Synthesis of dihydroxyoligophenylenes containing π-deficient or π-excess hetero-aromatic rings and their solvatochromic behavior

Article abstract of DOI:10.1016/j.tet.2010.06.087

Dihydroxyoligophenylenes (HO-ArPh(m)-OHs) with 9,9-dihexyl-2,7-fluorene (Ar=Flu), 2,5-dioctyloxy-1,4-benzene (Ar=Dob), pyridine (Ar=Py), or thiophene (Ar=Th) rings were synthesized by the Suzuki coupling reaction. Absorption maxima (λ_max) of HO-ArPh(m)-OHs shifted progressively toward long wavelengths due to the expansion of the π-conjugation system with an increase in the number of benzene rings. Deprotonation of the OH groups of HO-ArPh(m)-OHs by treatment with NaH caused a bathochromic shift of λ_max. The bathochromic shift of the deprotonated species increased with the donor numbers (DNs) of the solvents. The emission peak positions of NaO-ArPh(m)-ONas depended on the DNs of the solvents; therefore, the emission color could be tuned by changing the solvent.

Full text of DOI:10.1016/j.tet.2010.06.087

Tetrahedron 66 (2010) 6725e6732
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Synthesis of dihydroxyoligophenylenes containing
p-deficient or p-excess
hetero-aromatic rings and their solvatochromic behavior
*
Isao Yamaguchi , Kenji Seo, Yukari Kawashima
Department of Material Science, Faculty of Science and Engineering, Shimane University, 1060 Nishikawatsu, Matsue 690-8504, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
Dihydroxyoligophenylenes (HO-ArPh(m)-OHs) with 9,9-dihexyl-2,7-fluorene (Ar¼Flu), 2,5-dioctyloxy-
1,4-benzene (Ar¼Dob), pyridine (Ar¼Py), or thiophene (Ar¼Th) rings were synthesized by the Suzuki
coupling reaction. Absorption maxima (lmax) of HO-ArPh(m)-OHs shifted progressively toward long
Received 18 May 2010
Received in revised form
25 June 2010
Accepted 28 June 2010
Available online 3 July 2010
wavelengths due to the expansion of the
p-conjugation system with an increase in the number of
benzene rings. Deprotonation of the OH groups of HO-ArPh(m)-OHs by treatment with NaH caused
a bathochromic shift of lmax. The bathochromic shift of the deprotonated species increased with the
donor numbers (DNs) of the solvents. The emission peak positions of NaO-ArPh(m)-ONas depended on
the DNs of the solvents; therefore, the emission color could be tuned by changing the solvent.
Ó 2010 Elsevier Ltd. All rights reserved.
Keywords:
Dihydroxyoligophenylene
Suzuki coupling
Hetero-aromatic ring
Photoluminescence
Solvatochromism
1. Introduction
2,5-dioctyloxy-1,4-benzene (Ar¼Dob) units were used as building
blocks, and 9,9-dihexylfluorene-2,7-diboronic acid bis(1,3-pro-
Oligo(p-phenylene)s (OPPs) are an important class of
p
-con-
panediol) ester (1) and 2,5-dioctyloxy-1,4-benzenediboronic acid
(2) were reacted with Br-OPP(n)-OHs (n¼1, 2, and 3).
jugated oligomers because they are useful as luminophores for
light-emitting materials,1e6 as semiconductors for field-effect
transistors,7 as rigid-rod cores for liquid crystalline materials,8e10
and as amphiphilic materials for biological applications.11e15
The abovementioned solvatochromism exhibited by OPP(n)-
ONas and NaO-OPP(3)-ONa was attributed to an intramolecular
charge shift from the sodium phenoxy group(s) to the adjacent
rings.5 In this study, in addition to soluble HO-ArPh(m)-OHs
A
systematic investigation of OPPs containing various sub-
stituents has revealed that the chemical and physical properties of
substituted OPPs depend on the type of substituents employed.
Recently, we have reported OPPs with an OH group located at one
end and at both ends, namely, OPP(n)-OHs (where n is the
number of benzene rings) and HO-OPP(3)-OH, respectively.16 The
OPPs exhibited significant solvatochromism; the deprotonation of
the OH groups of OPP(n)-OHs and HO-OPP(3)-OH, when treated
with NaH, caused a bathochromic shift of lmax that increased with
the donor numbers (DNs) of the solvents. Furthermore, the
emission peak positions of OPP(n)-ONas and NaO-OPP(3)-ONa
depended on the DNs of the solvents; therefore, the emission color
could be tuned by changing the solvent. However, we were unable
to investigate the optical properties of OPP(n)-OH and HO-OPP
(n)-OH (n>4) in detail because of their low solubility. In this study,
to obtain soluble dihydroxyoligophenylenes, namely, HO-ArPh
(m)-OHs (where m is the number of benzene rings), with a longer
p-phenylene group (mꢀ4), 9,9-dihexyl-2,7-fluorene (Ar¼Flu) and
(Ar¼Flu and Doc), HO-ArPh(m)-OHs with a
(Ar¼Py) ring or a -excess thiophene (Ar¼Th) ring were synthe-
sized by the Suzuki coupling reaction. The presence of -deficient
or -excess aromatic rings in HO-ArPh(m)-OHs would significantly
affect the optical properties of HO-ArPh(m)-OHs because the
charge shift from the sodium phenoxide groups to the adjacent
rings depends on the electronic properties of the accepting site
(Ar). To the best of our knowledge, however, no systematic studies
have been conducted on the optical properties of HO-ArPh(m)-OHs
p-deficient pyridine
p
p
p
with
p-deficient or p-excess hetero-aromatic rings. Elucidation of
the optical properties of HO-ArPh(m)-OHs before and after the
deprotonation of the OH groups will lead to a better understanding
of the intramolecular charge shift in the
p-conjugated oligoar-
ylenes and toward the development of new functional materials.
Additionally, HO-ArPh(m)-OHs can be useful starting materials for
highly luminescent and thermally stable polymers.
Herein, we report the synthesis of HO-ArPh(m)-OHs with
a longer p-phenylene group (mꢀ4) and
p-deficient or p-excess
hetero-aromatic rings as well as their optical properties before and
after the deprotonation of the OH groups.
* Corresponding author. E-mail address: iyamaguchi@riko.shimane-u.ac.jp
(I. Yamaguchi).
0040-4020/$ e see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2010.06.087

6726
I. Yamaguchi et al. / Tetrahedron 66 (2010) 6725e6732
2. Results and discussion
instead yielded a 1:1 coupling product (HO-ThPh(2)); the reason
for this result is not entirely clear. However, the reaction of
4-bromo-4-hydroxybiphenyl with thiophene-2,5-diboronic acid in
a 2:1 molar ratio yielded a 2:1 coupling product (HO-ThPh(4)-OH),
as expected (Scheme 2b).
2.1. Synthesis
The reaction of 1 with 4-bromophenol, 4-bromo-40-hydrox-
ybiphenyl, and 4-bromo-400-methoxy[1,10;40,100]terphenyl (Br-OPP
(3)-OMe) in a 1:2 molar ratio afforded HO-FluPh(4)-OH, HO-FluPh
(6)-OH, and MeO-FluPh(8)-OMe in 59%, 73%, and 56% yields, re-
spectively (Scheme 1a and b). The Suzuki coupling reaction of 1
with 4-bromo-400-hydroxy[1,10;40,100]terphenyl (Br-OPP(3)-OH)
was not used for the synthesis of HO-FluPh(8)-OH. This is because
the solubility of HO-FluPh(8)-OH in organic solvents was low, and
therefore, it could not be purified by column chromatography.
Instead of the above method, the reaction between 4-bromo-400-
methoxy[1,10;40,100]terphenyl Br-OPP(3)-OMe and 1 and depro-
tection of the OMe groups was used for the synthesis of HO-FluPh
(8)-OH (Scheme 1b). HO-DobPh(m)-OHs were obtained by the
reaction of 2 with Br-OPP(n)-OHs (n¼1, 2, and 3) in 55%, 63%, and
51% yields, respectively (Scheme 1c). In order to compare the
chemical properties with HO-DobPh(5)-OH, EtO-DobPh(5)-OEt
was synthesized by the hydrolysis of HO-DobPh(5)-OH with EtOH.
HO-AntPh(2)-OH with an anthracene (Ar¼Ant) luminophore was
synthesized by the reaction of 4-hydroxyphenylboronic acid with
9,10-dibromoanthracene (Scheme 1d).
The structures of the newly synthesized compounds were
determined by 1H and 13C NMR spectroscopy and elemental
analysis. OPP(5)-OH, which consisted of five benzene rings,
showed considerably low solubility in polar organic solvents.16
Despite the larger number of benzene rings in HO-FluPh(6)-OH
and HO-DobPh(5)-OH than in OPP(5)-OH, HO-FluPh(6)-OH and
HO-DobPh(5)-OH showed good solubility in organic solvents
because of the presence of the long alkyl chains. They were
soluble in polar organic solvents such as 1,4-dioxane, N,N-
dimethylformamide (DMF), and dimethyl sulfoxide (DMSO) as
well as in less polar organic solvents such as dichloromethane
and toluene. However, HO-FluPh(8)-OH and HO-DobPh(7)-OH
were completely soluble in chloroform and dichloromethane but
sparingly soluble in DMF and DMSO. HO-PyPh(2)-OH was solu-
ble in DMF and DMSO but insoluble in dichloromethane and
chloroform because of the presence of a hydrophilic pyridine
ring.
The melting points of HO-FluPh(m)-OHs and HO-DobPh(m)-
OHs increased as the number of the benzene ring (m) increased.
O
O
O
O
Pd(PPh3)4
(a)
+
B
B
OH
HO
OH
2 Br
n
K2CO3(aq)
n
n
H
H
C
H
C
C H
13 6
C H
6
13
13
6
6
13
6 13
n = 1 and 2
Br-OPP(n)-OH
HO-FluPh(m)-OH (m = 4 and 6)
O
O
O
O
Pd(PPh3)4
K2CO3(aq)
(b)
+
OMe
MeO
OMe
2 Br
Br-OPP(3)-OMe
MeO-FluPh(8)-OMe
B
B
3
3
3
H
C
C H
6
C
C H
6
13
6
13
13
MeO-FluPh(8)-OMe
BBr3
HO
OH
3
3
H
C
C H
6
13
6
13
HO-FluPh(8)-OH
OC H
OC H
8
17
8
17
Pd(PPh3)4
K2CO3(aq)
(c)
+
(HO) B
B(OH)
17
OH
2 Br
HO
OH
2
2
n
n
n
OC H
8
n = 1, 2, and 3
Br-OPP(n)-OH
OC H
8 17
HO-DobPh(m)-OH (m = 3, 5, and 7)
OC H
8
17
KOH
+
2
EtOH
HO-DobPh(5)-OH
EtO
OEt
2
2
OC H
8
17
HO-DobPh(5)-OEt
Pd(PPh3)4
K2CO3(aq)
(d)
+
HO
B(OH)
2
2
Br
Br
HO
OH
HO-AntPh(2)-OH
Scheme 1. Synthesis of soluble OPPs with hydroxyl groups at both ends.
Dihydroxyoligoarylenes bearing a central heterocyclic aromatic
ring HO-ArPh(m)-OHs (Ar¼Py and Th) were synthesized by the
Suzuki coupling reactions shown in Scheme 2. The Suzuki coupling
reaction of 4-bromophenol with thiophene-2,5-boronic acid in
a 2:1 molar ratio did not yield an expected 2:1 coupling product but
2.2. IR and NMR spectra
The main features of the IR spectra of HO-FluPh(m)-OHs were
identical: the absorption peaks resulting from OeH stretching,
presence of a phenyl ring, and out-of-plane CeH bending vibrations
Pd(PPh3)4
+
(a)
2 HO
B(OH)
Br
Br
HO
OH
2
K2CO3(aq)
N
N
HO-PyPh(2)-OH
Pd(PPh3)4
K2CO3(aq)
+
(b)
Br
OH
2 HO
(HO) B
B(OH)
HO
2
2
S
S
HO-ThPh(4)-OH
Scheme 2. Synthesis of HO-ArPh(m)-OHs with a central aromatic heterocycle.

I. Yamaguchi et al. / Tetrahedron 66 (2010) 6725e6732
6727
of p-phenylene were observed at approximately 3440 cmꢁ1
,
1.0
0.8
(a)
1250 cmꢁ1, and 815 cmꢁ1, respectively. Similarly, the main features
of the IR spectra of HO-DobPh(m)-OHs were identical: the ab-
sorption peaks resulting from OeH stretching, presence of a phenyl
ring, and out-of-plane CeH bending vibrations of p-phenylene
HO-FluPh(8)-OH
HO-FluPh(6)-OH
HO-FluPh(4)-OH
0.6
were observed at approximately 3350 cmꢁ1, 1250 cmꢁ1
, and
820 cmꢁ1, respectively.
0.4
0.2
0
Deprotonationof the OHgroupsof HO-ArPh(m)-OHs was carried
out by treating themwith an excess amount of NaH in DMSO-d6. The
disappearance of the signal ascribes to OH group from the 1H NMR
spectra of solutions of HO-ArPh(m)-OHs, except for HO-FluPh(8)-
OH and HO-DobPh(7)-OH, and NaH indicated that the deprotona-
tion proceeded quantitatively. The signals ascribed to particular
protons of NaO-ArPh(m)-ONas (Ar¼Flu and Dob) shifted to higher
magnetic fields than those of HO-ArPh(m)-OHs (Ar¼Flu and Dob).
These chemical shifts increase with decreasing the distance of the
protons from the ONa group; therefore, theyare largest in the case of
protons adjacent to the ONa groups. These observations can be at-
tributed to the electron-donating effect of the ONa groups. These
data indicated the possibility of the occurrence of a charge shift from
the phenolate groups to the adjacent rings in the deprotonated
species. Such a charge shift in NaO-ArPh(m)-ONas may significantly
(b)
HO-DobPh(3)-OH HO-DobPh(5)-OH
0.6
HO-DobPh(7)-OH
0.4
0.2
0
affect theiroptical properties. The 1H NMR chemical shifts (d1 and d2
)
250
300
350
400
450
of protons adjacent to the OH groups in HO-ArPh(m)-OHs and the
ONa groups in NaO-ArPh(m)-ONas and their differences
Wavelength/ nm
Figure 1. UVevis spectra of HO-ArPh(m)-OHs (Ar¼Flu (a) and Dob (b)) in DMSO.
(
Dd
¼
d1 d2) are summarized in Table 1. The Dd values depended on
ꢁ
the electron density of the central ring in NaO-ArPh(m)-ONas. That
is, the Dd values of NaO-ArPh(m)-ONas (Ar¼Flu and Dob) were
smaller than those of OPP(n)-ONas because of the presence of the
electron-donating alkyl groups on the central phenylene ring,
whereas, the Dd value of NaO-PyPh(2)-ONa (Dd¼0.90) was larger
than those of NaO-ArPh(m)-ONas (Ar¼Flu and Dob)
The treatment of the DMSO solutions of HO-ArPh(m)-OHs
(Ar¼Flu and Dob) with NaH causes bathochromic shift of lmax by
approximately 50e80 nm. The formation of NaO-ArPh(m)-ONas
(Ar¼Flu and Dob) was mainly responsible for the shift of lmax to-
ward a longer wavelength. Similar solvatochromic behavior was
observed in the case of OPP(n)-OHs (n¼3, 4, and 5) and their
deprotonated species reported earlier.16 To prove that these ob-
servations were due to the deprotonation of the OH groups after
treatment with NaH, we confirmed that there was no change in the
absorption spectra of MeO-FluPh(8)-OMe and EtO-DobPh(5)-OEt
after the addition of NaH.
Bathochromic shift attributable to deprotonation depends on
the donor number (DN) of the solvents. As shown in Figures 2
and 3, the lmax values of HO-ArPh(m)-OHs (Ar¼Flu and Dob) and
their deprotonated species shifted to longer wavelengths as the
DNs of the solvents increased.
In contrast to the small bathochromic shift of HO-ArPh(m)-OHs
(Ar¼Flu and Dob) with an increase in the DNs of the solvents, the
lmax values of the deprotonated species were larger than those of
HO-ArPh(m)-OHs (Ar¼Flu and Dob). For example, the lmax value of
NaO-FluPh(4)-ONa moves from 332 nm in CH2Cl2 (DN¼0) to
414 nm in DMSO (DN¼29.8) through to a value of 373 nm in THF
(DN¼20.0). The large Dl value can be attributed to the fact that
solvents with a high DN solvate effectively with Naþ to stabilize the
deprotonated species in the solutions. Similar solvatochromic be-
havior was observed in the case of OPP(n)-OHs (n¼4 and 5) and
OPP(n)-ONas (n¼4 and 5) reported earlier.5 The lmax and Dl values
of NaO-FluPh(4)-ONa were larger than those of NaO-DobPh(5)-
ONa despite the smaller number of benzene rings in NaO-FluPh
(4)-ONa than in NaO-DobPh(5)-ONa. This was because of the re-
(
Dd¼0.64e0.80). This difference was apparently due to the presence
of the central electron-accepting pyridine ring that easily induced
the shift in charge from the phenolate groups tothe adjacent rings in
the deprotonated species.
Table 1
1H NMR chemical shift
d1
d2
Dd
¼d1ꢁd2
HO-FluPh(4)-OH
HO-FluPh(6)-OH
HO-FluPh(8)-OH
HO-DobPh(5)-OH
HO-AntPh(2)-OH
HO-PyPh(2)-OH
HO-ThPh(4)-OH
6.94
6.88
6.88
6.86
7.03
6.88
6.86
NaO-FluPh(4)-ONa
NaO-FluPh(6)-ONa
NaO-FluPh(8)-ONa
NaO-DobPh(5)-ONa
NaO-AntPh(2)-ONa
NaO-PyPh(2)-ONa
NaO-ThPh(4)-ONa
6.14
6.08
6.08
6.22
6.24
5.98
6.05
0.80
0.80
0.80
0.64
0.79
0.90
0.81
The 13C NMR peaks corresponding to the phenyl carbons
adjacent to the ONa groups were observed at higher magnetic
field positions (
OH groups of HO-PyPh(2)-OH (
servations are attributed to the electron-donating effect of the
d
¼117.2 and 126.8) than those adjacent to the
d
¼118.9 and 127.7). These ob-
ONa groups in NaO-PyPh(2)-ONa.
2.3. UVevis absorption and solvatochromism
duced
p-conjugation length in NaO-DobPh(5)-ONa, which was
Figure 1 shows the UVevis spectra of HO-ArPh(m)-OHs (Ar¼Flu
and Dob) in DMSO. The UVevis data of HO-ArPh(m)-OHs (Ar¼Flu
and Dob) and their deprotonated species are summarized in
Table 2. The absorption maxima (lmax) of HO-ArPh(m)-OHs
(Ar¼Flu and Dob) shifted progressively toward longer wavelengths
attributed to the bond twisting between dioctyloxybenzene and
the adjacent benzene rings induced by the steric hindrance of the
dioctyloxy groups. In CH2Cl2, 1,4-dioxane, and THF, the absorption
positions of NaO-FluPh(8)-ONa and NaO-DobPh(7)-ONa were
longer than those of NaO-FluPh(6)-ONa and NaO-DobPh(5)-ONa
because of the larger number of benzene rings in NaO-FluPh(8)-
ONa and NaO-DobPh(7)-ONa. However, in DMF and DMSO, the
because of the expansion of the
p-conjugation system as the
number of benzene rings (m) increased.

6728
I. Yamaguchi et al. / Tetrahedron 66 (2010) 6725e6732
420
400
380
360
340
320
300
280
0
5
10
15
20
25
30
DN of solvent
Figure 2. Dependence of lmax of HO-FluPh(m)-OHs (m¼4 (B), 6 (6), and 8 (,);
dotted line) and their deprotonated species (m¼4 (C), 6 (:), and 8 (-); solid line) on
the DNs of solvents. In the case that two absorption peaks were observed, the longer
wavelength was adopted for the data point.
420
400
380
360
340
320
300
280
10
15
20
25
30
DN of solvent
Figure 3. Dependence of lmax of HO-DobPh(m)-OHs (m¼3 (B), 5 (6), and 7 (,);
dotted line) and their deprotonated species (m¼4 (C), 6 (:), and 8 (-); solid line) on
the DNs of solvents. In the case that two absorption peaks were observed, the longer
wavelength was adopted for the data point.
absorption positions of NaO-FluPh(8)-ONa and NaO-DobPh(7)-
ONa were shorter than those of NaO-FluPh(6)-ONa and NaO-
DobPh(5)-ONa. These observations are attributed to the low
solubility of HO-FluPh(8)-OH and HO-DobPh(7)-OH in DMF and
DMSO, which makes it difficult to form NaO-FluPh(8)-ONa and
NaO-DobPh(7)-ONa by deprotonation of the OH groups with NaH.
Approximate yields for NaO-FluPh(8)-ONa and NaO-DobPh(5)-
ONa, estimated from the integration of the 1H NMR peaks at d1 and
d2, were 30% and 25%, respectively.
As mentioned above, the bathochromic shift in the lmax of
HO-FluPh(m)-OHs increased as the DNs of the solvents in-
creased. In order to investigate the effect of pH of solvents on the
optical properties of HO-FluPh(m)-OHs, the UVevis measure-
ments of HO-FluPh(6)-OH in the mixture of DMSO and aqueous
buffer solutions (pH¼1e10) were carried out. The UVevis spectra
of HO-FluPh(6)-OH in the solutions under pH of 7 showed a lmax
at approximately 330 nm, while those in the solutions above pH
of 8 showed a lmax at approximately 370 nm. The results that
lmax values of HO-FluPh(6)-OH in the basic solutions were larger
than those in the acid solutions corresponded to the results that
lmax value of NaO-FluPh(6)-ONa was larger than that of
HO-FluPh(6)-OH in solution.
UVevis data of HO-ArPh(m)-OHs (Ar¼Py and Th) and their
deprotonated species are summarized in Table 3. A bathochromic
shift caused by deprotonation was observed in the case of HO-ArPh

I. Yamaguchi et al. / Tetrahedron 66 (2010) 6725e6732
6729
(m)-OHs (Ar¼Py and Th). The Dl values of NaO-PyPh(2)-ONa in
DMF and DMSO were larger than those of NaO-FluPh(6)-ONa de-
spite the smaller number of benzene rings in NaO-PyPh(2)-ONa
than in NaO-FluPh(6)-ONa. The larger bathochromic shift of NaO-
PyPh(2)-ONa may be assumed to be caused by an effective shift in
charge from the phenolate groups at both ends to the central
electron-withdrawing pyridine ring. This assumption is in good
agreement with the result that the 1H NMR peak shifts of the
protons adjacent to the ONa groups of NaO-PyPh(2)-ONa
CH2Cl2 (DN¼0), THF (DN¼20.0), and DMSO (DN¼29.8), re-
spectively, as shown in Figure 4.
The quantum yields of the PLs of the THF solutions of NaO-
FluPh(m)-ONas (m¼4, 6, and 8) were 16%, 9%, and 9%, respectively,
while those of HO-DobPh(m)-OHs (m¼3, 5, and 7) were 12%, 10%,
and 11%, respectively. The fact that the quantum yields of the PLs of
NaO-ArPh(m)-ONas are lower than those of HO-ArPh(m)-OHs is
attributed to the intramolecular charge shift (ICT) in NaO-ArPh(m)-
ONas. It has been reported that the ICT in
p-conjugated molecules
(
Dd¼0.90) produced by deprotonation were larger than those of
reduces their PL emission efficiencies.19
NaO-FluPh(6)-ONa (Dd¼0.80). The Dd values of NaO-ThPh(4)-ONa
in THF and DMSO were smaller than those of NaO-PyPh(2)-ONa
despite the larger number of benzene rings in NaO-ThPh(4)-ONa.
Figures 5 and 6 show the dependence of the emission peak posi-
tions of HO-ArPh(m)-OHs (Ar¼Flu and Dob) and their deprotonated
species on the DNs of the solvents. Thus, by alternating solvents such
as CH2Cl2 and 1,4-dioxane, which have small DN values, and those
such as DMF and DMSO, which have large DN values, it is observed
that the emission peak positions of HO-ArPh(m)-OHs (Ar¼Flu and
Dob) shift only by 3e10 nm. However, a significantly large shift in the
This is because of the presence of the central p-rich thiophene ring
in NaO-ThPh(4)-ONa, which makes the shift in charge difficult
from the phenolate groups to the adjacent rings in the deproto-
nated species.
Table 3
UVevis data of HO-AntPh(2)-OH, HO-PyPh(2)-OH, HO-ThPh(4)-OH, and their deprotonated species
Solvent
DNb
Absorption,a nm
HO-AntPh(2)-OH
NaO-AntPh(2)-ONa
HO-PyPh(2)-OH
NaO-PyPh(2)-ONa
HO-ThPh(4)-OH
NaO-ThPh(4)-ONa
c
c
Dichloromethane
1,4-Dioxane
THF
DMF
DMSO
0
339, 358, 376, 397
340, 358, 376, 396
342, 358, 376, 396
342, 360, 378, 398
342, 361, 380, 400
348
299
289
301
314
321
278, 351
269, 355
271, 369
403
c
c
14.8
20.0
26.6
29.8
340, 358, 376, 391
358, 378, 397, 433
285, 327, 375, 474
294, 334, 376, 485
278
283, 328
322
273, 348
293, 389
404, 487
399, 479
a
Concentration of solution was 1.0ꢂ10ꢁ5 M.
DN¼donor number.
b
c
Not measured due to low solubility.
2.4. Photoluminescence
emission peaks of NaO-ArPh(m)-ONas (Ar¼Flu and Dob) occurred as
the DNs of the solvents increased. These observations are comparable
to the results that lmax of NaO-ArPh(m)-ONas (Ar¼Flu and Dob) in
solution shifts to a longer wavelength than that of HO-ArPh(m)-OHs
(Ar¼Flu and Dob) with an increase in the DNs of the solvents. The
remarkable solvatochromic shift of the PL peak position of NaO-ArPh
It has been reported that OPPs exhibit photoluminescence (PL)
with
high quantum yield.17,18 HO-ArPh(m)-OHs and their
a
deprotonated species are photoluminescent in solution. The PL data
are summarized in Tables 4 and 5.
Table 4
PL data of HO-FluPh(m)-OHs and HO-DobPh(m)-OHs
Solvent
DNb
HO-FluPh(m)-OH,a nm
NaO-FluPh(m)-ONa,a nm
HO-DobPh(m)-OH,a nm
NaO-DobPh(m)-ONa,a nm
m¼4
369, 386
(329)
370, 388
(339)
372, 390
(341)
377, 394
(343)
379, 396
(345)
6
8
m¼4
6
8
m¼3
384
(328)
383
(327)
381
(329)
386
(330)
387
5
7
c
m¼3
5
c
7
c
c
Dichloromethane
1,4-dioxane
THF
0
392, 408
(341)
396, 410
(345)
395, 410
(344)
398, 411
(348)
401, 413d
(348)
368, 385
(330)
370, 389
(336)
451
(373)
495
(400)
492
392
(340)
396
(341)
401, 507
(344)
534, 538
(415)
555
403
404
(336)
403
(337)
402
(338)
405
(341)
408
(343)
(348)
399, 484
(350)
534
(381)
518
(393)
526
(404)
14.8
20.0
26.6
29.8
398, 413d
(347)
409
(341)
408
(342)
413
(344)
415
385
(327)
382
(328)
447
(373)
451
458
(358)
484
(362)
548
(379)
552
429
(334)
510
(381)
511
(381)
510
401, 415d
(349)
DMF
403, 420d
(353)
DMSO
401, 415
(347)
406, 425d
(354)
(402)
(420)
(331)
(347)
(372)
(382)
(382)
a
Concentration of solution was 1.0ꢂ10ꢁ6 M. Excitation wavelength was shown in parenthesis.
b
c
DN¼donor number.
Not measured due to low solubility.
Shoulder peak.
d
The quantum yields of the PLs of the THF solutions of HO-FluPh
(m)-ONas (Ar¼Flu and Dob) appeared to be due to the charge shift
from the phenolate group to the adjacent rings. In addition to the
charge shift effect, a large amount of stabilization energy produced by
the solvation of NaO-ArPh(m)-ONas (Ar¼Flu and Dob) may con-
tribute to the solvatochromic red shift as the DNs of the solvents in-
crease. There was no change in the PL spectra of MeO-FluPh(8)-OMe
and EtO-DobPh(5)-OEt after the addition of NaH, which suggested
that the solvatochromism in NaO-ArPh(m)-ONas (Ar¼Flu and Dob)
(m)-OHs (m¼4, 6, and 8) were 41%, 19%, and 34%, respectively,
while those of HO-DobPh(m)-OHs (m¼3, 5, and 7) were 36%, 34%,
and 34%, respectively. The emission peak positions of HO-ArPh(m)-
OHs and their deprotonated species depended on the DNs of the
solvents; therefore, the emission color can be tuned by changing
the solvent. For example, NaO-DobPh(5)-ONa exhibited purple,
blue, and yellow emissions after it was irradiated with UV light in

6730
I. Yamaguchi et al. / Tetrahedron 66 (2010) 6725e6732
Table 5
PL data of HO-ArPh(m)-OHs (Ar¼Ant, Py, and Th) and their deprotonated species
Solvent
DNb
Photoluminescence,a nm
HO-AntPh(2)-OH
NaO-AntPh(2)-ONa
HO-PyPh(2)-OH
NaO-PyPh(2)-ONa
HO-ThPh(4)-OH
NaO-ThPh(4)-ONa
c
c
Dichloromethane
1,4-Dioxane
THF
0
421, 437d
(396)
401, 420d
(348)
401, 418,d 445d
(348)
401, 419,d 447d
(351)
443
(366)
476
(372)
531
(399)
532
c
c
14.8
20.0
26.6
29.8
423, 441d
(396)
401, 418d
(360)
358,d 375, 393d
(328)
424, 443d
(395)
433
(397)
436
401, 415, 509
(360)
526
(398)
532
375, 389d
(328)
386, 401
(329)
430
(367)
481
(392)
486
363,d 377, 398d
(328)
387
(328)
391
DMF
DMSO
383
(399)
(401)
(328)
(394)
(329)
(399)
a
Concentration of solution was 1.0ꢂ10ꢁ6 M. Excitation wavelength was shown in parenthesis.
b
c
DN¼donor number.
Not measured due to low solubility.
Shoulder peak.
d
Figure 4. Photographs of NaO-DobPh(5)-ONa when it was irradiated with UV light in CH2Cl2 (DN¼0), THF (DN¼20.0), and DMSO (DN¼29.8).
560
540
520
500
480
460
440
420
400
380
360
560
540
520
500
480
460
440
420
400
380
360
10
15
20
25
30
0
5
10
15
20
25
30
DN of solvent
DN of solvent
Figure 5. Dependence of PL peak position of HO-FluPh(m)-OHs (m¼4 (B), 6 (6), and
8 (,); dotted line) and their deprotonated species (m¼4 (C), 6 (:), and 8 (-); solid
line) on the DNs of solvents. In the case that two PL peaks were observed, the longer
wavelength was adopted for the data point.
Figure 6. Dependence of PL peak position of HO-DobPh(m)-OHs (m¼3 (B), 5 (6),
and 7 (,); dotted line) and their deprotonated species (m¼4 (C), 6 (:), and 8 (-);
solid line) on the DNs of solvents.
was attributed to the deprotonation of the OH group after treatment
with NaH.
In DMF and DMSO, the PL peak positions of NaO-FluPh(8)-ONa
and NaO-DobPh(7)-ONa were shorter than those of NaO-FluPh(6)-
ONa and NaO-DobPh(5)-ONa despite the larger number of
benzene rings in NaO-FluPh(8)-ONa and NaO-DobPh(7)-ONa than
in NaO-FluPh(6)-ONa and NaO-DobPh(5)-ONa. These results are
comparable to those that suggest lmax positions of NaO-FluPh(8)-
ONa and NaO-DobPh(7)-ONa were lower than those of NaO-FluPh
(6)-ONa and NaO-DobPh(5)-ONa.

I. Yamaguchi et al. / Tetrahedron 66 (2010) 6725e6732
6731
The PL peak position of HO-FluPh(6)-OH in the solutions under
pH of 7 was observed at 401 nm, while that in the solutions above
pH of 8 was 536 nm. These wavelengths are comparable to those of
the DMSO solutions of HO-FluPh(6)-OH and NaO-FluPh(6)-ONa,
respectively.
solution was treated with 0.5 N HCl(aq) (25 mL) and neutralized
with NaOH(aq) to give a precipitate from the solution. The pre-
cipitate was collected by filtration and dried in vacuo to give HO-
FluPh(4)-OH as a white powder (0.31 g, 59%). 1H NMR (400 MHz,
CDCl3):
4H), 6.94 (d, J¼8.4 Hz, 4H), 4.80 (br, 2H), 2.01 (m, 4H), 1.06 (m, 12H),
0.75 (m, 10H). 13C NMR (100 MHz, CDCl3):
155.0, 151.6, 139.6,
d
7.73 (d, J¼7.6 Hz, 2H), 7.56 (d, J¼8.8 Hz, 4H), 7.49e7.53 (m,
Similar to the case of HO-ArPh(m)-OHs (Ar¼Flu and Dob) and
their deprotonated species, the emission peak positions of HO-
ArPh(m)-OHs (Ar¼Ant, Py, and Th) and their deprotonated species
depended on the DNs of the solvents. The PL data are summarized
in Table 5. The emission peak positions of NaO-AntPh(2)-ONa and
NaO-ThPh(4)-ONa in the solvents with a high DN value (DMF and
DMSO) were considerably higher than those in the solvents with
a low DN value (CH2Cl2 and 1,4-dioxane). Quantum yields of the PLs
of the THF solutions of HO-ArPh(m)-OHs (Ar¼Ant, Py, and Th) were
8%, 4%, and 15%, respectively, while those of NaO-ArPh(m)-ONas
(Ar¼Ant, Py, and Th) were 7%, 3%, and 7%, respectively. These re-
sults are comparable to the results that quantum yields of the PL of
HO-ArPh(m)-OHs (Ar¼Flu and Dob) were higher than those of
NaO-ArPh(m)-ONas (Ar¼Flu and Dob).
d
139.5, 134.5, 132.2, 128.4, 125.6, 121.1, 119.8, 115.7, 55.2, 40.5, 31.5,
29.7, 23.8, 22.6, 14.0. IR (KBr, cmꢁ1): 3333 (OH), 3031, 2926, 2856,
1604, 1514, 1459, 1248, 1175, 817. Anal. Calcd for C37H42O2: C, 85.67;
H, 8.16. Found: C, 85.53; H, 7.83. Mp¼119e121 ꢃC.
4.3. Synthesis of HO-FluPh(6)-OH and MeO-FluPh(8)-OMe
HO-FluPh(6)-OH and MeO-FluPh(8)-OMe were synthesized by
the reaction of
analogously.
1 with Br-OPP(2)-OH and Br-OPP(3)-OMe
4.3.1. Data of HO-FluPh(6)-OH. Yield¼73%. 1H NMR (400 MHz,
CDCl3):
d
7.79 (d, J¼8.0 Hz, 2H), 7.74 (d, J¼8.4 Hz, 4H), 7.61e7.67 (m,
3. Conclusions
8H), 7.56 (d, J¼8.4 Hz, 4H), 6.94 (d, J¼8.4 Hz, 4H), 4.88 (s, 2H), 2.07
(m, 4H), 1.13 (m, 12H), 0.77 (m, 10H). 13C NMR (100 MHz, CDCl3):
A series of dihydroxyoligophenylenes, namely, HO-ArPh(m)-
OHs, containing 9,9-dihexyl-2,7-fluorene (Ar¼Flu), 2,5-dioctyloxy-
1,4-benzene (Ar¼Dob), pyridine (Ar¼Py), or 2,5-thiophene (Ar¼Th)
rings were synthesized by the Suzuki coupling reaction. The alkyl
groups of HO-ArPh(m)-OHs (Ar¼Flu and Dob) contributed toward
improving their solubility. The treatment of HO-ArPh(m)-OHs with
a base produced the deprotonated species NaO-ArPh(m)-ONas,
whose absorption and PL peak positions in solution shifted toward
longer wavelengths with an increase in the DNs of the solvents. The
emission colors of the solutions of the deprotonated species could
be tuned by changing the solvent. The optical properties of NaO-
d 155.2, 151.7, 140.1, 139.6, 133.6, 128.3, 127.5, 127.1, 125.9, 121.4,
115.7, 55.3, 40.5, 31.5, 29.7, 23.8, 22.6, 14.0. IR (KBr, cmꢁ1): 3442
(OH), 2926, 2854, 1603, 1458, 1257, 1024, 817. Anal. Calcd for
C49H50O2: C, 87.72; H, 7.51. Found: C, 87.53; H, 7.43.
Mp¼193e195 ꢃC.
4.3.2. Data of MeO-FluPh(8)-OMe. Yield¼56%. 1H NMR (400 MHz,
CDCl3):
d
7.72e7.82 (m, 14H), 7.59e7.68 (m, 10H), 7.02 (d, J¼8.4 Hz,
4H), 3.88 (s, 6H), 2.07 (m, 4H), 1.12 (m, 12H), 0.77 (m, 10H). 13C NMR
(100 MHz, CDCl3): 159.3, 151.8, 140.6, 140.2, 139.8, 139.5, 139.0,
d
133.2, 128.1, 127.6, 127.5, 127.4, 127.2, 127.1, 126.0, 121.4, 120.1, 114.3,
55.38, 55.32, 40.5, 31.5, 29.7, 23.8, 22.6, 14.0. IR (KBr, cmꢁ1): 3031,
2925, 2855, 1607, 1510, 1459, 1248, 1175, 817. Anal. Calcd for
C63H62O2: C, 88.90; H, 7.34. Found: C, 88.61; H, 7.09.
Mp¼300e302 ꢃC.
ArPh(m)-ONas were significantly affected by the
p-electron den-
sity in the central aromatic ring. From the results of this study, it can
be concluded that new luminescent materials can be developed on
the basis of the remarkable solvatochromic behavior of NaO-ArPh
(m)-ONas.
4.4. Synthesis of HO-FluPh(8)-OH
4. Experimental section
4.1. General
After BBr3 (1 mL) was added to a dichloromethane solution
(70 mL) of MeO-FluPh(3)-OMe (0.078 g, 0.091 mmol) under N2, the
solution was stirred at 20 ꢃC for 24 h. To the solution was water
(50 mL), the organic layer was extracted with dichloromethane and
dried over sodium sulfonate. The solvent was removed by evapo-
ration to give a white solid, which was washed with hexane. HO-
FluPh(8)-OH was collected by filtration, dried in vacuo, and
obtained as a white powder (0.042 g, 56%). 1H NMR (400 MHz,
Solvents were dried, distilled, and stored under nitrogen.
Br-OPP(3)-OH, Br-OPP(3)-OMe, and 2 were synthesized according
to the literatures.16,20 Other reagents were purchased and used
without further purification. Reactions were carried out with
standard Schlenk techniques under nitrogen.
IR and NMR spectra were recorded on a JASCO FT/IR-660 PLUS
spectrophotometer and a JEOL AL-400 spectrometer, respectively.
Elemental analysis was performed on a Yanagimoto MT-5 CHN
corder. UVevis and PL spectra were obtained by a JASCO V-560
CDCl3):
4H), 6.94 (d, J¼8.4 Hz, 4H), 4.82 (s, 2H), 2.07 (m, 4H), 1.09 (m, 12H),
0.77 (m, 10H). 13C NMR (100 MHz, DMSO-d6):
157.3, 151.4, 149.1,
148.0, 139.7, 139.3, 138.5, 137.4, 135.5, 130.3, 127.6, 127.2, 126.9,
126.4, 125.5, 120.9, 120.4, 115.8, 55.0, 32.1, 30.8, 28.9, 23.4, 21.9, 13.7.
IR (KBr, cmꢁ1): 3426 (OH), 3029, 2926, 2856, 1604, 1514, 1489, 1459,
1251, 1176, 815. Anal. Calcd for C61H58O2: C, 89.01; H, 7.10. Found: C,
88.79; H, 6.58. Mp¼252e254 ꢃC.
d
7.72e7.82 (m, 14H), 7.63e7.67 (m, 8H), 7.56 (d, J¼8.4 Hz,
d
spectrometer and
a JASCO FP-6200 spectrofluorometer, re-
spectively. Quantum yields were calculated by using a diluted
ethanol solution of 7-dimethylamino-4-methylcoumarin as the
standard.
4.2. Synthesis of HO-FluPh(4)-OH
4.5. Synthesis of HO-DobPh(m)-OHs
4-Bromophenol (0.35 g, 2.0 mmol) and 1 (0.50 g, 1.0 mmol)
were dissolved in 25 mL of dry THF under N2. K2CO3(aq) (2.0 M,
10 mL; N2 bubbled before use) and Pd(PPh3)4 (0.049 g, 0.042 mmol)
were added to the solution. After the mixture was refluxed for 48 h,
the solvent was removed under vacuum. The resulting solid was
washed with water and hexane and dried under vacuum to give
a light yellow solid, which was dissolved in methanol (150 mL). The
HO-DobPh(m)-OHs were synthesized by the Suzuki coupling
reaction of 2 with Br-Ph(n)-OHs (n¼1, 2, and 3).
4.5.1. Data of HO-DobPh(3)-OH. Yield¼55%. 1H NMR (400 MHz,
CDCl3):
d
7.49 (d, J¼8.4 Hz, 4H), 6.93 (s, 2H), 6.88 (d, J¼8.4 Hz, 4H),
3.89 (t, J¼6.0 Hz, 4H), 3.50 (s, 2H), 1.68 (m, 4H), 1.25e1.35 (m, 20H),
0.88 (t, J¼6.8 Hz, 6H). 13C NMR (100 MHz, DMSO-d6):
d 156.4, 149.5,

6732
I. Yamaguchi et al. / Tetrahedron 66 (2010) 6725e6732
130.3, 129.1, 128.6, 115.4, 114.7, 68.6, 31.2, 28.8, 28.64, 28.57, 25.5,
22.1, 14.0. IR (KBr, cmꢁ1): 3363 (OH), 2925, 2853, 1611, 1524, 1496,
1461, 1383, 1211, 1173, 1054, 831, 631. Anal. Calcd for C34H46O4: C,
78.72; H, 8.94. Found: C, 78.48; H, 8.75. Mp¼117e119 ꢃC.
J¼3.2 and 6.8 Hz, 4H), 7.23 (d, J¼8.4 Hz, 4H), 7.03 (d, J¼8.4 Hz,
4H). 13C NMR (100 MHz, DMSO-d6):
d 156.9, 136.5, 132.0, 129.7,
128.3, 126.6, 125.1, 115.4. IR (KBr, cmꢁ1): 3359 (OH), 3031, 1659,
1604, 1510, 1438, 1384, 1233, 1172, 827, 768. Anal. Calcd for
C26H18O2: C, 86.16; H, 5.01. Found: C, 86.48; H, 5.11.
Mp¼310e312 ꢃC.
4.5.2. Data of HO-DobPh(5)-OH. Yield¼63%. 1H NMR (400 MHz,
CDCl3):
d
7.69 (d, J¼8.0 Hz, 4H), 7.61 (d, J¼8.4 Hz, 4H), 7.56 (d,
J¼8.4 Hz, 4H), 7.05 (s, 2H), 6.94 (d, J¼7.6 Hz, 4H), 4.73 (s, 2H), 3.96 (t,
4.7.2. Data of HO-ThPh(4)-OH. Yield¼42%. 1H NMR (400 MHz,
J¼6.4 Hz, 4H), 1.72 (m, 4H), 1.27e1.39 (m, 20H), 0.87 (t, J¼6.0 Hz,
DMSO-d6):
d
9.59 (s, 2H), 7.69 (d, J¼8.4 Hz, 4H), 7.63 (d, J¼8.4 Hz,
6H). 13C NMR (100 MHz, CDCl3):
d
155.0, 150.4, 139.2, 136.8, 133.8,
4H), 7.53 (d, J¼8.0 Hz, 4H), 7.15 (t, J¼4.4 Hz, 2H), 6.86 (d, J¼8.4 Hz,
130.3, 129.9, 128.3, 126.2, 116.2, 115.6, 69.6, 31.8, 29.4, 29.3, 26.1,
22.7, 14.1. IR (KBr, cmꢁ1): 3340 (OH), 3031, 2925, 2856, 1603, 1482,
1381, 1218, 820. Anal. Calcd for C46H54O4: C, 82.35; H, 8.94. Found:
C, 82.15; H, 8.70. Mp¼211e213 ꢃC.
4H). 13C NMR (100 MHz, DMSO-d6):
d 143.1, 139.2, 132.9, 128.5,
127.5, 126.4, 125.8, 125.4, 123.4, 115.8. IR (KBr, cmꢁ1): 3418 (OH),
2925, 1604, 1491, 1450, 1378, 1256, 818, 696. Anal. Calcd for
C26H20O2S: C, 78.76; H, 5.08. Found: C, 78.84; H, 4.60.
Mp¼292e294 ꢃC.
4.5.3. Data of HO-DobPh(7)-OH. Yield¼51%. 1H NMR (400 MHz,
CDCl3):
d
7.74e7.77 (m, 12H), 7.68 (d, J¼8.4 Hz, 4H), 7.59 (d,
4.7.3. Data of HO-PyPh(2)-OH. Yield¼35%. 1H NMR (400 MHz,
J¼6.4 Hz, 4H), 6.97 (d, J¼8.8 Hz, 4H), 4.90 (s, 2H), 4.01 (t, J¼6.4 Hz,
DMSO-d6):
d
9.73 (s, 1H), 9.66 (s, 1H), 8.83 (d, J¼2.4 Hz, 1H), 8.01
4H), 1.76 (m, 4H), 1.28e1.43 (m, 20H), 0.89 (t, J¼6.8 Hz, 6H). 13C
(dd, J¼2.4 and 4.0 Hz, 1H), 7.96 (d, J¼8.8 Hz, 2H), 7.87 (d, J¼8.4 Hz,
NMR (100 MHz, DMSO-d6):
d 149.8, 139.2, 131.8, 129.9, 128.5, 127.7,
1H), 7.59 (d, J¼8.4 Hz, 2H), 6.88 (t, J¼8.4 Hz, 4H). 13C NMR
127.6, 127.0, 126.9, 126.7, 125.9, 121.9, 115.8, 115.6, 68.8, 31.2, 28.8,
28.7, 28.6, 25.6, 22.1, 13.9. IR (KBr, cmꢁ1): 3371 (OH), 3030, 2925,
2854, 1610, 1594, 1485, 1380, 1258, 1208, 1111, 1003, 815. Anal. Calcd
for C58H64O4: C, 84.63; H, 7.59. Found: C, 84.90; H, 7.00.
Mp¼256e257 ꢃC.
(100 MHz, DMSO-d6): d 158.4, 157.6, 153.9, 146.4, 134.1, 133.0,
129.2, 127.7, 118.9, 115.9, 115.5. IR (KBr, cmꢁ1): 3399 (OH), 1602,
1517, 1469, 1374, 1252, 1176, 821. Anal. Calcd for C17H13NO2: C,
77.55; H, 4.98;
N 5.32. Found: C, 77.93; H, 4.84; N, 5.00.
Mp¼352e354 ꢃC.
4.6. Synthesis of EtO-DobPh(5)-OEt
References and notes
Ethyl iodide (0.20 mL, 120 mmol) was added dropwise to the
EtOH solution (6 mL) of HO-DobPh(5)-OH (0.40 g, 0.60 mmol) and
KOH (0.13 g, 2.8 mmol). After the solution was refluxed for 24 h,
resulting precipitate was collected by filtration and washed with
water and acetone. EtO-DobPh(5)-OEt was collected by filtration,
dried in vacuo, and obtained as a white powder (0.34 g, 78%). 1H
1. Era, M.; Tsutsui, T.; Saito, S. Appl. Phys. Lett. 1995, 67, 2436e2438.
2. Meghdadi, F.; Leising, G.; Fisher, W.; Stelzer, F. Synth. Met. 1996, 76, 113e115.
3. Kauffman, J. M.; Litak, P. T.; Novinski, J. A.; Kelly, C. J.; Ghiorghis, A.; Qin, Y.
J. Fluoresc. 1995, 5, 295e305.
4. Wang, Y. Z.; Sun, R. G.; Meghdadi, F.; Leising, G.; Epstein, A. J. Appl. Phys. Lett.
1999, 74, 3613e3615.
5. Li, Z.-H.; Wong, M.-S.; Tao, Y.; D’Iorio, M. J. Org. Chem. 2004, 69, 921e927.
6. Ahn, K.-H.; Ryu, G. Y.; Youn, S.-W.; Shin, D.-M. Mater. Sci. Eng., C 2004, 24,
163e165.
NMR (400 MHz, CDCl3):
d
7.68 (d, J¼8.4 Hz, 4H), 7.61 (d, J¼8.4 Hz,
4H), 7.61 (d, J¼8.0 Hz, 4H), 7.04 (s, 2H), 6.99 (d, J¼8.8 Hz, 4H), 4.10
(q, J¼7.2 Hz, 4H), 3.95 (t, J¼6.4 Hz, 4H), 1.72 (m, 4H), 1.47 (t,
J¼6.8 Hz, 6H), 1.24e1.29 (m, 20H), 0.86 (t, J¼6.0 Hz, 6H). 13C NMR
7. Grundlach, D. J.; Lin, Y. Y.; Jackson, T. N.; Schlom, D. G. Appl. Phys. Lett. 1997, 71,
3853e3855.
€
8. Deeg, O.; Kirsch, P.; Pauluth, D.; Bauerle, P. Chem. Commun. 2002, 2762e2763.
9. Yu, Z. N.; Tu, H. L.; Wan, X. H.; Chen, Z. F.; Zhou, Q. F. Mol. Cryst. Liq. Cryst. 2003,
391, 41e45.
(100 MHz, CDCl3):
d 158.5, 150.4, 139.3, 136.7, 133.3, 130.3, 129.9,
128.0, 126.2, 116.1, 114.8, 69.6, 63.5, 31.8, 29.4, 29.3, 26.1, 22.7, 14.9,
14.1. IR (KBr, cmꢁ1): 3033, 2924, 2854, 1607, 1508, 1492, 1477, 1388,
1273,1250, 1216,1174,1045, 921, 822, 802. Anal. Calcd for C50H62O4:
C, 82.60; H, 8.60. Found: C, 82.85; H, 8.08. Mp¼168e170 ꢃC.
10. Sultana, N. H.; Kelly, S. M.; Mansoor, B.; O’Neill, N. Liq. Cryst. 2007, 34,
1307e1316.
11. Sidorov, V.; Douglas, T.; Dzekunov, S. M.; Abdallah, D.; Ghebremariam, B.;
Roepe, P. D.; Matile, S. Chem. Commun. 1999, 1429e1430.
12. Baumeister, B.; Matile, S. Chem. Commun. 2000, 913e914.
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4.7. Synthesis of HO-AntPh(2)-OH, HO-ThPh(4)-OH, and
HO-PyPh(2)-OH
HO-AntPh(2)-OH, HO-ThPh(4)-OH, and HO-PyPh(2)-OH were
synthesized using a procedure similar to that used for HO-FluPh
(4)-OH.
4.7.1. Data of HO-AntPh(2)-OH. Yield¼10%. 1H NMR (400 MHz,
DMSO-d6):
d
9.69 (s, 2H), 7.65 (dd, J¼3.2 and 6.8 Hz, 4H), 7.40 (dd,