Self-assembled triphenylamine-hexaazatriphenylene two-photon absorption dyes

Article abstract of DOI:10.1016/j.tet.2012.10.070

This paper reports the self-assembling and two-photon absorption natures of donor-acceptor molecules, tri(phenanthro)hexaazatriphenylene (TPHAT-C) and tri(phenanthrolino)hexaazatriphenylene (TPHAT-N), bearing six electron-donating moieties. In the ¹H NMR spectra, a line-broadening effect, arising from self-assembled aggregation was observed. Several hundred nanometer scale aggregates were detected in dynamic light scattering. The one-dimensional aggregation of the TPHAT molecules was indicated by the concentration dependence in UV/vis one-photon absorption and one-photon excited fluorescence spectroscopies. An enhancement of the two-photon absorption cross-section was observed in the self-assembled TPHAT system. The order of the two-photon absorption nature is in agreement with the order of the aggregative nature.

Full text of DOI:10.1016/j.tet.2012.10.070

Tetrahedron 69 (2013) 29e37
Contents lists available at SciVerse ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Self-assembled triphenylamine-hexaazatriphenylene two-photon
absorption dyes
,
a
a
a
b
Tsutomu Ishi-i a , Shogo Amemori , Chie Okamura , Kaori Yanaga , Rempei Kuwahara ,
*
Shuntaro Mataka c, Kenji Kamada d
,
*
a Department of Biochemistry and Applied Chemistry, Kurume National College of Technology, 1-1-1 Komorino, Kurume 830-8555, Japan
b Interdisciplinary Graduate School of Engineering Sciences, Kyushu University, 6-1 Kasuga-koh-en, Kasuga 816-8580, Japan
c Institute for Materials Chemistry and Engineering, Kyushu University, 6-1 Kasuga-koh-en, Kasuga 816-8580, Japan
d Research Institute for Ubiquitous Energy Devices, National Institute of Advanced Industrial Science and Technology (AIST), 1-8-31 Midorigaoka, Ikeda, Osaka 563-8577, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 10 August 2012
Received in revised form 22 October 2012
Accepted 25 October 2012
Available online 2 November 2012
This paper reports the self-assembling and two-photon absorption natures of donoreacceptor molecules,
tri(phenanthro)hexaazatriphenylene (TPHAT-C) and tri(phenanthrolino)hexaazatriphenylene (TPHAT-N),
bearing six electron-donating moieties. In the 1H NMR spectra, a line-broadening effect, arising from
self-assembled aggregation was observed. Several hundred nanometer scale aggregates were detected in
dynamic light scattering. The one-dimensional aggregation of the TPHAT molecules was indicated by the
concentration dependence in UV/vis one-photon absorption and one-photon excited fluorescence
spectroscopies. An enhancement of the two-photon absorption cross-section was observed in the
self-assembled TPHAT system. The order of the two-photon absorption nature is in agreement with the
order of the aggregative nature.
Keywords:
Two-photon absorption
Self-assembly
Supramolecules
Donoreacceptor
Hexaazatriphenylenes
Ó 2012 Elsevier Ltd. All rights reserved.
1. Introduction
relationships have been discussed.6e9 Two-photon absorption cross-
sections can also be enhanced by intermolecular interactions, such as
Supramolecular self-assembly of organic
p
-conjugated mole-
intercalation20 and self-assembling to form dimers and
aggregates.21e30 For self-assembled systems, the two-photon
absorption properties of porphyrins,21,27 pseudoisocyanines,22
squaryliums,23 [(aminostyryl)styryl]anthracenes,24 and tetraphenyl-
ethylenes29 have been reported; however, the variety of systems is
still limited. In thispaper, we reportnewself-assembled systems with
donoreaccepter moieties within the molecular structures and the
corresponding two-photon absorption properties. The new systems
have structural cores of tri(phenanthro)hexaazatriphenylene
(TPHAT-C) or tri(phenanthrolino)hexaazatriphenylene (TPHAT-N),
and each core demonstrates both electron-accepting and self-
assembling characters.31 Six triphenylamine (TPA)-based, electron-
donating groups were introduced at the periphery of the TPHAT-C
and TPHAT-N cores to form donoreacceptor conjugated molecules
with self-assembling abilities (Chart 1). Combinations of the TPA
groups with the TPHAT-C and TPHAT-N cores resulted in TPHAT-C-
cules, has been of much interest in view of the potential applications
to electronics, optoelectronics, and photonics.1 For example, in or-
ganic light-emitting diodes, field-effect transistors, and photovol-
taics, self-assembled p-conjugated molecules have beenwidely used
as donor and acceptor functional materials.2e4 Furthermore, interest
in self-assembling donoreacceptor conjugated molecules as attrac-
tive new targets for ambipolar functional materials has grown.5
Donoreacceptor substituted
p-conjugated structures have also
been developed in the field of two-photon absorption materials,6e12
which have a wide range of potential applications, including optical
power limitation,13 microfabrication,14 three-dimensional optical
data storage,15 two-photon laser scanning fluorescence imaging,16
and photodynamic therapy.17 Donoreacceptor substitution can
enhance the two-photon absorption activity of molecules6,9,11,18
through an increase in the transition dipole moment11,19 or the di-
pole moment difference between the ground and excited states.
Various types of conjugated systems incorporating donor and
acceptor moieties have been studied to enhance the two-photon
absorption cross-section, and the resultant structureeproperty
TPA and TPHAT-N-TPA molecules, respectively. The
p-electron
expanded TPHAT-C-ETPA, bearing an ethylene spacer, was also
designed as a superior self-assembling molecule. The TPHAT-C-
TPA-tBu molecule, containing bulky tert-butyl groups, was prepared
as non-aggregative reference. The aggregative nature of the TPHAT-C
and TPHAT-N derivatives were studied by MALDI-TOF mass spec-
trometry, and 1H NMR, dynamic light scattering, one-photon ab-
sorption, and one-photon excited fluorescence spectroscopies, and
* Corresponding authors. Tel.: þ81 942 35 9404; fax: þ81 942 35 9400; e-mail
addresses: ishi-i@kurume-nct.ac.jp (T. Ishi-i), k.kamada@aist.go.jp (K. Kamada).
0040-4020/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tet.2012.10.070

30
T. Ishi-i et al. / Tetrahedron 69 (2013) 29e37
2.2. Spectral properties and aggregative nature
Ar
X
Direct evidence for the aggregation of TPHAT-N-TPA, TPHAT-C-
TPA, and TPHAT-C-ETPA was obtained from MALDI-TOF mass spec-
trometry, in which aggregate species can be detected up to the tet-
ramer (Figs. S6eS8, Supplementary data). For example, in addition to
the parent ion of TPHAT-N-TPA (m/z 2149), significant peaks are seen
at several multiples of the parent ion, up to m/z 8596, and these in-
dicate assembly of four molecules.
In dynamic light scattering, several hundred nanometer scale
aggregates were detected in TPHAT-N-TPA (90 nm), TPHAT-C-TPA
(530 nm), and TPHAT-C-ETPA (300 nm) in toluene solution
(0.2 mM). In TPHAT-C-TPA-tBu, such aggregate species could not be
detected under the same conditions (Fig. S9, Supplementary data).
The one-dimensional aggregation of the TPHAT-N and TPHAT-C
molecules is indicated by concentration dependence in UV/vis one-
photon absorption spectroscopy (Fig. 1). The UV/vis spectra of
TPHAT-C-TPA in toluene show the longest absorption band at around
470 nm, which can be assigned to the charge-transfer transition from
the TPA chromophore to the TPHAT-C chromophore (Fig. 1(b)). The
intensity of the absorption band increased with decreasing concen-
tration, indicating a dynamic exchange from the aggregate species
with a weak absorption band to the monomer species with a strong
absorption band. This trend is similar to that for the previously re-
Ar
Ar
X
X
Ar
Ar
N
N
N
N
N
N
X
X
X
Ar
TPHAT-N-TPA
X = N
TPHAT-C-TPA
X = CH
Ar =
N
Ar =
N
t
Bu
Bu
t
TPHAT-C-TPA- Bu
TPHAT-C-ETPA
X= CH
ported one-dimensional
p-stacked TPHAT-N/TPHAT-C molecules
with an H-type parallel stacking mode.31 The concentration de-
pendence for the TPHAT-N-TPA was less than for the TPHAT-C-TPA
(Fig. 1(a,b)), indicating the superior aggregative nature of the
phenanthroline-fused TPHAT-N system.31b For TPHAT-C-ETPA, the
spectra were almost unchanged, irrespective of the concentration,
and the weak absorption band that appeared as a shoulder at around
500 nm was observed even at the more dilute concentration of
0.001 mM (Fig.1(c)). The enhanced aggregation could be attributed to
X= CH
Ar =
N
Ar =
N
t
Chart 1. Hexaazatriphenylenes TPHAT-N and TPHAT-Cs.
the expansion of the
p-electron system by introduction of the addi-
the two-photon absorption cross-sections were measured by the
femtosecond Z-scan method.
tional ethylene -spacer between the TPHAT-C core and the TPA
p
moieties. In contrast, in THPAT-C-TPA-tBu a strong absorption band
was observed at around 485 nm even at higher concentrations
(1.0 mM), indicating a non-aggregative nature (Fig. 1(d)). As a sum-
mary of the foregoing results, one can conclude that the order of the
aggregative nature increased in the order TPHAT-C-TPA-tBu<TPHAT-
C-TPA<TPHAT-N-TPA<TPHAT-C-ETPA.
2. Results and discussion
2.1. Preparation
Key synthetic intermediates, 2,9-bis(diphenylaminophenyl)-
1,10-phenanthroline-5,6-dione (3) and 3,4-disubstituted 9,10-
phenanthrenequinone 5aec were obtained from cross-coupling
reactions of the corresponding dibromide 131b and 4,32 re-
spectively, mediated by a palladium(0) catalyst (Scheme 1). The
obtained 3 and 5aec were condensed with hexaaminobenzene 933
to produce the desired TPHATs (Scheme 1). The obtained TPHAT-N-
TPA, TPHAT-C-TPA, TPHAT-C-TPA-tBu, and TPHAT-C-ETPA were
identified using spectroscopic methods and elemental analysis.
In the 1H NMR spectra at room temperature, a line-broadening
effect arising from aggregation was observed in halogenated
solvents, such as chloroform-d1 and 1,1,2,2-tetrachloroethane-d2.
At higher temperatures (120 ꢀC) in 1,1,2,2-tetrachloroethane-d2, the
broad peaks of the phenanthrene-fused system TPHAT-C-TPA be-
came sharp due to aggregate dissociation (Fig. S2, Supplementary
data). The resulting spectra provided eight aromatic proton sig-
nals from the phenanthrene rings and TPA moieties; from this, the
structure of TPHAT-C-TPA could be assigned. In contrast, the broad
peaks from the phenanthroline-fused systems TPHAT-N-TPA and
The aggregation of the TPHAT molecules is reflected in the one-
photon excited fluorescence spectra. As a result of the aggregation,
a bathochromic shift of the emission band was observed along with
a reduction in the emission intensity (Fig. 2). A moderate 18 nm
bathochromic shift and a moderate 0.50 fluorescence quantum
yield (FFL) are produced in the TPHAT-C-TPA system (Fig. 2(b)). In
the enhanced aggregation system, the bathochromic shift increases
to 43 nm in TPHAT-N-TPA and 76 nm in TPHAT-C-ETPA, and the FFL
values are reduced to 0.02 in TPHAT-N-TPA and 0.03 in TPHAT-C-
ETPA (Fig. 2(a,c)). In contrast, a small bathochromic shift of 5 nm
and a large fluorescence quantum yield (FFL) of 0.91 are produced
in the non-aggregative TPHAT-C-TPA-tBu system (Fig. 2(d)).
The aggregate structure can be visualized by atomic force
microscopy(AFM, Fig. 3). Theaggregatedtoluenesolution (0.01 mM)
of TPHAT-C-TPA was casted on freshly cleaved mica. The AFM image
indicates a nanoscale fibrous structure with a height of ca. 3.4 nm,
which is comparable to the molecular size of TPHAT-C-TPA.
the
p-electron expanded system TPHAT-C-ETPA still appeared even
2.3. Two-photon absorption nature
at the higher temperature, indicating the highly aggregative nature
of these compounds (Figs. S1, S4, Supplementary data). In TPHAT-C-
TPA-tBu, the proton signals are sharp even at room temperature,
because the steric hindrance of the tert-butyl groups disturbs ag-
gregation (Fig. S3, Supplementary data).
Thetwo-photonabsorptioncross-sections(d)weredeterminedby
the open-aperture Z-scan method with a femtosecond Ti:sapphire
laser as a light source (Figs. S10eS15, Supplementary data). The
shorter wavelength region of the two-photon absorption spectra

T. Ishi-i et al. / Tetrahedron 69 (2013) 29e37
31
O
N
O
N
O
B
O
N
O
N
O
N
2a
N
N
Pd(PPh3)4 / Na2CO3 aq
DME
Br
Br
1
3 (Y. 45%)
O
O
R
O
O
N
B
O
O
2a: R = H
2b: R = tBu
R
N
N
R
R
Br
Br
Pd(PPh3)4 / Na2CO3 aq
DME
4
R
R
5a: R = H (Y. 91%)
5b: R = tBu (Y. 80%)
O
O
N
6
4
Pd(OAc)2 / P(o-tolyl)3
Et3N / DMF
N
N
5c (Y. 58%)
t
t
Bu
Bu
Bu
HO
HO
NBS
DMF
1) BuLi / THF
2) B(OCH3)3
N
N
Br
2b (Y. 54%)
CH2Cl2
t
t
Bu
7
8 (Y. 94 %)
NH2
TPHAT-N-TPA (Y. 11%)
TPHAT-C-TPA (Y. 16%)
TPHAT-C-TPA- Bu (Y. 6%)
H2N
H2N
NH2
NH2
CH3COOH
3HCl
3, 5a-c
t
TPHAT-C-ETPA(Y. 12%)
NH2
9
Scheme 1. Preparation of hexaazatriphenylenes TPHAT-N and TPHAT-Cs.
overlapswiththetailsoftheone-photonabsorptionspectra,resulting
in a saturable absorption phenomenon. The saturable absorption was
corrected to precisely examine the two-photon absorption cross-
sections.34 The corrected two-photon absorption spectra indicated an
absorption band from 850 to 870 nm, which is located at nearly
double of the charge-transfer transition from the one-photon spectra
(Fig. 4(a)). However, the two-photon absorption maxima were ob-
served at higher transition energies than the one-photon absorption
maxima (Fig.1). This blue shift is due probably to intensity borrowing
of the one-photon excited state from a strongly allowed two-photon
excited state close to it through the vibronic coupling12q,35 or direct
transition to the low-laying two-photon allowed excited state just

32
T. Ishi-i et al. / Tetrahedron 69 (2013) 29e37
Fig. 1. UV/vis one-photon absorption spectra of (a) TPHAT-N-TPA, (b) TPHAT-C-TPA, (c) TPHAT-C-ETPA, and (d) TPHAT-C-TPA-tBu in toluene at room temperature.
Fig. 2. One-photon excited fluorescence spectra of (a) TPHAT-N-TPA (ex. 450 nm), (b) TPHAT-C-TPA (ex. 450 nm), (c) TPHAT-C-ETPA (ex. 460 nm), and (d) TPHAT-C-tBu (ex. 400 nm)
in toluene at room temperature.

T. Ishi-i et al. / Tetrahedron 69 (2013) 29e37
33
(1080 GM at 850 nm) system. The
sion of the
d
value increased with expan-
p
-electron system from TPHAT-C-TPA to TPHAT-C-ETPA
(2560 GM at 850 nm). Compared to the phenanthrene-fused
TPHAT-C-TPA system, the phenanthroline-fused TPHAT-N-TPA
demonstrated a larger
d value (2420 GM at 870 nm). Thus, the
order of the two-photon absorption nature was determined to be
TPHAT-C-TPA-tBu<TPHAT-C-TPA<TPHAT-N-TPA<TPHAT-C-ETPA,
which is in agreement with the aggregative nature. The en-
hancement of the two-photon absorption cross-section could be
ascribed to the expansion of the
p-electron system and/or the self-
assembled aggregation of the TPHAT molecules. In previous
studies, enhancement of the
d values was reported in some self-
assembled J-type aggregate systems.21e23 This enhancement can
be explained by the strong increase in the transition dipole mo-
ment arising from the dipole coupling interactions of the J-type
aggregates. A transition dipole coupling effect can also be expected
in our TPHAT-based H-type aggregate system.
Two of the four compounds were examined at wavelengths
shorter than 820 nm. In the spectral region, TPHAT-C-ETPA
showed a significant increase in
d
with decreasing wavelength,
value at
but TPHAT-C-TPA-tBu did not (Fig. 4(b)). The maximum
d
Fig. 3. Atomic force microscopy image of TPHAT-C-TPA. The sample was prepared by
drop-casting on mica from a 0.01 mM toluene solution.
649 nm was almost nine times larger than that at 850 nm
(Fig. S15, Supplementary data). This significant increase can be
interpreted as resonance enhancement of the two-photon tran-
sition near the one-photon resonance,18 because TPHAT-C-ETPA
has a considerable one-photon absorption tail at these wave-
lengths (Fig. 1(c)), whereas there is no overlap with the one-
photon absorption tail for TPHAT-C-TPA-tBu (Fig. 1(d)).
3. Conclusions
In conclusion, we created self-assembled two-photon absorp-
tion dyes based on a combination of an electron-accepting hex-
aazatriphenylene core and an electron-donating TPA moiety. The
donoreacceptor molecules are self-assembled one-dimensionally
to form H-type aggregates. The aggregative nature is enhanced
significantly in a
p-electron expanded system. The present self-
assembled system provides moderate two-photon absorption
cross-sections up to 2560 GM (for TPHAT-C-ETPA) in the
820e870 nm wavelength region, as well as a significant increase in
the shorter wavelength region. Aggregation dependence on the
two-photon absorption properties was observed in this H-type
aggregate system, similar to the J-type aggregate systems pre-
viously reported. We believe that the present study provides useful
information for the development of self-assembled two-photon
absorption systems.
4. Experimental
4.1. General
All melting points are uncorrected. IR spectra were recorded on
a JASCO FT/IR-470 plus Fourier transform infrared spectrometer,
and measured as KBr pellets. 1H and 13C NMR spectra were de-
termined in CDCl3 and CDCl2CDCl2 with a JEOL JNM-AL 400 spec-
trometer. Residual solvent protons were used as internal standard
Fig. 4. Two-photon absorption spectra of TPHAT-N-TPA (0.6 mM), TPHAT-C-TPA
(0.6 mM), TPHAT-C-ETPA (0.45 mM), and TPHAT-C-TPA-tBu (0.19 mM) in toluene in
the range (a) 820e1020 nm and (b) 620e820 nm.
and chemical shifts (d) are given relative to tetramethylsilane
(TMS). The coupling constants (J) are reported in hertz (Hz). Ele-
mental analysis was performed at the Elemental Analytical Center,
Kyushu University. Fast atom bombardment mass spectrometry
(FAB-MS) spectra were recorded with a JEOL JMS-70 mass spec-
trometer with m-nitrobenzyl alcohol (NBA) as a matrix. Matrix
assisted laser desorption ionization time-of-flight mass spectrom-
etry (MALDI-TOF-MS) was performed on a BRUKER AutoFLEX
spectrometer using delayed extraction mode and with an
above the one-photon allowed state.12g Further studies are needed to
distinguish the mechanisms.
An enhancement of the two-photon absorption cross-section
was observed for the self-assembled TPHAT-C-TPA system to
give a
d value of 1460 GM (at 870 nm), which is 1.4 times larger
than the value for the non-aggregative TPHAT-C-TPA-tBu

34
T. Ishi-i et al. / Tetrahedron 69 (2013) 29e37
acceleration voltage of 20 keV. Samples were prepared from a so-
lution of dichloromethane using dithranol as the matrix.
Gel permeation chromatography (GPC) was performed with
4.4. 3,6-Bis[4-bis(4-tert-butylphenyl)aminophenyl]-9,10-
phenanthrenequinone (5b)
a
Japan Analytical Industry LC-908 using JAIGEL-1H column
According to a method similar to the preparation of 3, 5b was
obtained in 80% yield (516 mg, 0.56 mmol) from 4 (256 mg,
0.7 mmol), 2b (723 mg, 1.54 mol), tetrakis(triphenylphosphine)
palladium (0) (162 mg, 0.14 mmol), deaerated DME (14 mL), and
deaerated aqueous 2 M sodium carbonate solution (7 mL). The
crude product was purified by silica gel column chromatography
(KANTO 60N) eluting with dichloromethane. An analytical sample
was obtained by recrystallization from dichloromethane/hexane.
Violet solid; mp 368e369 ꢀC; IR (KBr, cmꢂ1) 3035, 2962, 2903,
(20ꢁ600 mm) and JAIGEL-2H column (20ꢁ600 mm) eluting with
chloroform (3.0 mL/min). Analytical TLC was carried out on silica
gel coated on aluminum foil (Merck 60 F254). Column chromatog-
raphy was carried out on silica gel (KANTO 60N). THF was distilled
from sodium and benzophenone under an argon atmosphere just
before use. DMF was distilled from calcium hydride under reduced
pressure just before use. 2,9-Dibromo-1,10-phenanthroline (1),31b
2,2-dimethyl-1,3-propanediol 4-(diphenylamino)phenylboronate
(2a),36 3,6-dibromo-9,10-phenanthrenequinone (4),32 4-(dipheny-
lamino)styrene (6),12h N,N-bis(4-tert-butylphenyl)aniline (7),37 and
hexaaminobenzene trihydrochloride (9)33 were prepared accord-
ing to methods reported previously.
2867, 1671 (
NMR (CDCl3)
n
C]O), 1589, 1509, 1323, 1298, 1281, 1267, 1188, 825; 1H
d
1.33 (s, 36H, CH3), 7.10 (d, J¼8.8 Hz, 8H, ArH), 7.15 (d,
J¼8.8 Hz, 4H, ArH), 7.32 (d, J¼8.8 Hz, 8H, ArH), 7.57 (d, J¼8.8 Hz, 4H,
ArH), 7.65 (dd, J¼1.2, 7.8 Hz, 2H, ArH), 8.23 (d, J¼1.2 Hz, 2H, ArH),
8.25 (d, J¼7.8 Hz, 2H, ArH); 13C NMR (CDCl3)
d 31.4, 34.4, 121.5,
121.8, 124.8, 126.3, 127.3, 127.9, 129.3, 131.2, 131.3, 136.3, 144.4,
146.8, 148.2, 149.4, 180.1; FAB-MS (positive, NBA) m/z 920
[(Mþ1)þ]. Anal. Calcd for C66H66N2O2$0.7CH2Cl2 (919.24): C, 81.86;
H, 6.94; N, 2.86. Found: C, 81.77; H, 6.87; N, 2.91.
4.2. 2,9-Bis[4-(diphenylamino)phenyl]-1,10-phenanthroline-
5,6-dione (3)
To a mixture of 1 (552 mg, 1.5 mmol) and tetrakis(triphenyl-
phosphine)palladium (0) (347 mg, 0.3 mmol) in deaerated DME
(30 mL) were added 2a (954 mg, 3.3 mmol) and deaerated aqueous
2 M sodium carbonate solution (15 mL) at 60 ꢀC under an argon
atmosphere and the resulting mixture was heated at 85 ꢀC for 16 h.
The reaction mixture was poured into water (150 mL) and extracted
with dichloromethane (150 mLꢁ2). The organic layer was washed
with brine (400 mL) and water (400 mLꢁ4), dried over anhydrous
magnesium sulfate, and evaporated in vacuo to dryness. The residue
was purified by silica gel column chromatography (KANTO 60N)
eluting with dichloromethane to give 3 in 45% yield (471 mg,
0.68 mmol) as a violet solid. An analytical sample obtained by re-
crystallization from dichloromethane/hexane. Mp 137e138 ꢀC; IR
4.5. 3,6-Bis{2-[4-(diphenylamino)phenyl]ethenyl}-9,10-
phenanthrenequinone (5c)
To a suspension of 4 (915 mg, 2.5 mmol), 6 (1.60 g, 5.9 mmol),
and triethylamine (2.8 mL, 20 mmol) in dry DMF (20 mL) was added
a solution of palladium acetate (45 mg, 0.20 mmol) and tri(o-tolyl)
phosphine (122 mg, 0.40 mmol) in dry DMF (5 mL) at 100 ꢀC under
an argon atmosphere, and the mixture was allowed to stand at
100 ꢀC for 4.5 h. After the reaction mixture was cooled to 0 ꢀC, it was
quenched with aqueous 1 N hydrochloric acid solution and
extracted with dichloromethane (250 mLꢁ2). The organic layer was
washed with brine (400 mLꢁ8), dried over anhydrous magnesium
sulfate, and evaporated in vacuo to dryness. The residue was
purified by silica gel column chromatography (KANTO 60N) eluting
with dichloromethane/methanol (299:1, v/v) to give 5c in 58% yield
(KBr, cmꢂ1) 1667 (
696; 1H NMR (CDCl3)
nC]O),1568,1549,1489,1326,1283,1177, 827, 753,
d
7.11 (t, J¼7.4 Hz, 4H, ArH), 7.14e7.23 (m, 12H,
ArH), 7.31 (t, J¼7.4 Hz, 8H, ArH), 7.90 (d, J¼8.4 Hz, 2H, ArH), 8.20 (d,
J¼8.6 Hz, 4H, ArH), 8.47 (d, J¼8.4 Hz, 2H, ArH); 13C NMR (CDCl3)
(1.68 g, 1.44 mmol): violet solid; mp 165e167 ꢀC; IR (KBr, cmꢂ1
3058, 3027, 1666 ( C]O), 1580, 1507, 1486, 1280, 1236, 1172, 956,
923, 830, 750, 693; 1H NMR (CDCl3)
7.05e7.17 (m, 18 H, ArH and
)
d
120.3, 122.0, 124.1, 125.4, 125.9, 129.0, 129.5, 130.6, 137.6, 146.9,
n
150.7, 153.1, 162.2, 178.8; MALDI-TOF-MS m/z (positive, dithranol)
696.26 (Mþ, calcd for C48H32N4O2 696.25). Anal. Calcd for
C48H32N4O2$0.3CH2Cl2 (696.79): C, 80.32; H, 4.55; N, 7.76. Found: C,
80.05; H, 4.24; N, 7.69.
d
olefinic H), 7.30 (t, J¼8.3 Hz, 8H, ArH), 7.33 (d, J¼16.1 Hz, 2H, olefinic
H), 7.46 (d, J¼8.8 Hz, 4H, ArH), 7.61 (dd, J¼1.0, 8.3 Hz, 2H, ArH), 8.09
(d, J¼1.0 Hz, 2H, ArH), 8.19 (d, J¼8.3 Hz, 2H, ArH); 13C NMR (CDCl3)
d
122.0, 122.6, 123.6, 125.0, 125.1, 126.3, 128.1, 129.4, 129.7, 129.8,
131.0, 132.9, 136.1, 145.2, 147.2, 148.6, 179.7; FAB-MS (positive, NBA)
m/z 747 [(Mþ1)þ]. Anal. Calcd for C54H38N2O2$0.2CH2Cl2 (746.89):
C, 85.22; H, 5.07; N, 3.67. Found: C, 85.48; H, 5.04; N, 3.75.
4.3. 3,6-Bis[4-(diphenylamino)phenyl]-9,10-
phenanthrenequinone (5a)
According to a method similar to the preparation of 3, 5a was
obtained in 91% yield (630 mg, 0.907 mmol) from 4 (366 mg,
1.0 mol), 2a (636 mg, 2.2 mol), tetrakis(triphenylphosphine)palla-
dium (0) (231 mg, 0.2 mmol), deaerated DME(20 mL), and dea-
erated aqueous 2 M sodium carbonate solution (10 mL). The crude
product was purified by silica gel column chromatography (KANTO
60N) eluting with dichloromethane. An analytical sample was ob-
tained by recrystallization from dichloromethane/hexane. Brown
4.6. 3,6,13,16,23,26-Hexakis[4-(diphenylamino)pheny]-tri-
1,10-phenanthrolino[5,6-b:50,60-h:500,600-n]-1,4,5,8,9,12-
hexaazatriphenylene (TPHAT-N-TPA)
A mixture of 2 (447 mg, 0.64 mmol), hexaaminobenzene tri-
hydrochloride (65 mg, 0.235 mmol) in deaerated acetic acid (10 mL)
was heated at the refluxing temperature for 17 h under an argon
atmosphere. After the reaction mixture was cooled to room tem-
perature, it was poured into water (150 mL), and extracted with
dichloromethane (150 mLꢁ2). The organic layer was treated with
aqueous 1 M sodium hydrogen carbonate solution (200 mL),
washed with brine (200 mL) and water (200 mLꢁ2), dried over
anhydrous magnesium sulfate, and evaporated in vacuo to dryness.
The residue was subjected to silica gel column chromatography
(KANTO 60N) eluting with chloroform to give crude TPHAT-N-TPA.
The crude product was purified by GPC eluting with chloroform to
give TPHAT-N-TPA in 11% yield (53 mg, 0.025 mmol); dark brown
solid; mp >350 ꢀC; IR (KBr, cmꢂ1) 1577, 1488, 1369, 1315, 1282, 1217,
solid; mp 284e285 ꢀC; IR (KBr, cmꢂ1) 3060, 3034, 1662 (
1588, 1512, 1489, 1323, 1294, 1268, 1193, 1180, 925, 825, 753, 696;
1H NMR (CDCl3)
nC]O),
d
7.10 (t, J¼7.2 Hz, 4H, ArH), 7.16e7.20 (m, 12H,
ArH), 7.31 (t, J¼7.2 Hz, 8H, ArH), 7.59 (d, J¼8.8 Hz, 4H, ArH), 7.66 (dd,
J¼1.6, 8.4 Hz, 2H, ArH), 8.24 (d, J¼1.6 Hz, 2H, ArH), 8.26 (d, J¼8.4 Hz,
2H, ArH); 13C NMR (CDCl3)
d 121.7, 122.8, 123.8, 125.1, 127.4, 128.1,
129.4, 129.5, 131.2, 132.3, 136.2, 147.2, 148.1, 149.0, 180.0; FAB-MS
(positive, NBA) m/z 695 [(Mþ1)þ]. Anal. Calcd for C50H34N2O2･
0.1CH2Cl2 (694.82): C, 85.56; H, 4.90; N, 3.98. Found: C, 85.32; H,
4.86; N, 3.99.

T. Ishi-i et al. / Tetrahedron 69 (2013) 29e37
35
1176, 828, 753, 696; MALDI-TOF-MS (positive, dithranol) m/z
2148.79 (Mþ, calcd for C150H96N18 2148.81). Anal. Calcd for
C150H96 18$1.6CHCl3 (2150.49): C, 77.76; H, 4.20; N, 10.77. Found: C,
4.10. 4-Bis(4-tert-butylphenyl)amino-1-bromobenzene (8)
N
To a suspension of 7 (1.25 g, 3.5 mmol) in DMF (14 mL) was
added dropwise NBS (623 mg, 3.5 mmol) in DMF (1.4 mL) at 0 ꢀC
under an argon atmosphere and the mixture was stirred at room
temperature for 1 h. The reaction mixture was quenched with
water (15 mL). The formed precipitate was collected by filtration,
and washed with water (100 mL) and methanol (10 mL) to give 8 in
94% (1.442 g, 3.3 mmol) as white powder. An analytical sample was
obtained by recrystallization from methanol. Mp 158e159 ꢀC; IR
(KBr, cmꢂ1) 3037, 2960, 2900, 2864, 1580, 1509, 1485, 1323, 1295,
77.48; H, 4.49; N, 11.02.
4.7. 3,6,13,16,23,26-Hexakis[4-(diphenylamino)phenyl]-tri-
phenanthro[9,10-b:90,100-h:900,1000-n]-1,4,5,8,9,12-
hexaazatriphenylene (TPHAT-C-TPA)
According to a method similar to the preparation of TPHAT-N-TPA,
TPHAT-C-TPA was obtained in 16% yield (85 mg, 0.040 mmol) from
hexaaminobenzene trihydrochloride (83 mg, 0.3 mmol), 5a (521 mg,
0.75 mmol), and deaerated acetic acid (11.5 mL). The reaction mixture
was purified by silica gel column chromatography (KANTO 60N)
eluting with chloroform and GPC eluting with chloroform. Dark
brown solid; mp >350 ꢀC; IR (KBr, cmꢂ1) 3057, 3031,1588,1490,1272,
820, 750, 693; 1H NMR (1,1,2,2-tetrachloroetane-d2 (1 mM), 120 ꢀC)
1284, 1271, 828, 817; 1H NMR (CDCl3)
d 1.31 (s, 18H, CH3), 6.92 (d,
J¼8.8 Hz, 2H, ArH), 6.99 (d, J¼8.8 Hz, 4H, ArH), 7.25 (d, J¼8.8 Hz, 4H,
ArH), 7.28 (d, J¼8.8 Hz, 2H, ArH); 13C NMR (CDCl3)
d 31.4, 34.3, 113.8,
124.0, 124.3, 126.1, 131.9, 144.7, 146.1, 147.4; FAB-MS (positive, NBA)
m/z 435, 437 (Mþ). Anal. Calcd for C26H30BrN (436.43): C, 71.55; H,
6.93; N, 3.21. Found: C, 71.16; H, 6.94; N, 3.33.
d
7.12 (t, J¼7.6 Hz,12H ArH), 7.21 (d, J¼8.0 Hz, 24H, ArH), 7.19e7.24 (br
4.11. 2,2-Dimethyl-1,3-propanediol 4-bis(4-tert-butylpheny-
lamino)phenylboronate (2b)
d, 12H, ArH), 7.35 (t, J¼7.6 Hz, 24H, ArH), 7.64e7.74 (br d, 12H, ArH),
7.88e7.97 (br d, 6H, ArH), 8.47e8.57 (br s, 6H, ArH), 9.31e9.48 (br d,
6H, ArH); 13C NMR (1,1,2,2-tetrachloroetane-d2 (5 mM), 120 ꢀC)
To a suspension of 8 (1.658 g, 3.8 mmol) in dry THF (20 mL)
d
120.2, 123.5, 123.7, 125.1, 125.3, 126.2, 127.4, 128.2, 129.6, 129.7, 132.4,
was added dropwise 1.66
M butyllithium hexane solution
134.6, 141.4, 141.7, 148.0, 148.1; MALDI-TOF-MS (positive, dithranol)
(2.52 mL, 4.18 mmol) at ꢂ78 ꢀC for 4 min under an argon atmo-
sphere. After the mixture was allowed to stand at ꢂ78 ꢀC for 1 h,
a solution of trimethylborate (0.474 g, 4.56 mmol) in dry THF
(4 mL) was added at ꢂ78 ꢀC for 5 min. The mixture was allowed to
stand at ꢂ78 ꢀC for 30 min and warmed up to 0 ꢀC. The reaction
mixture was quenched with aqueous 1.2 N hydrochloric acid so-
lution (3.6 mL) and water (40 mL) at 0 ꢀC, and extract with ethyl
acetate (100 mLꢁ2). The organic layer was washed with brine
(40 mL) and water (40 mL), dried over anhydrous magnesium
sulfate, and evaporated in vacuum to dryness. The residue (1.50 g)
was treated with 2,2-dimethyl-1,3-propanediol (0.542 g,
5.2 mmol) in dichloromethane (4 mL) under an argon atmosphere
and the mixture was stirred at room temperature for 1 h. The
reaction mixture was dried over anhydrous magnesium sulfate
and evaporated in vacuum to dryness. The residue (1.90 g) was
purified by silica gel column chromatography (KANTO 60N) elut-
ing with hexane/dichloromethane, (1:9, v/v) to give 2b in 54%
yield (0.967 g, 2.06 mmol) as white solid. An analytical sample was
obtained by recrystallization from dichloromethane. Mp
213e214 ꢀC; IR (KBr, cmꢂ1) 3033, 2961, 2901, 2867, 1598, 1507,
m/z 2142.89 [Mþ, calcd for C150H96N18 2142.84]. Anal. Calcd for
C156H102N12$0.8CHCl3 (2144.56): C, 84.07; H, 4.63; N, 7.50. Found: C,
84.36; H, 4.80; N, 7.34.
4.8. 3,6,13,16,23,26-Hexakis{[4-bis(4-tert-butylphenyl)amino]
phenyl}-triphenanthro[9,10-b:90,100-h:900,1000-n]-1,4,5,8,9,12-
hexaazatriphenylene (TPHAT-C-TPA-tBu)
According to a method similar to the preparation of TPHAT-N-TPA,
TPHAT-C-TPA-tBu was obtained in 6% yield (28 mg, 0.010 mmol) from
hexaaminobenzene trihydrochloride (56 mg, 0.20 mmol), 5b
(460 mg, 0.50 mmol), deaerated acetic acid (4 mL), and deaerated
1,1,2,2-tetrachloroethane (2 mL). The reaction mixture was purified
by silica gel column chromatography (KANTO 60N) eluting with
chloroform and GPC eluting with chloroform. Brown solid; IR (KBr,
cmꢂ1) 3033, 2957, 2901, 2865, 1598, 1508, 1364, 1321, 1267, 824; 1H
NMR(1,1,2,2-tetrachloroetane-d2 (1mM),120ꢀC)
d1.44(s,108H,CH3),
7.16 (d, J¼8.7 Hz, 24H, ArH), 7.23 (d, J¼8.3 Hz, 12H, ArH), 7.38 (d,
J¼8.7 Hz, 24H, ArH), 7.74 (d, J¼8.3 Hz,12H, ArH), 8.05 (d, J¼7.8 Hz, 6H,
ArH), 8.70 (s, 6H, ArH), 9.64 (d, J¼7.8 Hz, 6H, ArH)); 13C NMR (1,1,2,2-
1316 (nBO), 1275, 1135, 830; 1H NMR (CDCl3)
d 1.01 (s, 6H, CH3), 1.31
tetrachloroetane-d2 (5 mM), 120 ꢀC)
d
31.7, 34.5, 120.2, 123.0, 124.9,
(s, 18H, CH3), 3.74 (s, 4H, CH2), 7.00 (d, J¼8.3 Hz, 2H, ArH), 7.02 (d,
126.3, 126.7, 127.6, 128.3, 129.2, 132.8, 133.9, 141.8, 142.3, 142.5, 145.3,
J¼8.3 Hz, 4H, ArH), 7.24 (d, J¼8.3 Hz, 4H, ArH), 7.63 (d, J¼8.3 Hz,
146.5, 148.5; MALDI-TOF-MS (positive, dithranol) m/z 2815.79 [Mþ,
2H, ArH); 13C NMR (CDCl3)
d 21.9, 31.4, 31.9, 34.3, 72.3, 121.2, 124.4,
calcd for C204H198N12 2815.59]. Anal. Calcd for C204H198
(2817.84): C, 84.43; H, 6.88; N, 5.77. Found: C, 84.35; H, 6.87; N, 5.81.
N
12$0.8CHCl3
126.0, 134.7, 144.8, 145.9, 150.4; FAB-MS (positive, NBA) m/z 469
(Mþ). Anal. Calcd for C31H40BNO2 (469.47): C, 79.31; H, 8.59; N,
2.98. Found: C, 79.18; H, 8.57; N, 3.02.
4.9. 3,6,13,16,23,26-Hexakis{2-[4-(diphenylamino)phenyl]
ethenyl}triphenanthro[9,10-b:90,100-h:900,1000-n]-1,4,5,8,9,12-
hexaazatriphenylene (TPHAT-C-ETPA)
4.12. UV/vis and fluorescence spectroscopy
UV/vis spectra were measured on a JASCO V-570 spectropho-
tometer in a 0.01 cm width quartz cell (1.0 mM), a 0.1 cm width
quartz cell (0.1 mM), a 1.0 cm width quartz cell (0.01 mM), and
10.0 cm width quartz cell (0.001 mM). Fluorescence spectra were
measured on a HITACHI F-4500 fluorescence spectrophotometer.
According to a method similar to the preparation of TPHAT-N-TPA,
TPHAT-C-ETPA was obtained in 12% yield (14 mg, 0.006 mmol) from
hexaaminobenzene trihydrochloride (17 mg, 0.06 mmol), 5c (112 mg,
0.15 mmol), deaerated acetic acid (1 mL), and deaerated 1,1,2,2-
tetrachloroethane (0.5 mL). The reaction mixture was purified by
silica gel column chromatography (KANTO 60N) eluting with chlo-
roform/hexane (3:1, v/v) and GPC eluting with chloroform. Dark
brownsolid; mp >350 ꢀC; IR (KBr, cmꢂ1) 3057, 3022,1586,1490,1274,
830, 750, 693; MALDI-TOF-MS (positive, dithranol) m/z 2299.59 [Mþ,
4.13. AFM observation
Atomic force microscopy (AFM) images were obtained on a SII
SPA400 DFM (tapping mode). SI-DF 20 type tips were used. Sam-
ples were prepared by drop casting from 0.01 mM toluene solutions
on freshly cleaved mica.
calcd for C168H114N12 2298.93]. Anal. Calcd for C168H114
N12$1.2CHCl3
(2300.78): C, 83.15; H, 4.75; N, 6.88. Found: C, 83.02; H, 4.77; N, 7.03.

36
T. Ishi-i et al. / Tetrahedron 69 (2013) 29e37
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at 1 kHz. The optical setup used for the Z-scan measurements is
described elsewhere.39 The laser beam was reshaped by passing
through a small iris aperture to obtain a near Gaussian spatial
profile. The pulse width of the laser beam was 110e130 fs in FWHM,
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a Gaussian temporal profile and used to calculate on-axis peak
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We thank Mr. Tomoyuki Ishikawa (Fukuoka Industrial Technol-
ogy Center) for the MALDI-TOF mass spectrometry measurement.
This work was partially supported by Tokuyama Science Founda-
tion, Yoshida Foundation for the Promotion of Learning and Edu-
cation, and by Grant-in-Aid for Scientific Research from the
Ministry of Education, Science, Culture, Sports, and Technology of
Japan (No. 22550132).
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scattering. Supplementary data associated with this article can be
found in the online version, at http://dx.doi.org/10.1016/
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most important compounds described in this article.
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