Three-Dimensional Structures Based on the Fusion of Chrysene and Spirobifluorene Chromophores for the Development of Blue OLEDs

Article abstract of DOI:10.1021/acs.joc.7b03008

A new deep-blue chromophore containing a three-dimensionally (3D) shaped CS core composed of fused chrysene and spirofluorene units is synthesized. A pair of m-terphenyl (TP) units is also substituted onto the CS core at two different sets of positions to

Full text of DOI:10.1021/acs.joc.7b03008

Subscriber access provided by MT ROYAL COLLEGE
Article
Three-Dimensional Structures Based on the Fusion of Chrysene and
Spirobifluorene Chromophores for the Development of Blue OLEDs
Hayoon Lee, Hyocheol Jung, Seokwoo Kang, Jin Hyuck Heo, Sang Hyuk Im, and Jongwook Park
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.7b03008 • Publication Date (Web): 19 Feb 2018
Downloaded from http://pubs.acs.org on February 20, 2018
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a service to the research community to expedite the dissemination
of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in
full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully
peer reviewed, but should not be considered the official version of record. They are citable by the
Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore,
the “Just Accepted” Web site may not include all articles that will be published in the journal. After
a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web
site and published as an ASAP article. Note that technical editing may introduce minor changes
to the manuscript text and/or graphics which could affect content, and all legal disclaimers and
ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or
consequences arising from the use of information contained in these “Just Accepted” manuscripts.
The Journal of Organic Chemistry is published by the American Chemical Society.
1155 Sixteenth Street N.W., Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.

Page 1 of 8
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
Three-Dimensional Structures Based on the Fusion of Chrysene and
Spirobifluorene Chromophores for the Development of Blue OLEDs
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Hayoon Lee†, Hyocheol Jung†, Seokwoo Kang†, Jin Hyuck Heo‡, Sang Hyuk Im‡ and Jongwook Park†*
†
Department of Chemical Engineering, College of Engineering, Kyung Hee University (KHU), 1732 Deogyeongꢀdaero,
Giheung, Youngin, Gyeonggi, 17104, Republic of Korea
‡
Department of Chemical and Biological Engineering, Korea University, 145 Anamꢀro, Seongbukꢀgu, Seoul 136ꢀ713, Reꢀ
public of Korea
ABSTRACT: A new deepꢀblue chromophore containing a threeꢀdimensionally (3D) shaped CS core composed of fused chrysene
and spirofluorene units is synthesized. A pair of mꢀterphenyl (TP) units is also substituted onto the CS core, at two different sets of
positions to form two additional compounds: CSꢀTPTP and TPꢀCSꢀTP. The TPꢀCSꢀTP compound showed the highest efficiency
with an external quantum efficiency (EQE) of 3.05%, and Commission Internationale de L’Eclairage coordinates (CIE) of (0.148,
0
.098) corresponding to the emission of blue light. This approach for forming a new chromophore is expected to the development
of functional organic materials with excellent characteristics.
In an OLED, the inclusion of materials that emit red, green,
and blue light is essential to realize a fullꢀcolor display. But
materials that emit blue light have a wide energy band gap,
which causes high barriers to the injection of charge into the
device. Thus, the blue OLED devices developed so far are
inferior to green and red OLEDs in terms of electroluminesꢀ
INTRODUCTION
Many studies are underway to develop materials with high
efficiency for various optoelectronic applications, such as
organic lightꢀemitting diodes (OLEDs), organic thin film tranꢀ
1ꢀ3
sistors (OTFTs), and organic photovoltaics (OPVs). By usꢀ
6
ing the coreꢀside concept of material development in these
fields, it is possible to design and develop materials having the
cence (EL) efficiency and device lifetime. Therefore, develꢀ
opment of materials that emit blue light with a pure color and
high efficiency is still required. In particular, Commission
Internationale de L’Eclairage coordinates (CIE x, y) of (0.14,
0.08) are required by the National Television System Commitꢀ
tee (NTSC); and highꢀdefinition television (HDTV) ITUꢀR
BT.709 requires a deeperꢀblue emission with CIE x, y of
4
desired properties.
In the case of OLEDs, the core group is responsible for the
main absorption and emission roles of the final compound;
and the side groups, which are capable of controlling the size,
arrangement, polarity, etc., of the final molecule, are substitutꢀ
ed onto the core to form compounds with a variety of shapes.
In particular, the emission characteristics can be adjusted by
changing the symmetry properties of the connections of the
side groups to the core and changing the positions on the core
(0.15, 0.06).
4
at which the side groups are substituted. We have also reportꢀ
ed a systematic study of a core composed of single, dual, and
triple chromophores, and the relationship between the final
5
compound and the substituted side groups. We used side
groups with different sizes, such as mꢀterphenyl (TP) and triꢀ
phenylbenzene (TPB), as well as different electronꢀdonating
effects, such as diphenylamine (DPA) and triphenylamine
Scheme 1. Chemical structures of the synthesized compounds.
5a,5d
(TPA).
ACS Paragon Plus Environment

The Journal of Organic Chemistry
D rather than planar shape. A fusion of these two component
Page 2 of 8
9
3
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
chromophores into a single chromophore (rather than a simple
coupling of the components using a carbonꢀcarbon single
bond) resulted in a product with increased rigidity, and hence
10
a reduced rate of nonꢀradiative relaxation. We also used CS
core to synthesize 2,7ꢀdi([1,1':3',1"ꢀterphenyl]ꢀ5'ꢀ
yl)spiro[fluoreneꢀ9,15'ꢀindeno[2,1ꢀg]chrysene] (CSꢀTPTP)
and 2,5'ꢀdi([1,1':3',1'ꢀterphenyl]ꢀ5'ꢀyl)spiro[fluoreneꢀ9,15'ꢀ
indeno[2,1ꢀg]chrysene] (TPꢀCSꢀTP), and investigated the efꢀ
fect of the substitution position of the bulky TP side group on
the emission wavelength and efficiency of the final molecule.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
RESULTS AND DISCUSSION
The chemical structures of the newly synthesized compounds
are shown in scheme 1. They were synthesized using the wellꢀ
known and generally simple Suzuki coupling, bromination,
and borylation reactions, and the details of the synthesis methꢀ
ods used are described in the experimental section and scheme
2
. The ultravioletꢀvisible (UVꢀVis) absorption and photolumiꢀ
nescence (PL) spectra of the synthesized materials are shown
in Figure 1. The optical properties, energy levels of the moꢀ
lecular orbitals, and thermal properties of these materials are
summarized in Table 1.
In the solution state and film state, CS showed UVꢀVis
maximum (UVmax) absorption peaks at wavelengths in the
range of 360 nm to 387 nm. We also acquired UV spectra of
chrysene and spirobifluorene; they showed, UVmax absorption
at wavelengths in the range of 250 nm to 321 nm, shorter than
those of CS and expected since they are deepꢀblue chromoꢀ
phores (Figure S1). The dihedral angle at the α position of the
bifluorene portion of CS was calculated via density functional
theory (DFT) at the B3LYP / 6ꢀ31G (d) level to be 110.5 °.
The C24 ꢀ C25 ꢀ C26 (α position) angle was confirmed from
the single crystal of CS to be 104.0 °, similar to the calculated
values and also indicative of the highly twisted structure (Figꢀ
ure 2, Figure S2, Table S1). Thus, CS still retained the UVꢀVis
absorption characteristics of chrysene and spirobifluorene in
Scheme 2. Synthetic routes of the synthesized materials.
5b,8
the shortꢀwavelength region. In addition, the electron densiꢀ
Three approaches using the coreꢀside concept mentioned
above have been described for developing materials that emit
deepꢀblue light. One approach involves the use of a core that
ty of CS was found not to be preferentially distributed to one
side or the other of the molecule, i.e., neither to the chrysene
portion nor the bifluorene portion of the molecule, and in this
manner CS displays a feature new for chromophores.
emits deepꢀblue light as the chromophore, with anthracene7,
pyrene, chrysene, and fluorene being examples of such cores.
CSꢀTPTP in the solution state and the film state also
showed UVmax absorption peaks in the wavelength range of
344 nm to 389 nm, similar to the results for CS. We attributed
this similarity to the conjugation of the CS moiety not extendꢀ
ing to the two attached TP side groups as a result of the highly
twisted nature of both fluorenes observed for CS. Moreover,
the same level of electron density was indicated to be present
in the CS moiety of CSꢀTPTP as in CS (i.e., without the subꢀ
stituted TPTP side groups), as shown in Figure 2.
The second involves using a molecule with a highly twisted
angle between its cores or between its core and side group in
order to limit the extent of conjugation in the molecule.
5b,8
And the third approach entails using bulky side groups with
relatively low inductive effects to sufficiently hinder intermoꢀ
5a,5d,7b
lecular packing.
So far, for deepꢀblue OLEDs, a chromoꢀ
phore mentioned above was selected as a single core and its
derivatives were synthesized. However, since the number of
chromophores that can be formed by a single core is limited, a
new core preparation method that can provide a new chromoꢀ
phore compound is required.
In this study, we propose a fused system based on a threeꢀ
dimensional (3D) shape between chromophores to design a
new deepꢀblue chromophore using a single core. We syntheꢀ
sized a new core, spiro[fluoreneꢀ9,15'ꢀindeno[2,1ꢀg]chrysene]
(
CS); we designed this compound as a fusion of chrysene and
spirobifluorene sharing a phenyl ring. Chrysene emits deepꢀ
blue light, compared to the emission of other chromophores
7
b
such as anthracene and pyrene. Spirobifluorene also has the
advantage of consisting of a highlyꢀtwisted fluorene that preꢀ
vents an increased extent of conjugation and that maintains a
Figure 1. UVꢀVis absorption and PL spectra of the syntheꢀ
ꢀ
5
sized materials: (a) in 1 × 10 M THF solution and (b) in vacꢀ
uumꢀdeposited films state.
2
ACS Paragon Plus Environment

Page 3 of 8
The Journal of Organic Chemistry
Table 1. Physical properties of the synthesized materials
1
2
3
4
5
6
7
8
9
band gap
eV)
tg
tm
td
λmax abs (nm)
λmax PL (nm)
solns /films
Φfc
HOMO
LUMO
compd
a
b
f
a
b
d
e
(
(°C)
(°C)
(°C)
solns /films
360, 377
344, 379
372, 387
ꢀ5
(eV)
(eV)
CS
CS-TPTP
TP-CS-TP
367, 387
346, 389
377, 396
417
420
440
436
436
454
0.61
0.59
0.87
ꢀ5.63
ꢀ5.79
ꢀ5.70
ꢀ2.59
3.04
3.02
2.92
108
195
191
250
ꢀ
ꢀ
358
522
522
ꢀ2.77
ꢀ2.78
c
a
b
ꢀ5
Measured in 1 × 10 M THF solution. Measured in 50 nm vacuumꢀdeposited films. Absolute PLQY in 1 × 10 M toluene soluꢀ
d
e
f
tion. Ultraviolet photoelectron spectroscopy (Rikenꢀkeiki, ACꢀ2). LUMO obtained from the HOMO and the optical band gap. 5%
weight loss.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
and CSꢀTPTP were both at 436 nm and that of TPꢀCSꢀTP was
shown to be at 454 nm. The red shift of the PLmax of TPꢀCSꢀ
TP compared to those of the other compounds was consistent
with the electron density distributions described above, where
no obvious difference was observed between the electron denꢀ
sity distributions of CSꢀTPTP and CS, but for TPꢀCSꢀTP, the
πꢀconjugation length was extended due to the side group subꢀ
stituted on the chrysene portion of the molecule (Figure 2).
The red shifts of the PLmax values in the film state relative to
those in the solution state were attributed to a decreased disꢀ
tance and hence formation of πꢀπ interactions between moleꢀ
cules in the film state. The somewhat smaller solutionꢀtoꢀfilm
red shifts of PLmax observed for CSꢀTPTP and TPꢀCSꢀTP, i.e.,
16 nm and 14 nm, respectively, than for CS, i.e., 19 nm, were
attributed to the intermolecular packing having been more
effectively prevented by the substituted side groups of CSꢀ
TPTP and TPꢀCSꢀTP. Also, all three synthesized materials
have CS, which is a 3D structure based on fusion of chrysene
with the highlyꢀtwisted spirobifluorene, and an excimer was
Figure 2. Optimized geometries and HOMO/LUMO elecꢀ
tron density distributions of (a) CS, (b) CSꢀTPTP, and (c) TPꢀ
CSꢀTP.
TPꢀCSꢀTP exhibited UVmax absorption peaks in the range of
372 nm to 396 nm, i.e., redꢀshifted approximately 10 nm comꢀ
pared to CS. This small difference was attributed to a small
increase in the extent of the πꢀconjugation in TPꢀCSꢀTP to the
TP side group substituted on the chrysene portion of the moleꢀ
cule. Electron density was indicated to be present in TPꢀCSꢀ
13
not expected to be generated in their film state.
The absolute PL quantum yield (PLQY, Φ ) values of CS
f
and CSꢀTPTP were measured to be 61% and 59%, respectiveꢀ
ly. The substitution of the side groups only on the fluorene
portion of the CS moiety was thought to slightly reduce the
efficiency of CS by generating nonꢀradiative decay caused by
the rotation and vibration of the molecule. In contrast, the
PLQY of TPꢀCSꢀTP was 87%, i.e., higher than that of CS by
approximately 43%. We attributed this increase in PLQY to an
increase in electron density of the CS moiety resulting from
the substitution of the TP side group on the chrysene portion
of the moiety; these results were also attributed to their EL
1
1
TP up to this TP side group.
The UVꢀVis absorption pattern in the solution and film
states of the three synthesized materials showed relatively
sharp absorption peaks for CS and TPꢀCSꢀTP, whereas CSꢀ
TPTP displayed a broad absorption peak. The sharpness of the
absorption peaks of CS was attributed to the rigidity of the
molecule, caused by the fusion of the chrysene and spirobifluꢀ
orene subunits. And TPꢀCSꢀTP apparently maintained not
only the rigidity in the CS moiety, but also the rigidity from
the side group attached to the chrysene portion of the molecule.
However, the broadness of the absorption peak of CSꢀTPTP
was attributed to it having two side groups attached to the
fluorene portion, which apparently caused a decreased rigidity
14
properties.
The radiative (k ) and nonꢀradiative rate constants (k ) of
rad
nr
the three synthesized compounds were calculated based on the
results of fluorescence lifetime measurements. The fluoresꢀ
cence lifetime of CS, CSꢀTPTP and TPꢀCSꢀTP was 3.14, 3.07,
and 2.14 ns, respectively. TPꢀCSꢀTP showed faster decay
compared to CS and CSꢀTPTP. It could be explained by that
TPꢀCSꢀTP has relatively weak intermolecular interaction
compared to other two compounds. CS and CSꢀTPTP showed
1
0b,12
compared to CS and TPꢀCSꢀTP.
This rigidity result was explained by comparing the DFTꢀ
calculated torsion angles for the connections of the CS moiety
to the TP side groups. Those on the fluorene (β position) and
chrysene (γ position) portions of the CS moiety were calculatꢀ
ed to be 37 ° and 54 °, respectively. The greater dihedral angle
for the connection to the chrysene portion would appear to
explain the relatively high rigidity of TPꢀCSꢀTP, which inꢀ
cludes such a connection, and the decreased rigidity of CSꢀ
TPTP, whose TP side groups only connect to the fluorene
portion.
8
7
the same k of 1.94 × 10 /s and k of 12.3 × 10 /s and 13.1
rad
nr
7
× 10 /s, respectively. However, TPꢀCSꢀTP showed the highest
krad of 4.09 × 10 /s and the lowest k of 5.80 × 10 /s. Thus,
the value of k /k for TPꢀCSꢀTP was 7.04, which is the largꢀ
est value among the three compounds. As a result, the trend in
krad/knr among the three compounds was same as that for fluoꢀ
rescence quantum efficiency (Figure S3, Table S2).
8
7
nr
rad nr
The highest occupied molecular orbital (HOMO) levels of
the three synthesized materials were determined to be ꢀ5.63
eV to ꢀ5.79 eV and the lowest unoccupied molecular orbital
In the solution state, the PL maximum (PLmax) value of CS
was observed at a wavelength of 417 nm, and that of CSꢀ
TPTP was similar, at 420 nm, but the PLmax of TPꢀCSꢀTP was
shown to be at 440 nm. In the film state, PLmax values of CS
(
LUMO) levels were from ꢀ2.59 eV to ꢀ2.78 eV. The electroꢀ
3
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 4 of 8
chemical properties of the three compounds were measured by
cyclic voltammetry (CV). All three compounds showed the
first oxida
tained for CS as shown in Figure S1, single crystals could not
be obtained for CSꢀTPTP and TPꢀCSꢀTP.
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
The synthesized compounds were used as nonꢀdoped emitꢀ
Table 2. EL Performance of Synthesized Compounds
a
a
a
a
b
compd
C.E. (cd/A)
P.E. (lm/W)
EQE (%)
CIE (x,y)
ELmax (nm)
CS
CS-TPTP
TP-CS-TP
1.21
0.84
2.39
0.70
0.44
1.19
3.01
2.12
3.05
(0.153, 0.050)
(0.154, 0.049)
(0.148, 0.098)
435
435
453
a
2 b
Measured at 10 mA/cm . Measured at 7 V.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
ting layers (EMLs) in OLEDs with the following structure:
ITO/NPB (40 nm)/TCTA (20 nm)/EML (30 nm)/TPBi (20
nm)/LiF (1 nm)/Al (200 nm). The OLED properties are sumꢀ
marized in Table 2 and Figure 3. CS showed a current effiꢀ
ciency (C.E.) of 1.21 cd/A, power efficiency (P.E.) of 0.70
lm/W, and external quantum efficiency (EQE) of 3.01%; it
also showed a CIE of (0.153, 0.050) and EL maximum (ELmax
)
value of 435 nm, indicative of emission in the deepꢀblue reꢀ
gion. CSꢀTPTP showed a C.E. of 0.84 cd/A, P.E. of 0.44
lm/W, and EQE of 2.12%, approximately 30% lower than that
of CS. As described above, CSꢀTPTP might undergo many
occurrences of nonꢀradiative decay caused by rotation and
vibration of the side group and promoted by the relatively
small approximately 37 ° dihedral angle of each of the two
bonds connecting its core and side groups. Instead, CSꢀTPTP
presumably has not only the highly twisted core structure of
CS but also the lack of any extended πꢀconjugation. CSꢀTPTP
showed a CIE of (0.154, 0.049) and ELmax of 435 nm, very
similar to those of CS and also indicative of emission in the
Figure 3. EL performances of the synthesized materials. (a)
14
Current densityꢀvoltageꢀluminance characteristics. (b) Current
and power efficiency as a function of current density at 10
deepꢀblue region.
Of the three synthesized materials, TPꢀCSꢀTP showed the
highest EL efficiency, with a C.E. of 2.39 cd/A, P.E. of 1.19
lm/W, and EQE of 3.05%. This current efficiency value was
twice that of the CS core compound. This result was due to the
high PLQY and can be also explained by the side group conꢀ
nected to the chrysene portion enriching the electron density
of the CS moiety. TPꢀCSꢀTP, however, showed a CIE of
2
mA/cm . (c) External quantum efficiency as a function of curꢀ
2
rent density at 10 mA/cm . (d) EL spectra at 7 V.
ꢀtion at around 1.0 V. After 30 CV cycles, the current intensity
shapes were maintained for all three compounds, indicating
that the compounds exhibited electrochemical stability for up
to 30 cycles (Figure S4).
(0.148, 0.098) and ELmax of 453 nm, i.e., redꢀshifted by 18 nm
that from CS. This difference was attributed to the intramolecꢀ
ularly lengthened πꢀconjugation of TPꢀCSꢀTP. The CIE and
ELmax v14alues of TPꢀCSꢀTP were nevertheless still in the blue
region.
The decomposition temperature (t ) values of CS, CSꢀTPTP,
d
and TPꢀCSꢀTP were measured to be 358 °C, 522 °C, and
5
22 °C, respectively. Generally, the larger the molecular
weight, the larger the t value; hence, the essentially identical
d
According to the increased current density of TPꢀCSꢀTP, the
efficiency of this compound was decreased compared to those
of CS and CSꢀTPTP. TPꢀCSꢀTP had a higher operating voltꢀ
age than did CS or CSꢀTPTP (Figure 3(a)). However, considꢀ
ering the band diagram (Figure S6), charge injection is exꢀ
pected to be similar for the three compounds. This means that
it is relatively difficult for TPꢀCSꢀTP to transport charge in the
emitter compared to CS and CSꢀTPTP. To confirm carrierꢀ
transport properties of synthesized materials, hole only device
(HOD) and electron only devices (EOD) were fabricated. The
configuration of HOD and EOD were ITO/ NPB (40 nm)/
TCTA (20 nm)/ EML (30nm)/ NPB (20 nm)/Al (100 nm) and
ITO/ TPBi (40 nm)/ EML (30nm)/ TPBi (20 nm)/LiF (1
nm)/Al (100 nm), respectively. As shown in HOD and EOD
data of Figure S7, the hole transporting property of three synꢀ
thesized materials was similar but the electron transporting
property of TPꢀCSꢀTP was slightly inferior to those of CS and
CSꢀTPTP. Thus, TPꢀCSꢀTP might give rise to significant effiꢀ
td values of CSꢀTPTP and TPꢀCSꢀTP were attributed to their
identical molecular weights, and their t values being larger
d
than that of CS was attributed to their greater molecular
weights due to the substituted side groups (Figure S5(a)).
CS, CSꢀTPTP, and TPꢀCSꢀTP were measured to have glass
transition temperature (t ) values of 108 °C, 195 °C, and
g
1
91 °C, respectively. This result was indicative of their high
thermal stabilities. This result was also consistent with the 3D
nature of the chemical structure promoting the formation of an
15
amorphous state. Using a chromophore with such a high
thermal stability has been proposed to be important for formꢀ
ing a stable OLED device whose morphology does not easily
change in the presence of the heat generated from the operaꢀ
16
tion of the device.
The melting temperature (t ) value of CS was measured at
m
2
50 °C, but the t values of CSꢀTPTP and TPꢀCSꢀTP were not
m
obtained. This indicated that CSꢀTPTP and TPꢀCSꢀTP became
more amorphous than CS, due to the TP side groups (Figure
S5(b)). Thus, although a single crystal could be easily obꢀ
17
ciency decay at high current density.
4
ACS Paragon Plus Environment

Page 5 of 8
The Journal of Organic Chemistry
quencies were not found. Geometry optimization in Cartesian
CONCLUSION
1
2
3
4
5
6
7
8
9
coordinates was shown in Table S3.
In this study, chrysene and spirobifluorene were fused, and a
new deepꢀblue core chromophore, CS, having structural comꢀ
ponents extending in three dimensions, was synthesized. Also,
in order to increase the efficiency or adjust the emission waveꢀ
length of the chromophore, we tested two additional comꢀ
pounds in which TP side groups were substituted at two difꢀ
ferent sets of positions of the CS core. In one of these comꢀ
pounds, i.e., TPꢀCSꢀTP, resulted in the highest current effiꢀ
ciency (with a value of 2.39 cd/A) and EQE (3.05%) of the
three compounds synthesized. We expect this fused system to
be used in future studies with other deep blue chromophores,
such as anthracene, carbazole, and phenanthrene, to develop
many additional new deepꢀblue 3D core chromophores. We
also expect various novel blue luminescent materials to be
made by systematically testing replacing the side group. This
approach should lead to the development of organic functional
materials with outstanding characteristics.
Fabricated OLED device. In each of the EL devices, N,N'ꢀ
bis(naphthalenꢀ1ꢀyl)ꢀN,N'ꢀbis(phenyl)benzidine (NPB) was
used for the hole injection layer (HIL), tris(4ꢀcarbazoylꢀ9ꢀ
ylphenyl)amine (TCTA) was used for the hole transporting
layer (HTL), one of the synthetic materials (CS, CSꢀTPTP, or
TPꢀCSꢀTP) was used as the emitting layer (EML), 1,3,5ꢀtris(1ꢀ
phenylꢀ1Hꢀbenzimidazolꢀ2ꢀyl)benzene (TPBi) was used for
the electron transporting layer (ETL), lithium fluoride (LiF)
was used for the electron injection layer (EIL), ITO was used
as the anode, and Al was used as the cathode. All organic layꢀ
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
ꢀ6
ers were deposited under 10 Torr, with a rate of deposition of
2
1
Å/s to create an emitting area of 4 mm . The LiF and Al
layers were continuously deposited under the same vacuum
conditions. The luminance efficiency data for the fabricated
EL devices were obtained by using a Keithley 2410
sourcemeter. Light intensities were obtained using a Minolta
CSꢀ1000A spectroradiometer. The operational stabilities of the
devices were measured under encapsulation in a glove box.
EXPERIMENTAL SECTION
1
13
General Methods. The H NMR spectra and C NMR specꢀ
tra were recorded on Bruker Avance 300 and Avance 500 specꢀ
trometers. The FAB+ꢀmass was recorded on a JEOL, JMSꢀ
AX505WA, HP5890 series II. The optical absorption spectra
were obtained by using a Lambda 1050 UV/Vis/NIR specꢀ
trometer (PerkinElmer). A PerkinElmer luminescence specꢀ
trometer LS55 (Xenon flash tube) was used to perform photoꢀ
luminescence (PL) spectroscopy. Absolute PL quantum yield
was measured using a JASCO FP8500 spectrometer in the
toluene solution state. Timeꢀresolved PL was estimated by
QuantaurusꢀTau fluorescence lifetime measurement sysꢀ
tem (C11367ꢀ03, Hamamatsu Photonics Co.) in toluene
solution state. Cyclic voltammetry (CV) was performed on
an AUTOLAB/PGꢀSTAT12 model system with a threeꢀ
electrode cell in a 0.1 M of tetrabutylammonium hexꢀ
afluorophosphate (TBAHFP) and 1 mM of sample in aceꢀ
tonitrile at a scan rate of 100 mV/s. The glass transition
temperatures (t ) and melting temperatures (t ) of the comꢀ
Single crystal X-ray diffraction data of CS. Each good
quality air stable single crystal was mounted on a Bruker
SMART CCD diffractometer. Diffraction data were collected
at room temperature using graphite monochromated Mo Ka
radiation (k = 0.71073 Å). The structure was solved by applyꢀ
ing the direct method using SHELXSꢀ97 and refined by a fullꢀ
19
matrix leastꢀsquares calculation on F2 using SHELXLꢀ97.
All nonꢀH atoms were refined with anisotropic displacement
parameters. Hydrogen atoms were fixed at ideal geometric
positions, and their contributions were included in the strucꢀ
tural factor calculations. The crystal data were as follows:
3
C H ; FW = 466.54, crystal size 0.30 × 0.29 × 0.27 mm ,
37
22
Triclinic, P–1, a = 11.082(4) Å, b = 11.456(4) Å, c = 11.777(4)
Å, α = 92.038(19) °, β = 110.429(19) °, γ = 118.082(16) °, V =
3
3
1
199.5(7) Å , Z = 2, Dc = 1.292 mg/m . The refinement conꢀ
verged to R = 0.0514, wR = 0.1300 (I > 2σ(I)). CCDC
1
2
1
557124.
g
m
pounds were determined using differential scanning calorimeꢀ
try (DSC) under a nitrogen atmosphere by using a DSC 4000
Synthesis. 6ꢀbromochrysene and 6,12ꢀdibromoꢀchrysene
were purchased from WITHCHEM co., Ltd. Compd 6 and 7
(
PerkinElmer). Samples were heated from room temperature
to 300 °C or 450 °C at a rate of 10 °C/min and cooled at
0 °C/min, then heated again under the same heating condiꢀ
tions as used in the initial heating process. Degradation temꢀ
20
were synthesized according to the literature.
1
6
-(2-Bromo-phenyl)-chrysene (1). 6ꢀbromochrysene (4.0 g,
peratures (t ) were determined with thermogravimetric analyꢀ
d
1.30 mmol) and Pd(PPh ) (0.76 g, 0.65 mmol) were added to
3
4
sis (TGA) by using a TGA 4000 (PerkinElmer). Samples were
heated from room temperature to 800 °C at a rate of 10 °C/min.
The highest occupied molecular orbital (HOMO) levels of the
synthesized materials were determined via photoelectron specꢀ
troscopy (Riken Keiki ACꢀ2) by using an ultraviolet light enꢀ
ergy source. The lowest unoccupied molecular orbital (LUMO)
energy levels were calculated from the HOMO levels and the
optical band gaps. The optical band gaps were derived by deꢀ
anhydrous toluene solution (200 mL) under nitrogen. Then, 2ꢀ
bromoꢀphenyl boronic acid (4.0 g, 2.00 mmol), which was
dissolved in anhydrous ethanol (20 mL), was dropped slowly
and 2 M K CO solution (100 mL) dissolved in H O was addꢀ
ed to the reaction mixture at 50 °C. The mixture was refluxed
for 1 hour. After the reaction was complete, the reaction mixꢀ
ture was extracted with chloroform and water. The organic
2
3
2
layer was dried with anhydrous MgSO and filtered. The soluꢀ
4
2
termining the absorption edges from plots of (hv) vs. (αhv) ,
where α, h, and v are the absorbance, Planck's constant, and
the frequency of light, respectively.
tion was evaporated. The product was isolated with silica gel
column chromatography using toluene : nꢀhexane (1:10) as the
1
eluent to obtain a white solid (1.5 g, 35%). H NMR (300
MHz, [D ]THF): δ= 8.96 (d, 1H), 8.88 (dd, 2H), 8.70 (s, 1H),
8
8
7
1
.08 (d, 1H), 8.02 (d, 1H), 7.83 (d, 1H), 7.72ꢀ7.50 (m, 7H),
13
Computational details. We determined the optimized strucꢀ
tures by using density functional theory (DFT) B3LYP/6ꢀ
.44 (m, 1H); C NMR (75 MHz, [D ]THF): δ= 143.1, 139.5,
8
33.8, 133.6, 133.3, 131.9, 131.8, 130.4, 129.5, 129.4, 128.8,
3
1G(d) calculations performed using the Gaussian09 proꢀ
128.6, 128.5, 127.7, 127.6, 127.4, 127.4, 125.5, 124.5, 124.4,
1
for C H Br 382.0357; Found 382.0359.
18
+
gram. All of the optimized structures were characterized to
be energy minima of the potential surfaces. Imaginary freꢀ
23.5, 122.1. HRMS (FAB/magnetic sector) m/z: [M] Calcd.
24 15
5
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 6 of 8
1
28.1, 128.0, 127.9, 127.9, 127.8, 126.7, 125.9, 125.8, 125.7,
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
125.5, 124.7, 124.2, 123.9, 123.1, 122.5, 122.2. HRMS
(FAB/magnetic sector) m/z: [M+H] Calcd. for C73
923.3633; Found, 923.3635. Anal. Calcd. for C73
H 5.02; Found: C 94.75, H 5.07.
Spiro[fluorene-9,15'-indeno[2,1-g]chrysene] (CS). Compd
1 (1.0 g, 2.61 mmol) was added to anhydrous THF solution
(20 mL) under nitrogen. Then, 2.0 M nꢀbutyllithium in cycloꢀ
hexane (1.56 mL) was added slowly at ꢀ78 °C. Next, 9ꢀ
fluorenone (0.56 g, 3.13 mmol) dissolved in anhydrous THF
+
H
,
47
H46: C 94.98,
(10 mL) was added to the reaction mixture, followed by satuꢀ
6-Bromo-12-[1,1';3',1'']terphenyl-5'-yl-chrysene (3). 6,12ꢀ
dibromoꢀchrysene (4.0 g, 10.4 mmol), compd 7 (4.08 g, 11.5
rated NaHCO solution (15 mL) at room temperature. The
3
mixture was stirred for 3 h. After the reaction was complete,
the reaction mixture was extracted with chloroform and water.
mmol), and Pd(PPh
hydrous toluene solution (500 mL) under nitrogen. Then, 2 M
CO solution (50 mL) dissolved in H O was added to the
) (0.48 g, 0.42 mmol) were added to anꢀ
3 4
The organic layer was dried with anhydrous MgSO and filꢀ
K
2
3
2
4
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
tered. The mixture was resolved acetic acid (50 mL) and 35 wt%
HCl (5 mL) was added. The mixture was refluxed for 1 h.
After the reaction was complete, the reaction mixture was
extracted with chloroform and water. The organic layer was
reaction mixture at 50 °C. The mixture was refluxed for 3 h.
After the reaction was complete, the reaction mixture was
extracted with chloroform and water. The organic layer was
dried with anhydrous MgSO and filtered. The solution was
evaporated. The product was isolated with silica gel column
chromatography using chloroform : nꢀhexane (1:10) as the
eluent to obtain a white solid (2.5 g, 49%). H NMR (300
MHz, [D ]THF): δ= 9.26 (s, 1H), 9.02ꢀ8.97 (m, 2H), 8.87 (s,
1H), 8.46ꢀ8.42 (m, 1H), 8.16 (d, 1H), 8.06 (s, 1H), 7.90 (s,
4
dried with anhydrous MgSO and filtered. The solution was
4
evaporated. The product was isolated with silica gel column
chromatography using chloroform : nꢀhexane (1:2) as the eluꢀ
1
1
ent to obtain a white solid (0.49 g, 45%). H NMR (300 MHz,
8
[
D ]THF): δ= 9.19 (d, 1H), 9.00 (d, 1H), 8.83 (d, 1H), 8.52 (d,
8
1
1
H), 8.10 (d, 2H), 7.89ꢀ7.82 (m, 3H), 7.67 (d, 1H), 7.61 (d,
2H), 7.84ꢀ7.73 (m, 7H), 7.65 (t, 1H), 7.49 (t, 4H), 7.38 (t, 2H);
13
H), 7.36ꢀ7.25 (m, 3H), 7.17 (t, 1H), 6.96ꢀ6.89 (m, 3H), 6.66
C NMR (75 MHz, [D ]THF): δ= 143.2, 143.1, 142.0, 141.1,
8
13
(d, 2H), 6.63 (t, 1H), 6.43 (d, 1H); C NMR (75 MHz,
132.9, 132.4, 131.8, 131.3, 129.8, 129.5, 128.8, 128.8, 128.6,
128.5, 128.3, 128.0, 127.9, 126.6, 126.0, 125.1, 124.7, 123.5,
123.2. HRMS (FAB/magnetic sector) m/z: [M] Calcd. for
[
D ]THF): δ= 152.8, 149.5, 143.1, 141.2, 141.0, 133.9, 133.2,
8
+
131.2, 130.6, 129.5, 129.2, 129.2, 128.9, 128.7, 128.6, 128.0,
127.9, 127.9, 127.8, 127.7, 126.5, 125.7, 125.5, 124.5, 124.1,
C H23Br, 534.0983; Found 534.0984.
36
123.9, 123.7, 122.9, 121.7. HRMS (FAB/magnetic sector) m/z:
+
[
M] Calcd. for C H 466.1722; Found, 466.1723. Anal.
6-(2-Bromo-phenyl)-12-[1,1';3',1'']terphenyl-5'-yl-
37 22
Calcd. for C H : C 95.25, H 4.75; Found: C 95.07, H 4.73.
chrysene (4). Compd 3 (5.0 g, 9.34 mmol) and Pd(PPh3)4
37
22
(0.48 g, 0.42 mmol) were added to anhydrous toluene solution
2
,7-Dibromospiro[fluorene-9,15'-indeno[2,1-g]chrysene]
(200 mL) under nitrogen. Then, 2ꢀbromoꢀphenyl boronic acid
(2.3 g, 11.5 mmol), which was dissolved in anhydrous ethanol
(20 mL), was dropped slowly and 2 M K CO solution (20 mL)
(2). This compound was synthesized with the same method as
for CS by using 2,7ꢀdibromoꢀ9ꢀfluorenone (1.05 g, 3.13
2
3
mmol). Accordingly, a white solid was obtained (0.70 g, 47%).
dissolved in H O was added to the reaction mixture at 50 °C.
2
1
H NMR (300 MHz, [D ]THF): δ= 9.20 (d, 1H), 9.04 (d, 1H),
The mixture was refluxed for 30 min. After the reaction was
complete, the reaction mixture was extracted with chloroform
and water. The organic layer was dried with anhydrous MgSO4
and filtered. The solution was evaporated. The product was
isolated with silica gel column chromatography using toluene :
nꢀhexane (1:10) as the eluent to obtain a white solid (1.1 g,
30%). H NMR (300 MHz, [D ]THF): δ= 9.04 (d, 1H), 8.99 (d,
1H), 8.94 (s, 1H), 8.77 (s, 1H), 8.17 (d, 1H), 8.07 (s, 1H), 7.93
(d, 2H), 7.85 (d, 5H), 7.71ꢀ7.33 (m, 14H); C NMR (75 MHz,
8
8.88 (d, 1H), 8.57 (d, 1H), 8.07 (d, 2H), 7.94ꢀ7.84 (m, 3H),
7.76 (d, 1H), 7.56 (t, 3H), 7.37 (t, 1H), 7.25 (t, 1H), 7.03 (t,
1
3
1H), 6.82 (s, 2H), 6.66 (t, 1H), 6.44 (d, 1H); C NMR (75
MHz, [D ]THF): δ= 151.7, 151.0, 141.2, 141.1, 139.4, 134.0,
8
1
1
1
33.4, 132.3, 131.5, 130.4, 129.4, 128.9, 128.5, 128.4, 128.3,
28.2, 126.8, 126.7, 125.8, 125.6, 124.8, 124.6, 123.6, 123.6,
23.2, 123.1. HRMS (FAB/magnetic sector) m/z: [M] Calcd.
1
8
+
13
for C H Br , 621.9932; Found 621.9930.
37
20
2
[
D ]THF): δ= 143.5, 143.1, 143.1, 142.1, 140.7, 139.6, 133.8,
8
2
,7-Di([1,1':3',1''-terphenyl]-5'-yl)spiro[fluorene-9,15'-
132.3, 132.3, 132.0, 131.9, 130.5, 129.8, 128.9, 128.5, 128.3,
127.8, 127.7, 127.6, 127.6, 127.5, 125.9, 125.6, 124.8, 123.4,
123.4. HRMS (FAB/magnetic sector) m/z: [M] Calcd. for
indeno[2,1-g]chrysene] (CS-TPTP). Compd 2 (0.6 g, 0.96
+
mmol), compd 7 (0.82 g, 2.30 mmol), Pd(OAC) (0.017 g,
2
0
.075 mmol), and tricyclohexylphosphine (0.044 g, 0.16 mmol)
C H27Br, 610.1296; found 610.1288.
42
were added to anhydrous THF (100 mL). Then, (Et) NOH (20
4
wt%, 10 mL) was added to the reaction mixture at 50 °C. The
mixture was refluxed for 3 h under nitrogen. After the reaction
was complete, the reaction mixture was extracted with chloroꢀ
form and water. The organic layer was dried with anhydrous
5'-([1,1':3',1''-Terphenyl]-5'-yl)-2-bromospiro[fluorene-
9,15'-indeno[2,1-g]chrysene] (5). Compd 4 (1.0 g, 1.64 mmol)
was added to anhydrous THF solution (20 mL) under nitrogen.
Then, 2.0 M nꢀbutyllithium in cyclohexane (0.98 mL) was
added slowly at ꢀ78 °C. Next, 2ꢀbromoꢀ9ꢀfluorenone (0.51 g,
1.95 mmol) dissolved in anhydrous THF (10 mL) was added
MgSO and filtered. The solution was evaporated. The product
4
was isolated with silica gel column chromatography using
chloroform : nꢀhexane (1:3) as the eluent to obtain a white
to the reaction mixture, followed by saturated NaHCO soluꢀ
3
1
solid (0.48 g, 60%). H NMR (500 MHz, [D8]THF): δ= 9.15
tion (15 mL) at room temperature. The mixture was stirred for
3 h. After the reaction was complete, the reaction mixture was
extracted with chloroform and water. The organic layer was
(d, 1H), 9.00 (d, 1H), 8.84 (d, 1H), 8.50 (d, 1H), 8.28 (d, 2H),
7
.92 (d, 1H), 7.83ꢀ7.77 (m, 5H), 7.70 (d, 1H), 7.64 (s, 2H),
7.55 (d, 8H), 7.42 (s, 4H), 7.34 (t, 8H), 7.32ꢀ7.23 (m, 5H),
7.20 (t, 1H), 7.02 (s, 2H), 6.98 (t, 1H), 6.68 (t, 1H), 6.62 (d,
dried with anhydrous MgSO and filtered. The mixture was
4
resolved in acetic acid (50 mL) and 35 wt% HCl (5 mL) was
added. The mixture was refluxed for 1 h. After the reaction
was complete, the reaction mixture was extracted with chloroꢀ
form and water. The organic layer was dried with anhydrous
1
3
1
1
1
H); C NMR (125 MHz, [D ]THF): δ= 152.6, 150.9, 143.2,
8
43.1, 142.5, 142.3, 142.1, 141.3, 141.3, 141.2, 133.8, 133.3,
31.3, 130.9, 129.6, 129.5, 129.4, 129.3, 128.5, 128.5, 128.2,
6
ACS Paragon Plus Environment

Page 7 of 8
The Journal of Organic Chemistry
MgSO and filtered. The solution was evaporated. The product
was isolated with silica gel column chromatography using
This research was supported by a grant from the Technology Deꢀ
velopment Program for Strategic Core Materials funded by the
Ministry of Trade, Industry & Energy, Republic of Korea (Project
No. 10047758). This research was supported by a grant from the
Core Technology Development Program for the Commercializaꢀ
tion of Functional Chemicals funded by the Ministry of Trade,
Industry and Energy, Republic of Korea (Project No. 10060523).
This research was supported by National R&D Program through
the National Research Foundation of Korea(NRF) funded by the
Ministry of Science & ICT (No.2017M3A7B4041699).
4
1
2
3
4
5
6
7
8
9
chloroform : nꢀhexane (1:2) as the eluent to obtain a white
1
solid (0.48 g, 43%). H NMR (300 MHz, [D ]THF): δ= 9.22
8
(d, 1H), 9.10 (d, 1H), 8.92 (s, 1H), 8.57 (d, 1H), 8.14 (d, 1H),
8
7
6
.09 (d, 1H), 8.01 (s, 1H), 7.91ꢀ7.78 (m, 9H), 7.70 (d, 1H),
.58 (dd, 1H), 7.47ꢀ7.31 (m, 8H), 7.16 (t, 1H), 7.02 (t, 2H),
.94 (s, 1H), 6.69ꢀ6.60 (m, 2H), 6.45 (d, 1H); C NMR (75
1
3
MHz, [D ]THF): δ= 152.0, 151.9, 149.2, 143.2, 143.1, 142.2,
8
1
1
1
42.1, 142.0, 141.5, 141.1, 140.3, 140.1, 133.3, 132.5, 132.1,
31.1, 130.8, 129.8, 129.6, 129.6, 129.2, 129.0, 128.8, 128.8,
28.5, 128.3, 128.2, 128.1, 128.0, 126.8, 126.7, 126.5, 125.9,
REFERENCES
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
(
1) Guo, J.; Li, X. L.; Nie, H.; Luo, W.; Gan, S.; Hu, S.; Hu, R.; Qin,
A.; Zhao, Z.; Su, S. J.; Tang, B. Z. Adv. Funct. Mater., 2017, 27,
606458.
2) Tseng, H. S.; Phan, H.; Luo, C.; Wang, M.; Perez, L. A.; Patel, S.
125.8, 125.8, 124.6, 124.4, 124.3, 123.8, 123.4, 122.7, 122.0.
+
HRMS (FAB/magnetic sector) m/z: [M] Calcd. for C H Br,
55
33
1
(
772.1766; Found 772.1775.
N.; Ying, L.; Kramer, E. J.; Nguyen, T. Q.; Bazan, G. C.; Heeger, A. J.
Adv. Mater., 2014, 26, 2993ꢀ2998.
(3) Wu, Q.; Zhao, D.; Yang, J.; Sharapov, V.; Cai, Z.; Li, L.; Zhang,
N.; Neshchandin, A.; Chen, W.; Yu, L. Chem. Mater., 2017, 29,
2
,5'-Di([1,1':3',1''-terphenyl]-5'-yl)spiro[fluorene-9,15'-
indeno[2,1-g]chrysene] (TP-CS-TP). Compd 5 (0.4 g, 0.52
mmol), compd 7 (0.22 g, 0.62 mmol), Pd(OAC) (0.004 g,
2
1
127ꢀ1133.
0
.018 mmol), and tricyclohexylphosphine (0.012 g, 0.043
mmol) were added to anhydrous THF (100 mL). Then,
Et) NOH (20 wt%, 10 mL) was added to the reaction mixture
(4) (a) Lorente, A.; Pingel, P.; Liaptsis, G.; Krüger, H.; Janietz, S.
Org. Electron., 2017, 41, 91ꢀ99. (b) Li, J.; Han, X.; Bai, Q.; Shan, T.;
Lu, P.; Ma, Y. J. Polym. Sci. A Polym. Chem., 2017, 55, 707ꢀ715.
(
4
at 50 °C. The mixture was refluxed for 3 h under nitrogen.
After the reaction was complete, the reaction mixture was
extracted with chloroform and water. The organic layer was
(
5) (a) Kim, S. K.; Yang, B.; Park, Y. I.; Ma, Y.; Lee, J. Y.; Kim, H.
J.; Park, J. Org. Electron., 2009, 10, 822ꢀ833. (b) Lee, H.; Kim, B.;
Kim, S.; Kim, J.; Lee, J.; Shin, H.; Lee J. H.; Park, J. J. Mater. Chem.
C, 2014, 2, 4737ꢀ4747. (c) Lee, J.; Kim, B.; Kwon, J. E.; Kim, J.;
Yokoyama, D.; Suzuki, K.; Nishimura, H.; Wakamiya, A.; Park, S. Y.;
Park, J. Chem. Commun., 2014, 50, 14145ꢀ14148. (d) Lee, H.; Jo, M.;
Yang, G.; Jung, H.; Kang, S.; Park, J. Dyes Pigm. 2017, 146, 27ꢀ36.
dried with anhydrous MgSO and filtered. The solution was
4
evaporated. The product was isolated with silica gel column
chromatography using chloroform : nꢀhexane (1:3) as the eluꢀ
1
ent to obtain a white solid (0.43 g, 90%). H NMR (300 MHz,
(
6) (a) Kuma, H.; Hosokawa, C. Sci. Techol. Adv. Mater., 2014, 15,
[
D ]THF): δ= 9.21 (d, 1H), 9.10 (d, 1H), 8.92 (s, 1H), 8.55 (d,
8
034201. (b) Zhao, Lei.; Wang, Shumeng.; Ding, Junqiao.; Wang,
Lixiang. Org. Electron., 2018, 53, 43ꢀ49. (c) Bai, Keyan.; Wang,
Shumeng.; Zhao, Lei.; Ding, Junqiao.; Wang, Lixiang. Polym. Chem.,
1
7
7
2
H), 8.28 (d, 1H), 8.17 (d, 1H), 7.99 (s, 1H), 7.88ꢀ7.80 (m,
H), 7.77 (d, 4H), 7.64 (s, 1H), 7.53 (t, 6H), 7.44 (q, 5H),
.35ꢀ7.23 (m, 7H), 7.20 (t, 4H), 7.00 (t, 2H), 6.70ꢀ6.64 (m,
2
017, 8, 2182ꢀ2188. (d) Yu, Mingquan.; Wang, Shumeng.; Shao,
1
3
H), 6.53(d, 1H); C NMR (75 MHz, [D ]THF): δ= 152.7,
Shiyang.; Ding, Junqiao.; Wang, Lixiang.; Jing, Xiabin.; Wang,
Fosong. J. Mater. Chem. C, 2015, 3, 861ꢀ869.
8
150.5, 149.8, 143.2, 143.0, 142.8, 142.6, 142.5, 142.1, 142.0,
41.5, 141.1, 141.0, 140.2, 133.2, 132.4, 131.3, 130.7, 129.7,
129.5, 129.1, 128.8, 128.4, 128.2, 128.2, 128.0, 127.9, 126.7,
26.2, 125.8, 124.5, 124.2, 123.9, 123.6, 122.5, 122.2, 121.8.
(7) (a) Kim, S.; Kim, B.; Lee, J.; Shin, H.; Park, Y. I.; Park, J. Mater.
Sci. Eng. R Rep., 2016, 99, 1ꢀ22. (b) Shin, H.; Jung, H.; Kim, B.; Lee,
J.; Moon, J.; Kim J.; Park, J. J. Mater. Chem. C, 2016, 4, 3833ꢀ3842.
(8) Huang, J.; Sun, N.; Dong, Y.; Tang, R.; Lu, P.; Cai, P.; Li, Q.;
Ma, D.; Qin, J.; Li, Z. Adv. Funct. Mater., 2013, 23, 2329ꢀ2337.
(9) (a) Lei, T.; Luo, J.; Wang, L.; Ma, Y.; Wang, J.; Cao, Y.; Pei, J.
New. J. Chem., 2010, 34, 699ꢀ707. (b) Luo, J.; Zhou, Y.; Niu, Z. Q.;
Zhou, Q. F.; Ma, Y.; Pei, J. J. Am. Chem. Soc., 2007, 129, 11314ꢀ
11315. (c) Liu, F.; Xie, L. H.; Tang, C.; Liang, J.; Chen, Q. Q.; Peng,
B.; Wei, W.; Cao, Y.; Huang, W. Org. Lett., 2009, 11, 3850ꢀ3853.
(10) (a) Lee, J.; Park, J. Org. Lett., 2015, 17, 3960ꢀ3963. (b) Park, S.
H.; Jin, Y.; Kim, J. Y.; Kim, S. H.; Kim, J.; Suh, H.; Lee, K. Adv.
Funct. Mater., 2007, 17, 3063ꢀ3068. (c) Skoog, D. A.; West, D. M.;
Holler, F. J.; Crouch, S. R. Molecular Fluorescence Spectroscopy.
Fundamentals of Analytical of Chemistry, 8; Brooks/Cole: Cengage
Learning, Belmont, CA, USA, 2004; pp 828.
1
1
+
HRMS (FAB/magnetic sector) m/z: [M+H] Calcd. for C H ,
73 47
9
23.3633; Found, 923.3639. Anal. Calcd. for C H : C 94.98,
73 46
H 5.02; Found: C 94.75, H 5.06.
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI:
Xꢀray data for CS
(11) Kim, E.; Koh, M.; Lim, B. J.; Kim, S. B. J. Am. Chem. Soc.,
UVꢀVis, PL spectrum, Xꢀray data, TRPL, CV, TGA, DSC data,
2
(
011, 133, 6642ꢀ6649
12) (a) Iannotta, S.; Toccoli, T.; Boschetti, A.; Scardi, P. Synth.
1
13
H NMR, and C NMR spectra.
Met., 2001, 122, 221ꢀ223. (b) Ichino, Y.; Ni, J. P.; Ueda, Y.; Wang, D.
K. Synth. Met., 2001, 116, 223ꢀ227. (c) Cornil, J.; Beljonne, D.; Shuai,
Z.; Hagler, T. W.; Campbell, I.; Bradley, D. D. C.; Brédas, J. L.;
Spangler, C. W.; Müllen, K. Chem. Phys. Lett., 1995, 247, 425ꢀ432.
(13) Danel, K.; Huang, T. H.; Lin, J. T.; Tao, Y. T.; Chuen, C. H.
Chem. Mater., 2002, 14, 3860ꢀ3865
AUTHOR INFORMATION
Corresponding Author
*
Eꢀmail: jongpark@khu.ac.kr
ORCID
(
14) Park, Y.; Kim, S.; Lee, J. H.; Jung, D. H.; Wu, C. C.; Park, J.
Sang Hyuk Im: 0000ꢀ0001ꢀ7081ꢀ5959
Jongwook Park: 0000ꢀ0002ꢀ6797ꢀ5211
Notes
Org. Electron., 2010, 11, 864ꢀ871.
(15) (a) Bach, U.; Cloedt, K. D.; Spreitzer, H.; Grätzel, M. Adv. Maꢀ
ter., 2000, 12, 1060ꢀ1036. (b) Salbeck, J.; Yu, N.; Bauer, J.; Weissörꢀ
tel, F.; Bestgen, H. Synth. Met., 1997, 91, 209ꢀ215.
The authors declare no competing financial interest.
(
16) O'Brien, D. F.; Burrows, P. E.; Forrest, S. R.; Koene, B. E.; Loy,
D. E.; Thompson, M. E. Adv. Mater., 1997, 10, 1108ꢀ1112.
(17) Giebink, N. C.; Forrest, S. R. Phys. Rev. B, 2008, 77, 235215.
ACKNOWLEDGMENT
7
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 8 of 8
(
18) Gaussian 09, Revision D.1, Frisch, M. J.; Trucks, G. W.; Schleꢀ
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
gel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani,
G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricaꢀ
to, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.;
Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.;
Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai,
H.; Vreven, T.; Montgomery, J. A.; Jr., Peralta, J. E.; Ogliaro, F.;
Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V.
N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Buꢀ
rant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J.
M.; Klene, M; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.;
Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A.
J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuꢀ
ma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J.
J.; Dapprich, S.; Daniels, A. D.; Farkas, Ö.; Foresman, J. B.; Ortiz, J.
V.; Cioslowski, J.; Fox, D. J. Gaussian, Inc., Wallingford CT, 2009.
(19) Sheldrick, G. M. Acta. Cryst., 2008, A64, 112.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
(20) Kim, B.; Park, Y.; Lee, J.; Yokoyama, D.; Lee, J. H.; Kido, J.;
Park, J. J. Mater. Chem. C, 2013, 1, 432ꢀ440.
8
ACS Paragon Plus Environment