 8C (5 vs. 1; 5 vs. 3), respectively.
Compounds with a meta-disposition between the arylamine-
containing conjugated segment and the benz[d]imidazolyl unit
FULL PAPER
disposition., that is to say, 6 vs. 1 and 8 vs. 3. This can be
rationalized by the greater energetic disorder in the meta
derivatives.[10b] It is interesting to note that compound 11 with
two meta 9-carbazolyl units has a higher Tg value than compound
10, which has one para 9-carbazolyl unit, by 31 8C.
2.3. Photophysical Properties
The main theme of this study is to construct molecules that are
capable of ambipolar transport and emit in the blue region or at
even-shorter wavelengths. Therefore, the arylamino group, a
popularly used hole-transporting unit, and the benz[d]imidazolyl
group, a well-known electron-transporting unit, are integrated in
the same molecules via a conjugated spacer. Because of its
moderate electron affinity among electron-transporting units,[12]
the benz[d]imidazolyl group was adopted to avoid a strong charge-
transfer character in the molecules, that may result in a red shift
of the emission spectra or aggregation of the molecules. The
photophysical data are collected in Table 1 and representative
absorption and emission spectra are shown in Figure 2. No
apparent solvatochromism was noticed in the absorption bands of
these compounds. The two major absorption bands ranging from
280 to 370 nm are attributed to the p-p transition. The
absorption of at longer wavelength has some charge-transfer
character and is more sensitive to the molecular structure. There is
red shift of the absorption (labs value) when the conjugation
between the arylamine and the imidazole units increases as: (1) the
conjugated spacer between the arylamine and the imidazole units
is more coplanar: 1 > 3 and 2 > 4; (2) the carbazole unit is replaced
by a stronger donor, diphenylamine: 1 > 2, 3 > 4, 6 > 7 and 8 > 9; (3)
the imidazole unit switches from the meta- to the para-disposition of
the conjugated spacer relative to diarylamine: 1 > 6, 2 > 7, 3 > 8

Table 1. Physical properties of the compounds.

Tm /Tg /Td labs, toluene labs, CH2Cl2 lem (Ff ), toluene lem (Ff ), CH2Cl2 lem (Ff ), film ET Eox (DEp) Ered (DEp) HOMO/LUMO
[8C] [a] [nm] [b] [nm] [b] [nm (%)] [c] [nm (%)] [c] [nm (%)] [c] [eV] [d] [mV] [e] [mV] [f ] [eV] [g]

1 284/104/373 310, 376 309, 372 428 (89) 478 (65) 466 (80) 2.30 (2.20) 386 (91)
2330 (i) 5.19/2.20
2 na/135/439 294, 346 294, 344 397 (98) 422 (92) 433 (74) 2.39 (2.27) 825 (120)
2350 (i) 5.63/2.38
3 212/106/430 306, 355 306, 354 425 (86) 472 (64) 457 (71) 2.46 (2.22) 484 (92)
2350 (i) 5.28/2.18
4 288/127/431 293, 329 294, 328 393 (76) 415 (80) 437 (69) 2.59 (2.33) 855 (70)
2290 (i) 5.66/2.28
5 396/170/467 309, 376 315, 376 428 (76) 475 (88) 457 (72) 2.30 (2.20) 413 (70)
2420 (i) 5.21/2.21
6 226/100/392 296, 370 297, 367 405 (87) 435 (95) 430 (63) 2.44 (2.30) 385 (90) na 5.19/2.08
7 241/124/430 294, 328 294, 328 375 (83) 393 (90) 399 (60) 2.55 (2.40) 818 (120) na 5.62/2.20
8 na/99/398 296, 346 296, 348 407 (77) 439 (82) 433 (63) 2.48 (2.31) 484 (92) na 5.28/2.08
9 na/114/445 294, 310 293, 310 377 (97) 400 (91) 388 (36) 2.65 (2.41) 852 (114)
2520 (i) 5.65/2.16
10 190/95/387 294, 308 293, 304 355 (39) 385 (41) 387 (31) 2.73 (2.61) 1120 (90) na 5.65/2.11
11 na/126/459 292, 340 292, 340 367 (36) 390 (18) 377 (22) 2.73 (2.62) 1155 (186) na 5.92/2.36

[a] The heating and cooling rates were 10 8C min
1 and 30 8C min
1, respectively; Tm: melting point; Tg: glass-transition temperature; Td: decomposition
temperature. [b] labs: absorption maximum. [c] lem: emission maximum. The quantum yields (Ff ) were measured both in solution and in thin films, see
ref. [14]. [d] ET: triplet energy measured in toluene at 77 K (and in film). [e] Eox ¼ (Epa þ Epc)/2, DEp ¼ Epa
Epc where Epa and Epc are the anodic and cathodic
potentials, respectively; measured in CH2Cl2; all of the potentials are reported relative to ferrocene, which was used as the internal standard in each
experiment. The ferrocene oxidation potential was located at þ272 mV, relative to the Ag/AgNO3 non-aqueous reference electrode. [f ] Measured in
dimethyl sulfoxide (DMSO); i: irreversible; na: not available. All of the potentials are reported as peak potentials, which are relative to ferrocene. The
ferrocene oxidation potential was located at þ90 mV, relative to the Ag/AgNO3 non-aqueous reference electrode. [g] The HOMO and LUMO energies
were determined from cyclic voltammetry and the absorption onset.

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Figure 2. a) Absorption spectra of 1, 2, 3, 6 and 8 recorded in CH2Cl2
solution. b) Emission spectra of 1, 2, 3, 6 and 8 recorded in CH2Cl2
solution.
and 4 > 9. All of the compounds are highly emissive in the blue
region, both in the solution and in the film state (Table 1). The
charge-transfer characteristics are more prominent in the
emission and there is a significant red shift of the emission band
from using toluene, to CH2Cl2 or in the film state. The trend of the
lem values among the different compounds is parallel with that of
labs values: (1) compounds with a more-planar fluorenylphenyl
spacer have larger lem values than those with a triphenyl spacer:
1 > 3, 2 > 4; (2) the diphenylamine-based compounds have larger
lem values than the carbazole-based compounds: 1 > 2, 3 > 4, 6 > 7
and 8 > 9; (3) the compounds with the para-disposition of the
arylamine vs. the imidazole units have larger lem values than their
congeners with the meta-disposition: 1 > 6, 2 > 7, 3 > 8 and 4 > 9.
By taking the highest energy peak of the phosphorescence as the
vibronic 0-0 transition energy of T1 ! S0, triplet energies (ET) of
compounds can be estimated. The triplet energy in the film state is
smaller than that in the solution by 0.1–0.2 eV. For example, the
triplet energies of 1 were measured to be 2.20 and 2.30 eV in the
film state (ET(film)) and in toluene solution (ET(toluene)),
respectively. Since the compounds are deposited as thin films in
OLEDs, mainly ET(film) will be used in the following discussions.
The ET(film) values of the compounds with the para-disposition
of the arylamine vs. the imidazole units remain constant at 2.2 eV
2664 ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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and increase slightly in the meta-congener. For example, 6
(2.30 eV) > 1 (2.20 eV) and 8 (2.31 eV) > 3 (2.20 eV). Use of the
9-carbazolyl electron donor frequently leads to a higher triplet
energy level due to reduced exchange energies.[13] Similarly,
we found that the triplet energy was enlarged by replacing
the diphenylamine moiety with a 9-carbazolyl moiety: 3
(ET(film) ¼ 2.22 eV) < 4 (ET(film) ¼ 2.33 eV) and 6 (ET(film) ¼
2.30 eV) < 7 (ET(film) ¼ 2.40 eV). Further increments of the triplet
energy can be achieved by decreasing the conjugation length of the
spacer in the meta-compound. For example, the values for
ET(toluene) of compounds 10 and 11 are as high as 2.60 eV.
2.4. Electrochemical Properties
The electrochemical properties of compounds 1–11 were
investigated by cyclic voltammetry and the redox potentials of
the compounds are collected in Table 1. All of these compounds
exhibit one quasi-reversible, one-electron redox wave due to the
oxidation of the diphenylamine or carbazole. Representative cyclic
voltammograms are shown in Figure S1 (Supporting Informa-
tion). In accordance with previous observations,[14,15] the weaker,
electron-donating 9-carbazole is oxidized at a higher potential
than the diphenylamine moiety. Rather weak interaction between
the arylamine and benz[d]imidazolyl units is evidenced from the
nearly identical oxidation potential between the para- and meta-
isomers: 1 vs. 6, 2 vs. 7, 3 vs. 8 and 4 vs. 9. The oxidation potentials
of arylamine are in order of 3 > 5 > 1, 8 > 6 and 4 > 2, indicating
that the oxidized nitrogen atom is more stabilized with a
neighboring 9,9-diethylfluorene compared to a neighboring
p-biphenyl or spirobifluorene. Similarly, the oxidized carbazolyl
nitrogen is better stabilized by a terphenyl unit than a biphenyl unit
and compounds 10 and 11 are oxidized at a higher potential than 9.
In dimethylformamide (DMF), no reduction waves were detected
for 6, 7, 8, 10 and 11, while compounds 1–5 and 9 exhibited an
irreversible reduction wave ranging from
2290 to
2520 mV,
relative to ferrocene. The HOMO energy levels of the compounds
were calculated from cyclic voltammetry and by comparison with
ferrocene (4.8 eV).[16] These data, together with the absorption
spectra, were then taken to obtain the LUMO energy levels
(Table 1).[15]
2.5. Charge-Transport Properties
The carrier-transport properties of 1–11 were investigated by the
time-of-flight (TOF) transient-photocurrent technique[17] at
room temperature. Figure S2 (Supporting Information) shows
the representative TOF transient for electrons and holes of the
compounds. The carrier-transit time, tT, needed to determine
the carrier mobilities can be evaluated from the intersection point
of two asymptotes in the double-logarithmic representation of the
TOF transient (Figure S2 in the Supporting Information). All of the
compounds exhibit ambipolar carrier-transport behavior, with
either dispersive or non-dispersive carrier-transport characteris-
tics. Figure S3 (Supporting Information) shows the dependence of
the carrier mobilities of various compounds on the electric field.
The field dependence of the carrier mobilities follows the nearly
universal Poole–Frenkel relationship, in Equation (1), where b is
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the Poole–Frenkel factor:[18] somewhat-balanced hole and the electron mobilities (within

FULL PAPER
one order) render these compounds potentially useful for single-
 
1= component, single-layer OLEDs (vide infra).
m / exp bE 2 (1)

The values of the carrier mobilities in these compounds at 2.6. Electroluminescent Properties
specified electric fields are given in Table 2. The carrier mobilities
of glassy materials are affected by positional and energetic
In view of the ambipolar carrier-transport characteristics of
disorders and a wide range of carrier mobilities exist for both
the compounds under study, single-layer EL devices with
electrons and holes, depending on the carrier-transporting units
device structure I: ITO/1–9 (80 nm)/LiF (1 nm)/Al (150 nm),
and molecular geometries.[19] The hole mobilities of 1–11 are in
were studied. The performance parameters of these devices are
the range of 10
4–10
6 cm2 V
1 s
1. In comparison, commonly-
collected in Table 3 and Table S1 (Supporting Information).
used, diphenylamino-based hole-transport materials, 1,4-bis(1-
The devices using the diphenylamine derivatives (1, 3, 5, 6 and
naphthylphenylamino)-biphenyl (NPB)[20] and N,N0 -diphenylben-
8) have higher efficiencies than those using the 9-carbazolyl
zidine (TPD)[21] have hole mobilities at 10
3 cm2 V
1 s
1,
derivatives (2, 4, 7 and 9). The larger energy barrier between the
whereas, the 9-carbazole-containing compounds, 3-(9-carbazolyl)-
indium tin oxide (ITO) Fermi level (4.7 eV) and the HOMO level
9-hexylcarbazole and 3,6-di(9-carbazolyl)-9-octylcarbazole,[22] have
of the 9-carbazolyl derivatives (>5.6 eV) possibly hampers hole
hole mobilities at 10
5 cm2 V
1 s
1 and 10
3 cm2 V
1 s
1,
injection, as is evidenced from the lower turn-on voltages of the
respectively. The electron mobilities of 1–11 lie in the range of
diphenylamine-based devices. Balancing of the electron and
10
4–10
5 cm2 V
1 s
1, which is comparable to or slightly
hole mobilities may also play an important role. For instance, 6
better than those of the typical electron-transport material, 1,3,5-
and 8 have electron mobilities nearly one order higher than their
tris(N-phenylbenzimidazol-2-yl)-benzene) (TPBI) (10
5 cm2 V
1
hole mobilities, and devices using 6 and 8 exhibit lower efficiencies
s
1)[23] and N-arylbenzimidazole-containing analogues (10
5–
compared to those using 1, 3 and 5. Of the devices I, the best
10
6 cm2 V
1 s
1).[24]
performance was achieved with the single-layer devices based on 1,
In general, several trends were observed regarding the
3 and 5. Representative current–voltage–luminance (I–V–L)
correlation between the molecular structures and the carrier-
characteristics, EL spectra and current-efficiency–current-density
transport properties for all of the compounds under study.
plots of these devices are shown in Figure 3. At a current density of
1) Compounds containing the diphenylamine moiety have higher
100 mA cm
2, they still retain high performance: 1: luminance,
electron mobilities than hole mobilities. On the other hand,
L ¼ 2378 cd m
2; external quantum efficiency, hext ¼ 2.4%; power
compounds containing the carbazole moiety show the tendency of
efficiency, hp ¼ 1.2 lm W
1; current efficiency, hc ¼ 2.4 cd A
1; 3:
having electron mobilities lower than or close to their hole
L ¼ 1925 cd m
2, hext ¼ 2.4%, hp ¼ 1.1 lm W
1, hc ¼ 1.9 cd A
1; 5:
mobilities. 2) The TOF signals are more dispersive for compounds
L ¼ 1750 cd m
2, hext ¼ 1.4%, hp ¼ 0.9 lm W
1, hc ¼ 1.8 cd A
1.
incorporating the (phenyl-2-benzimidazolyl) benzene moiety at
Moreover, all of the CIE coordinates of the single-layer devices
the meta-position, than those of compounds incorporating the
I using 1–9 fell in the blue region. Of these, the single-layer device
(phenyl-2-benzimidazolyl) benzene moiety at the para-position.
using 3 has the CIE coordinate of (0.14, 0.09), which is the exact
3) When using a fluorene spacer, the TOF signals become less
pure-blue point in the CIE diagram. Such a pure-blue, single-layer
dispersive, but both electron and hole mobilities decrease. These
device with high performance may be useful for simplifying the
trends may provide useful information for the further design and
fabrication process of full-color displays.
implementation of ambipolar OLED materials. In any case, the
For comparison, two types of double-layer devices: II: ITO/
NPB (40 nm)/1–9 (40 nm)/LiF (1 nm)/Al(150 nm) and III: ITO/
Table 2. Electron and hole mobilities of compounds measured from the 1–9 (40 nm)/TPBI (40 nm)/LiF (1 nm)/Al(150 nm) were also
time-of-flight method. fabricated and tested. Compounds NPB and TPBI served as the
hole- and electron-transporting materials, respectively, and LiF
me mh Electric Field
served as the electron-injection layer. In general, devices II have a
[cm2 V
1 s
1] [a] [cm2 V
1 s
1] [b] [V cm
1]
better performance than the devices I. There is more-significant
1 65.7  10
6 (nd) 20.5  10
6 (nd) 5.2  105 improvement (both performance and turn-on voltage) in
2 0.68  10
6 (nd) 0.34  10
6 (nd) 6.8  105 the9-carbazolyl-derivatives-based devices, re-emphasizing the
3 19.3  10
6 (nd) 7.32  10
6 (nd) 6.7  105 importance of hole injection; that is, addition of the NPB layer
4 78.9  10
6 (nd) 147  10
6 (d) 6.5  105 (HOMO ¼ 5.2 eV)[25] reduces the hole-injection barrier. Insertion
5 11.7  10
6 (nd) 23.8  10
6 (nd) 6.3  105 of TPBI (device III) does not appear to have a prominent
6 90.1  10
6 (nd) 11.2  10
6 (nd) 5.7  105
improvement on the device performance except for in those with
7 4.52  10
6 (nd) 4.36  10
6 (nd) 6.1  105
6 and 8, possibly due to the large gap between the Fermi level of
8 144  10
6 (d) 17.6  10
6 (nd) 5.4  105
9 27.2  10
6 (d) 111  10
6 (d) 6.5  105
LiF/Al (ca. 3.3–3.51 eV)[26] and the LUMO of TPBI (2.70 eV).
10 11.0  10
6 (d) 80.1  10
6 (d) 6.7  105 Compounds 6 and 8 have an electron mobility that is
11 61.4  10
6 (d) 15.3  10
6 (d) 6.1  105 approximately 1 order higher than that of TPBI (10
5 cm2
V
1 s
1),[23] and than their own hole mobility. Consequently, the
[a] me: electron mobility. [b] me: hole mobility; d: dispersive; nd: non- hole-blocking capability and lower electron mobility of TPBI
dispersive. (HOMO ¼ 6.2 eV) may lead to a better confinement of excitons.

Adv. Funct. Mater. 2009, 19, 2661–2670 ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 2665
 www.afm-journal.de

Table 3. Electroluminescent data of the devices I, II, III. The measured values are given in order of the devices I, II and III.
FULL PAPER

Von Lmax (voltage) lem CIE FWHM hext,max hp,max hc,max L hext hp hc
[V] [a] [cd m
2 (V)] [b] [nm] [c] (x,y) [d] [nm] [e] [%] [f ] [lm W
1] [g] [cd A
1] [h] [cd m
2] [b,i] [%] [f,i] [lm W
1] [g,i] [cd A
1] [h,i]

1 2.9; 2.7; 16178 (13.5); 452; 456; 0.15, 0.12; 60; 62; 2.5; 3.0; 2.0; 2.3; 2.5; 2.8; 2378; 2626; 2.4; 2.8; 1.2; 1.9; 2.4; 2.6;
5.0 21663 (14.0); 446 0.14, 0.11; 64 2.0 0.7 2.2 1125 1.2 0.24 1.2
5713 (20.5) 0.15, 0.12
3 3.0; 3.5; 11 669 (12.0); 456; 460; 0.14, 0.09; 58; 62; 2.4; 4.7; 1.5; 3.0; 1.9; 4.6; 1925; 3920; 2.4; 4.0; 1.1; 1.5; 1.9; 4.0;
3.5 25 046 (12.5); 454 0.14, 0.12; 60 2.3 1.0 1.4 1355 2.2 0.59 1.4
7351 (14.0) 0.14, 0.07
5 2.9; 2.7; 10 011 (13.5); 458; 454; 0.15, 0.15; 68; 62; 1.4; 1.6; 1.1; 1.6; 1.8; 1.7; 1750; 1432; 1.4; 1.4; 0.9; 0.9; 1.8; 1.4;
4.5 10 418 (14.0) 464 0.15, 0.12; 72 1.6 1.0 2.3 1139 0.81 0.26 1.1
3171 (16.0) 0.15, 0.18
6 3.5; 3.5; 2212 (12.0); 436; 440; 0.15, 0.07; 62; 68; 0.85; 0.87; 0.43; 0.38; 0.56; 0.63; 513; 584; 0.78; 0.82; 0.24; 0.26; 0.51; 0.59;
4.5 3553 (14.0); 432 0.15, 0.08; 56 2.3 0.54 1.1 548 1.1 0.17 0.55
1928 (15.0) 0.15, 0.06
8 3.5; 3.0; 2576 (12.5); 434; 440; 0.16, 0.07; 56; 56; 1.0; 2.1; 0.46; 1.0; 0.62; 1.1; 589; 1052; 0.97; 1.9; 0.28; 0.59; 0.59; 1.1;
3.5 7988 (13.5); 438 0.15, 0.06; 56 3.5 1.2 1.7 971 2.0 0.40 1.0
2556 (13.0) 0.15, 0.05

[a] Von (turn-on voltage) was obtained from the x-intercept of the plot of log(luminance) against applied voltage. [b] L: luminance; max: maximum. [c] lem,
emission wavelength. [d] CIE (x,y): Commission Internationale de l0 Eclairage coordinates. [e] FWHM: full width at half maximum. [f ] hext: external quantum
efficiency; max: maximum. [g] hp: power efficiency; max: maximum. [h] hc: current efficiency; max: maximum. [i] Luminance and efficiencies measured at a
current density of 100 mA cm
2.

The hole-blocking effect of TPBI is also evident from the smaller
current densities of the devices III compared to those of I and II.
In view of the strong blue fluorescence of the compounds and
the good performance of the single-layer OLEDs, use of the
compounds as the host for phosphorescent materials was also
tested. Compounds with smaller triplet energies were first studied
as hosts for orange/red phosphorescent OLEDs. In view of its
triplet energy (ET(film) ¼ 2.20 eV; ET(toluene) ¼ 2.46 eV), 5 was
considered to be possible candidate to host orange/red-emitting
phosphorescent materials. Compound 5 has been successfully
used as the host for an orange-yellow phosphorescent iridium
complex, (fbi)2Ir(acac) (fbi ¼ 2-(9,9-diethyl-9H-fluoren-2-yl)-1-phenyl-
1H-benzimidazole; acac ¼ acetylacetonate),[25] (ET(film) ¼ 2.13 eV).
The single-layer device IV: ITO/5, with 5% (fbi)2Ir(acac) (80 nm)/LiF
(1 nm)/Al (150 nm) has efficiency (6.9%; 4.4 lm W
1; 20 cd A
1;
19 637 cd m
2 at 100 mA cm
2) rivalling that of the multilayer device
using 4,40 -N,N0 -dicarbazole-biphenyl (CBP) (ET(film) ¼ 2.56 eV)[27] as
the host.[25] The I–L characteristics and the EL spectrum of device
IV are shown in Figure 4 and relevant performance parameters for
the device are summarized in Table 4.
Use of the compounds with a larger triplet energy as the host for
the green-emitting phosphorescent complex, Ir(ppy)3 (ET(film) ¼
2.42–2.46 eV),[28] were also tested. Compound 7 (ET(film) ¼
2.40 eV), 9 (ET(film) ¼ 2.41 eV) and 10 (ET(film) ¼ 2.61 eV) were
selected for this purpose. The single-layer devices V of the
configuration: ITO/(7 9, or 10) with 5% Ir(ppy)3 (80 nm)/LiF
(1 nm)/Al (150 nm), were fabricated and the performance
parameters are also presented in Table 4. A device with the
same single-layer configuration using the commonly used
phosphorescent host CBP (ET(film) ¼ 2.56 eV) was also fabricated
and tested for comparison. The I–L characteristics and the EL
spectrum of the device V are also shown in Figure 4. When
compound 5 was used as the host for the green-emitting Ir(ppy)3,
the emission came from both the 5 and the Ir(ppy)3, which is
consistent with the smaller triplet (ET(film) ¼ 2.20 eV) energy gap
of 5. In comparison, using compounds 7, 9 and 10, that possessed
larger singlet and triplet energy gaps than 5, as the host, complete
suppression of emission from the host can be achieved. The
efficiencies of the devices Vare in order of 10 > 9  7, which seems
correlated with the triplet energy gaps of the host materials.
Perhaps, in the device of 10, triplet excitons are better confined on
dopants due to its sufficiently large triplet energy, suggesting that
energy back-transfer from the guest to the host also plays an
important role for device performance. Using 10 as the host for the
single-layer device gives a rather-impressive peak EL quantum
efficiency of 9.3% (34.3 cd A
1). It is also interesting to note that
even the 7- and 9-based single-layer devices show better
performances than the CBP-based single-layer device, even
though CBP (ET(film) ¼ 2.56 eV) has a slightly larger triplet energy
than 7 and 9 (ET(film) ¼ 2.40 and 2.41 eV, respectively). This may
imply the importance of the balanced charge transport in the host.
Besides being used as the host for hue-tuning, the feasibility of
using these blue-emitting fluorescent materials for white-light-
emitting OLEDs (WOLEDs)[29] is also demonstrated. According to
the data above, the CIE coordinates of the single-layer device I using
blue-emitting 5 and those of device IV using 5 as a host for an
orange-yellow phosphorescent iridium complex, (fbi)2Ir(acac),
were (0.15, 0.15) and (0.53, 0.47), respectively. In view that the line
connecting the two CIE coordinates passes through the white
region, WOLEDs may be achieved by appropriate color mixing
from 5 and (fbi)2Ir(acac). After some trials, we were able to achieve a
WOLED with device configuration VI(a): ITO/5 (72 nm)/5 with
5% (fbi)2Ir(acac) (8 nm)/BCP (10 nm)/LiF/Al, where the thin
layer of hole-blocking bathocuproin (BCP) (HOMO ¼ 6.1 eV;
LUMO ¼ 2.8 eV; ET(film) ¼ 2.5 eV)[3] was used to prevent the holes
from escaping the doping layer. Device VI(a) had its CIE
coordinates at (0.33, 0.35) and performance parameters of 2.2%,
1.7 lm W
1, 5.4 cd A
1 and 5379 cd m
2 at 100 mA cm
2. Further

2666 ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Funct. Mater. 2009, 19, 2661–2670
www.afm-journal.de
Figure 3. a) Current density and luminance plotted against applied electric
field, characteristic for the devices I, made with 1, 3 and 5. b) EL spectra for
single-layer devices of 1, 3 and 5. c) Current efficiency plotted against
current density for single-layer devices I, made with 1, 3 and 5.
improvement in the current density, as well as in the device
performance, was achieved with a device of configuration VI(b):
ITO/NPB (5 nm)/5 (72 nm)/5 with 5% (fbi)2Ir(acac) (8 nm)/BCP
(10 nm)/LiF/Al. NPB possibly helps to suppress the leakage of
electrons from the excitons to the anode. The CIE coordinates of
VI(b) were slightly sensitive to the operating voltage and the best
performance was achieved at 8 V: 3.0%, 2.8 lm W
1, 7.0 cd A
1,
4306 cd m
2 and (0.31, 0.33) at 100 mA cm
2. The EL spectra of
device VI(b) at different operating voltages are shown in Figure 5. It
is interesting that white WOLEDs can also be achieved with a device
configuration VI(c): ITO/NPB (10 nm)/5 with 5% (fbi)2Ir(acac)
Adv. Funct. Mater. 2009, 19, 2661–2670 ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
FULL PAPER
Figure 4. a) I–L for single-layer devices (V) of 7, 9 and 10 with 5% of
Ir(ppy)3 dopant and device IV, of 5 with 5% of (fbi)2Ir(acac) dopant. b) EL
spectra for single-layer devices (V) of 7, 9 and 10 with 5% of Ir(ppy)3 dopant
and device IV, of 5 with 5% of (fbi)2Ir(acac) dopant.
(8 nm)/5 (72 nm)/BCP (10 nm)/LiF/Al. The orange emission of
(fbi)2Ir(acac) likely stems from energy transfer from the host to the
guest when the blue light emits toward the anode and passes
through the doping layer. The CIE coordinates of VI(c) at 8 V are
(0.33, 0.30). The color-rendering index (CRI) values for devices
VI(a)–VI(c) are 72, 71 and 76, respectively, while the correlated
color temperature (CCT) values are 6791, 6660 and 5324 K,
respectively. The CRI values in these WOLEDs are somewhat lower
than those of single-layer devices (CRI  90) using a polyfluorene
with blue, green and red units tethered to the side chain of the
polymer.[30] Though these CRI values are also slightly lower than
that of a multilayer device using small blue-emitting hosts doped
with orange and green phosphors (CRI ¼ 82),[31] they appear to be
much better than that of a device using the same fluorescent blue
host, N,N0 -di-1-naphthalenyl- N,N0 -diphenyl-[1,10 ,:40 ,100 :400 ,1000 ;-
quaterphenyl]-4,4000 ;-diamine (4P-NPD), doped with a yellow-
emitting phosphorescent complex (CRI ¼ 38).[31]
3. Conclusions
In summary, we have established a convenient synthesis of highly
emissive compounds containing benzimidazole and arylamines.
With a systematic variation of the molecular structures and studies
2667
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Table 4. Electroluminescent data of the devices IV and V.

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Von Lmax (voltage) lem CIE FWHM hext,max hp,max hc,max L hext hp hc
[V] [a] [cd m
2 (V)] [b] [nm] [c] (x,y) [d] [nm] [e] [%] [f ] [lm W
1] [g] [cd A
1] [h] [cd m
2] [b,i] [%] [f,i] [lm W
1] [g,i] [cd A
1] [h,I]

IV (5) 3.1 79 750 (21.5) 572 0.53, 0.47 76 7.8 7.5 22 19 637 6.9 4.4 20
V (7) 4.5 38 269 (24.0) 526 0.33, 0.63 70 4.6 6.5 17.1 13 260 3.5 2.2 13.3
V (9) 4.0 62 082 (26.5 526 0.33, 0.62 74 4.8 7.0 17.8 15 514 4.2 2.6 15.5
V (10) 5.0 66 027 (28.5) 522 0.31, 0.63 70 9.3 13.5 34.3 17 237 4.7 2.7 17.3
V (CBP) 6.5 5566 (20.0) 520 0.30, 0.63 64 1.71 1.44 6.19 4122 1.14 0.73 4.13

[a] Von (turn-on voltage) was obtained from the x-intercept of plot of log(luminance) against applied voltage. [b] L: luminance; max: maximum. [c] lem,
emission wavelength. [d] CIE (x,y): Commission Internationale de l0 Eclairage coordinates. [e] FWHM: full width at half maximum. [f ] hext: external quantum
efficiency; max: maximum. [g] hp: power efficiency; max: maximum. [h] hc: current efficiency; max: maximum. [i] Luminance and efficiencies measured at a
current density of 100 mA cm
2.
Figure 5. EL spectra for white-light-emitting device VI(b) at 6 V, 8 V, 10 V
and 12 V, respectively. The EL was normalized to the peak at 567 nm.
of their properties, a series of ambipolar blue-emitting materials
with tunable blue-emitting wavelengths, tunable ambipolar
carrier-transport properties and tunable triplet energy gaps was
developed. These blue-emitting compounds, which have intri-
guing ambipolar carrier-transport properties, were successfully
used to fabricate single-layer, blue-emitting, fluorescent EL devices
with promising performance compared to multilayered blue-
emitting devices. Using different conjugated spacers and linking
topologies allowed tuning of the triplet energies of these
ambipolar, blue-emitting materials from 2.20 to 2.62 eV in the
film state, rendering them also useful as hosts in both yellow-
orange and green single-layer, phosphorescent OLEDs. The
concept presented here can possibly be extended to further
generate a new class of advanced materials for full-color OLED
displays and white-emitting OLEDs with simplified device
structures.
4. Experimental
General Details: The starting material, 4,40 -dibromobiphenyl, was
purchased from Acros and was used without further purification. 2,7-
Dibromo-9,9-diethyl-9H-fluorene [32] and 2,7-dibromo-20 ,70 -di-tert-butyl-
9,90 -spirobi[fluorene] [33] were prepared by adopting literature procedures.
All of the reactions and manipulations were carried out under N2 with the
use of a standard inert atmosphere and Schlenk techniques. The solvents
were dried by standard procedures. All of the column-chromatography
measurements were performed using silica gel (230–400 mesh, Macherey–
Nagel GmbH & Co.) as the stationary phase in a column 30 cm in length
and 4.0 cm in diameter. The NMR spectra were recorded on aBruker
AMX400 and AV500 spectrometers. The electronic absorption spectra were
measured using a Cary 50 Probe UV-vis spectrophotometer. The
fluorescence spectra were recorded using a Jasco FP-6500 fluorescence
spectrometer. The emission quantum yields were measured with reference
to coumarin-1 dye (7-diethylamino-4-methylcoumarin) in ethyl acetate [34].
The phosphorescence spectra of the compounds (in the toluene solution
and in thin films) were measured using a HORIBA Jobin–Yvon FluoroMax-
P spectrometer at 77 K, with a 10 ms delay time between the excitation with
a microsecond flash lamp and the measurement. The cyclic-voltammetry
experiments were performed using a CHI-621B electrochemical analyzer.
All of the measurements were carried out at room temperature with a
conventional three-electrode configuration consisting of a platinum
working electrode, an auxiliary electrode and a non-aqueous Ag/AgNO3
reference electrode. The E1/2 values were determined as (Epa þ Epc)/2,
where Epa and Epc are the anodic and cathodic peak potentials, respectively.
The solvent in all of the experiments was CH2Cl2 and the supporting
electrolyte was 0.1 M tetrabutylammonium hexafluorophosphate. The DSC
measurements were carried out using a Perkin–Elmer 7 series thermal
analyzer at a heating rate of 108 min
1. The TGA measurements were
performed on a Perkin–Elmer TGA7 thermal analyzer. The fast atom
bombardment (FAB)-mass spectra were collected using a JMS-700 double-
focusing mass spectrometer (JEOL, Tokyo, Japan) with a resolution of 8000
(5% valley definition). For the FAB-mass spectra, the source accelerating
voltage was operated at 10 kV with a Xe gun, using 3-nitrobenzyl alcohol as
the matrix. Elementary analyses were performed using a Perkin–Elmer 2400
CHN analyzer.
Synthesis of 2-(4-Bromophenyl)-1-phenyl-1H-benz[d]imidazole (p-
BPBI): 2-Methoxyethanol (50 mL) was added to a flask containing
N-phenyl-o-phenylenediamine (9.21 g, 50 mmol) and 4-bromobenzalde-
hyde (9.25 g, 50 mmol). After the mixture was refluxed for 48 h, the volatile
was removed under vacuum and the residue was extracted with CH2Cl2.
The organic extract was washed with brine, dried over anhydrous MgSO4,
filtered and pumped dry. The crude product was purified by column
chromatography using CH2Cl2/hexanes (1:1 by vol) as the eluent.
Analytically pure 2-(4-bromophenyl)-1-phenyl-1H-benz[d]imidazole was
isolated as a white solid in a 72% (9.77 g) yield.
1
H NMR (400 MHz, CDCl3, d): 7.68 (d, J ¼ 8.0 Hz, 1 H), 7.35–7.29 (m, 4
H), 7.24–7.20 (m, 1 H), 7.15–7.02 (m, 7 H). FABMS (m/z): 348.9 [Mþ].
Anal. calcd. for C19H13BrN2: C 65.35, H 3.75, N 8.02; found: C 65.22, H
3.78, N, 8.01.
Synthesis of 2-(3-Bromophenyl)-1-phenyl-1H-benz[d]imidazole (m-
BPBI): m-BPBI was prepared according to the same procedure as
2-(4-bromophenyl)-1-phenyl-1H-benz[d]imidazole from N-phenyl-o-pheny-
lenediamine and 4-bromobenzaldehyde. The isolated yield of the
compound was 85%. It has the same spectroscopic data as that as
the bona fide compound [35].
Syntheses of Compounds 1a–5a, 10a and 11a: Compounds 7-bromo-9,9-
diethyl-N,N-diphenyl-9H-fluoren-2-amine (1a), 40 -bromo-N,N-diphenylbiphenyl-

2668 ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Funct. Mater. 2009, 19, 2661–2670
www.afm-journal.de
4-amine (3a), and 7-bromo-20 ,70 -di-tert-butyl-N,N-diphenyl-9,90 -spirobi[fluoren]-
2-amine (5a) were synthesized by similar procedures. Compounds
9-(7-bromo-9,9-diethyl-9H-fluoren-2-yl)-9H-carbazole (2a) 9-(40 -bromobi-
phenyl-4-yl)-9H-carbazole (4a), 9-(4-bromophenyl)-9H-carbazole (10a) and
9,90 -(5-bromo-1,3-phenylene)bis(9H-carbazole) (11a) were synthesized by
similar procedures. Only the preparation of 1a and 2a will be described in
detail. All of the others are in Supporting Information.
Synthesis of Compound 1a: Dry toluene (80 mL) was added to a flask
containing a mixture of 2,7-dibromo-9,9-diethyl-9H-fluorene (4.18 g,
11.0 mmol), diphenylamine (0.85 g, 5.0 mmol), sodium tert-butoxide
(0.72 g, 7.5 mmol), Pd(dba)2 (0.032 g, 0.055 mmol) and 1,10 -bis(diphenyl-
phosphino)ferrocene (dppf) (0.033 g, 0.06 mmol). The reaction mixture
was heated to 80 8C and stirred for 16 h, then 100 8C for 24 h. After cooling,
the solution was removed under reduced pressure and the residue was
extracted with CH2Cl2/brine. The organic layer was dried over magnesium
sulfate, then filtered and dried. The crude product was further purified by
column chromatography using CH2Cl2/hexanes (1:10 by vol) as the eluent
to give 1a as a white powder (2.11 g, 90%).
1
H NMR (400 MHz, CDCl3, d): 7.51 (d, J ¼ 8.0 Hz, 1 H), 7.38–7.47 (m, 3
H), 7.21–7.26 (m, 4 H), 7.09 (d, J ¼ 8.0 Hz, 4 H), 6.97–7.06 (m, 4 H), 1.84–
2.02 (m, 4 H), 0.34 (t, J ¼ 7.3 Hz, 6 H); FABMS (m/z): 468.1 [Mþ þ H].
Synthesis of Compound 2a: A mixture of 2,7-dibromo-9,9-diethyl-9H-
fluorene (2.85 g, 7.5 mmol), carbazole (0.85 g, 7.5 mmol), CuI (0.14 g,
0.75 mmol), 18-Crown-6 (0.066 g, 0.25 mmol), K2CO3 (2.07 g, 15.0 mmol)
and 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (DMPU) (2 mL)
was heated to 170 8C for 16 h under nitrogen. After cooling to room
temperature, the mixture was quenched with 1 N HCl then extracted with
CH2Cl2/brine. The organic layer was dried over magnesium sulfate, then
filtered and dried. The crude product was further purified by column
chromatography using CH2Cl2/hexanes (1:10 by volume) as the eluent to
give 2a as a white powder (2.10 g, 60%).
1
H NMR (400 MHz, CDCl3, d): 8.15 (d, J ¼ 7.7 Hz, 2 H), 7.86 (d,
J ¼ 8.0 Hz, 1 H), 7.62 (d, J ¼ 8.0 Hz, 1 H), 7.47–7.54 (m, 4 H), 7.37–7.44
(m, 4 H), 7.26–7.31 (m, 2 H), 1.86–2.06 (m, 4 H), 0.43 (t, J ¼ 7.3 Hz, 6 H);
FABMS (m/z): 465.1 [Mþ].
Syntheses of 1b–5b, 10b and 11b: The boron reagents (1b–5b, 10b and
11b) of 1a–5a, 10a and 11a were synthesized by similar procedures. Only
the preparation of 7-(diphenylamino)-9,9-diethyl-9H-fluoren-2-ylboronic
acid (1b) will be described in detail.
Synthesis of Compound 1b: A solution of n-butyllithium (16.7 mL, 1.6 M
in n-hexane) was added drop-wise to a solution of 7-bromo-9,9-diethyl-
N,N-diphenyl-9H-fluoren-2-amine (1a) (2.11 g, 4.5 mmol) in THF (40 mL)
prechilled to
78 8C. After the solution had been stirred at
78 8C for 1 h,
B(OMe)3 (1.51 mL, 13.5 mmol) was added slowly. After addition, the
solution was stirred at
78 8C for another 30 minutes then brought back to
room temperature overnight. The reaction was quenched by adding dilute
HCl solution (10%, 50 mL), and the mixture was extracted with
dichloromethane. The combined organic layer was washed with brine
solution and dried over anhydrous MgSO4. After filtration and removal of
the solvent, the product 1b was yielded as a pale-yellow solid (1.93 g, 99%)
and used for the next step without further purification.
Syntheses of Compounds 1–11: Compounds 9,9-diethyl-N,N-diphenyl-7-
(4-(1-phenyl-1H-benz[d]imidazol-2-yl)phenyl)-9H-fluoren-2-amine (1), 9-(9,9-
diethyl-7-(4-(1-phenyl-1H-benz[d]imidazol-2-yl)phenyl)-9H-fluoren-2-yl)-9H-
carbazole (2), N,N-diphenyl-40 -(4-(1-phenyl-1H-benz[d]imidazol-2-yl)phenyl)-
biphenyl-4-amine (3), 9-(40 -(4-(1-phenyl-1H-benz[d]imidazol-2-yl)phenyl)-
biphen-4-yl)-9H-carbazole (4), 20 ,70 -di-tert-butyl-N,N-diphenyl-7-(4-(1-
phenyl-1H-benz[d]imidazol-2-yl)phenyl)-9,90 -spirobi[fluorene]-2-amine (5),
9,9-diethyl-N,N-diphenyl-7-(3-(1-phenyl-1H-benz[d]imidazol-2-yl)phenyl)-
9H-fluoren-2-amine (6), 9-(9,9-diethyl-7-(3-(1-phenyl-1H-benz[d]imidazol-
2-yl)phenyl)-9H-fluoren-2-yl)-9H-carbazole (7), N,N-diphenyl-40 -(3-(1-
phenyl-1H-benz[d]imidazol-2-yl)phenyl)-biphenyl-4-amine (8), 9-(40 -(3-(1-
phenyl-1H-benz[d]imidazol-2-yl)phenyl)-biphen-4-yl)-9H-carbazole (9), 9-
[30 -(1-phenyl-1H-benzimidazol-2-yl)-biphenyl-4-yl]-9H-carbazole (10), and
9,90 -(30 -(1-phenyl-1H-benz[d]imidazol-2-yl)biphenyl-3,5-diyl)bis(9H-carbazole)
(11) were synthesized by similar procedures. Only the preparation of 1 will
be described in detail. All of the other synthesis procedures can be found in
the Supporting Information.
Adv. Funct. Mater. 2009, 19, 2661–2670 ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Synthesis of Compound 1: Dry toluene (40 mL) was added to a flask
FULL PAPER
containing a mixture of 7-(diphenylamino)-9,9-diethyl-9H-fluoren-2-ylboro-
nic acid (1b) (1.91 g, 4.0 mmol), 2-(4-bromophenyl)-1-phenyl-1H-benz[d]i-
midazole (1.40 g, 4.4 mmol), Na2CO3 (2 M in H2O, 8.0 mL, 16.0 mmol),
and Pd(PPh3)4 (0.19 g, 0.16 mmol). After the reaction mixture had been
refluxed for 48 h, the solvent was removed and the residue was extracted
with CH2Cl2/brine. The organic layer was dried over magnesium sulfate,
then filtered and dried. The crude product was further purified by column
chromatography using CH2Cl2/hexanes (1:1 to 5:1 by vol) as the eluent to
give 1 as a pale-yellow solid (2.1 g, 71%).
1
H NMR (400 MHz, CDCl3, d): 7.91 (d, J ¼ 8.0 Hz, 1 H), 7.49–7.68 (m,
12 H), 7.35–7.38 (m, 3 H), 7.22–7.26 (m, 5 H), 7.13–7.09 (m, 5 H),
6.97–7.04 (m, 3 H), 1.85–2.02 (m, 4 H), 0.36 (t, J ¼ 7.3 Hz, 6 H); 13C NMR
(125 MHz, CDCl3, d): 152.3, 151.8, 150.8, 148.2, 147.6, 143.2, 142.7, 141.4,
138.3, 137.6, 137.4, 136.3, 130.1, 130.0, 129.4, 128.8, 128.5, 127.7, 127.0,
126.3, 124.1, 123.8, 123.6, 123.3, 122.7, 121.4, 120.7, 120.0, 119.6, 119.5,
100.6, 56.4, 32.9, 8.8; FABMS (m/z): 658.3 [Mþ þ H]; HRMS (m/z):
[Mþ þ H] calcd for C48H40N3: 658.3222; found: 658.3218. Anal. calcd. for
C48H39N3: C 87.64, H 5.98, N 6.39; found: C 87.77, H 5.88, N 6.32.
OLED Fabrication and Measurement: The hole-transporting material,
1,4-bis(1-naphthylphenylamino)-biphenyl (NPB) [15] and electron-
transporting material 1,3,5-tris(N-phenylbenzimidazol-2-yl)-benzene) (TPBI)
[36] were prepared by procedures described in the literature. All of the
materials were sublimed prior to use. Pre-patterned ITO substrates were
cleaned using standard procedures before use. The EL devices were
prepared by vacuum deposition of the compounds, sequentially, with
desired thickness, with or without the phosphorescence dopant. Inorganic
LiF (1 nm thick) was then deposited as the electron-injection layer.
Aluminum was finally deposited as the cathode (150 nm). The effective area
of each individual device was 3.14 mm2, as defined by the ITO and Al
electrode patterns. The I–V curves were measured using a Keithley 2400
Source Meter under the ambient environment. The light intensity was
measured using a Newport 1835 Optical Meter.
Time-of-flight (TOF) Mobility Measurement: The mobilities of com-
pounds 1–11 were characterized using the transient photocurrent
technique: the time-of-flight (TOF) technique. The TOF measurement
were performed using the sample structure of: glass/Ag (30 nm)/1–11 (1–
2 mm)/Al (150 nm) with an active area of 2 mm  2 mm, as described in a
previous report [17]. The organic layer was deposited by vacuum
deposition. In the TOF measurement, a frequency-tripled Nd:YAG laser
(355 nm) with 10 ns pulse duration was used for pulsed illumination
through the semitransparent Ag. Under an applied dc bias, the transient
photocurrent was recorded as a function of time using a digital-storage
oscilloscope. The TOF measurements were typically performed in a 10
5
Torr vacuum chamber. Depending on the polarity of the applied bias V,
selected photogenerated carriers (holes or electrons) were swept across
the sample thickness D with a transit time tT; the applied electric field E was
then V/D, and the carrier mobility is given by m ¼ D/(tT  E) ¼ D2/(V  tT).
Acknowledgements
We thank the Academia Sinica, National Taiwan University and the
National Science Council for supporting this work. Supporting Information
is available online from Wiley InterScience or from the author.
Received: April 1, 2009
Published online: July 24, 2009
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