Synthesis of amide group containing triphenylene derivatives as discotic liquid crystals and organic gelators

Article abstract of DOI:10.1080/15421400903112069

Intermolecular hydrogen bond is an efficient way to anchor columnar assembly of discotic liquid crystals, and would result in more ordered columnar mesphase and faster charged carrier mobility. In this report, a series of peripheral functionalized triphenylene derivatives, C₁₈H ₆(OC₆H₁₃)₄(OCH₂CONHR) ₂, which contains amide groups at the 2,7-positions, have been synthesized. The polarized optical microscopy (POM) and differential scanning calorimetry (DSC) results showed that these compounds exhibit hexagonal columnar mesophases. The triphenylene derivatives gelate in the solution of octane, petroleum ether, cyclohexane and p-xylene and form stable organic gels. The xerogels formed from organic solvents were analyzed by scanning electron microscope (SEM) and showed fiber-like or sponge-like morphology. It is demonstrated that intermolecular hydrogen bonds stabilize the columnar molecular organization and assembly in mesomorphic state and organic gel. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/15421400903112069

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Synthesis of Amide Group
Containing Triphenylene
Derivatives as Discotic Liquid
Crystals and Organic Gelators
Y. F. Bai a , K. Q. Zhao a , P. Hu a , B. Q. Wang a & Y.
Shimizu b
a College of Chemistry and Materials Science,
Sichuan Normal University, Chengdu, Sichuan, China
b Synthetic Nano-Function Materials Group,
Nanotechnology Research Institute, National
Institute of Advanced Industrial Science and
Technology, Ikeda, Osaka, Japan
Published online: 05 Oct 2009.
To cite this article: Y. F. Bai , K. Q. Zhao , P. Hu , B. Q. Wang & Y. Shimizu (2009)
Synthesis of Amide Group Containing Triphenylene Derivatives as Discotic Liquid
Crystals and Organic Gelators, Molecular Crystals and Liquid Crystals, 509:1, 60/
[802]-76/[818], DOI: 10.1080/15421400903112069
To link to this article: http://dx.doi.org/10.1080/15421400903112069
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Mol. Cryst. Liq. Cryst., Vol. 509, pp. 60=[802]–76=[818], 2009
Copyright # Taylor & Francis Group, LLC
ISSN: 1542-1406 print=1563-5287 online
DOI: 10.1080/15421400903112069
Synthesis of Amide Group Containing Triphenylene
Derivatives as Discotic Liquid Crystals and
Organic Gelators
Y. F. Bai1, K. Q. Zhao1, P. Hu1, B. Q. Wang1, and
Y. Shimizu2
1College of Chemistry and Materials Science, Sichuan Normal
University, Chengdu, Sichuan, China
2Synthetic Nano-Function Materials Group, Nanotechnology Research
Institute, National Institute of Advanced Industrial Science and
Technology, Ikeda, Osaka, Japan
Intermolecular hydrogen bond is an efficient way to anchor columnar assembly of
discotic liquid crystals, and would result in more ordered columnar mesphase and
faster charged carrier mobility. In this report, a series of peripheral functionalized
triphenylene derivatives, C18H6(OC6H13)4(OCH2CONHR)2, which contains amide
groups at the 2,7-positions, have been synthesized. The polarized optical microscopy
(POM) and differential scanning calorimetry (DSC) results showed that these
compounds exhibit hexagonal columnar mesophases. The triphenylene derivatives
gelate in the solution of octane, petroleum ether, cyclohexane and p-xylene and form
stable organic gels. The xerogels formed from organic solvents were analyzed by
scanning electron microscope (SEM) and showed fiber-like or sponge-like morphol-
ogy. It is demonstrated that intermolecular hydrogen bonds stabilize the columnar
molecular organization and assembly in mesomorphic state and organic gel.
Keywords: discotic liquid crystal; hydrogen bond; self-assembly; small molecular mass
organic gelator; supramolecular organic gel; triphenylene
1. INTRODUCTION
The supramoleculer organization of discotic liquid crystals (DLCs),
such as triphenylene and hexabenzocoronene derivatives, have been
Project supported by National Nature Science Foundation of China (Project Nos.
50473062, 50673069, and 50811140156).
Address correspondence to K. Q. Zhao, College of Chemistry and Materials
Science, Sichuan Normal University, Chengdu 610066, Sichuan, China. E-mail:
kqzhao@sicnu.edu.cn
60=[802]

Synthesis of Amide Group Containing Triphenylene
61/[803]
attracting considerable interests since 1977 [1–5], as they can self
assemble to highly ordered hexagonal columnar mesophases promoted
by the p-p interactions between the polyaromatic cores [6], and this
leads to the formation of one-dimensional pathway for transport of
charged carriers along the columns. The charged carries mobility rate
in DLCs arrives at 0.12 cm2 Vꢀ1 sꢀ1, this value is comparable to the
commercially used silicon semiconductors [7]. Therefore DLC materi-
als are potential candidate materials as photovoltaic devices, field
effect transistors and organic light emitting diodes, gas sensors and
other molecular electronics [8–12].
In the columnar assemblies, the DLC molecules can fluctuate in the
column, slide out of the column, or rotate around the columnar axis, it
therefore significantly disturbs the charged carrier mobility [13]. Thus
restricting and controlling the molecular movements in the columnar
mesophase are desired. Usually some approaches such as using
b-oxygen effect [14–16], fluorophobic-fluorophilic effect [17–19], hydro-
philic-hydrophobic effect [20,21], donor-acceptor interaction [22,23],
and ionic interaction [24,25] have been used to provide such kind of
controlling. Hydrogen-bonding is an important self-assembling tool
as its moderate bonding energy, directionality, selectivity, and rever-
sibility. H-bondings make the adjacent polyaromatic cores approach
each other more closely, the HOMO-LUMO splitting increase, and a
high charge carrier mobility ensure.
H-bonding interactions provide a promise way for the stabilization of
columnar organization, and different approaches have been developed
for H-bonding stabilization of triphenylene derivatives. However,
not all H-bonding system results in stable columnar mesophase. For
example, Shimizu’s group synthesized a series of triphenylene deriva-
tives, C18H6(OC6H13)4(OCnH2nCOOH)2, with carboxylic groups at the
terminal of 2,3-position [26,27]. The spacer length between carboxylic
group and triphenylene core was changed, only few triphenylenes
exhibited narrow monotropic mesophases. Kumar prepared series
of mono-, di-, and tri-acetylamino hexabutyloxytriphenylenes, C18H6
(OC4H9)6(NHAc)n, n ¼ 1–3, only 1-acetylamine-2,3,6,7,10,11-hexabuty-
loxy- triphenylene showed monotropic mesophase [28]. Shinkai
reported six-fold H-bonding triphenylenes, C18H6(OCH2CONHR)6,
R ¼ C4H9 and C12H15, no thermotropic liquid crystalline properties
was reported [29]. Marcelis synthesized several triphenylene deriva-
tives with amide, urea or thiourea group in one of peripheral chains,
and the amide-containing triphenylenes did not show mesomorphism
[30]. Some H-bonding triphenylenes indeed show stabilized Colho
phase and higher charge mobility. For example, Zhao has prepared
series of amide-containing triphenylene, C18H6(OCnH2nþ1 6-x
)
(OCH2

62/[804]
Y. F. Bai et al.
SCHEME 1 Synthesis of triphenylene discotic intermediate.
CONHR)x, x ¼ 1, 3, n ¼ 4–9, and wider columnar mesophase ranges
were found [31–33]. Marcelis and Zuihof synthesized a H-bond triphe-
nylene and displayed the highest charge carrier mobility value. The
above examples tell us that rational molecular design is important
for the success of stable Colho phase and high charge mobility.
Small molecular mass organic gels are attracting lot of attentions
for the academic interests and potential industrial application in
membrane and separation technology, catalysis or drug delivery
[34–36]. The investigation showed that aromatic p-p interactions,
SCHEME 2 Synthesis of amide group containing triphenylene discogens.

Synthesis of Amide Group Containing Triphenylene
63/[805]
H-bondings, and van de Waals interactions are the mechanism for
stable organic gels. From these points of views, H-bonding discotic
liquid crystals and organic gels have similarity, and it has demon-
strated that organic gelation improved the light emitting properties
and charge carrier mobility of discotic triphenylene derivatives
[29,37].
In this paper, we synthesize a series of triphenylene derivatives,
C18H6(OC6H13)4(OCH2CONHR)2, which contain amide functional
group at 2,7-positions. The polarity, size and length of the peripheral
chains have been modified, and these compounds showed stable hexa-
gonal columnar mesophases. Further more, these discogens formed
stable organic gel in some hydrocarbon organic solvents, and these
behaviors are explained with the intermolecular hydrogen bonding
among the discotic molecules. The synthetic route of target molecules
is shown in Schemes 1 and 2.
2. RESULTS AND DISCUSSION
2.1. Synthesis
Triphenylene derivatives are well known discotic liquid crystals,
and its synthetic methodology has been well developed. In most case,
these synthetic methods can be divided into three categories [38]:
(1) terphenyl route; (2) benzene and biphenyl route; (3) statistic route.
The benzene and biphenyl route is longer than others, however it has
better selectivity, therefore it is favorite to synthesis triphenylene
derivatives with multiple functional groups. In this report, we use
benzene and biphenyl route preparing the target molecules. See
Schemes 1 and 2.
In this report, the key triphenylene intermediate, 7 synthesized
by oxidative coupling of 1,2-bis(hexyloxy)benzene (6) and 3,30-Bis
(hexyloxy)-4,40-dimethoxy-biphenyl (5). The tetraalkoxybiaryls
usually synthesized from homo-coupling of aryl halides in presence
of a stoichiometric amount of copper, called Ullmann reaction. High
temperature and more active copper of Ullmann coupling often
resulted in low yield. In this synthesis, copper has been replaced by
palladium, zinc and aqueous solution of KOH, and this modification
makes the reaction very simple and reduces the reaction time to only
7–10 h and the palladium catalyst can be recycled. It is noted that in
this synthetic route, compound 2 was prepared in low yield (34%), as
compound 1 is not electron-rich enough in the iodization reaction,
and the electron-donating ability of methoxy group in 1 is weaker than
that of other alkoxyl group, such as hexyloxy.

64/[806]
Y. F. Bai et al.
All the synthesized compounds were characterized with 600 MHz
1H NMR, elemental analysis, high resolution Mass and the analytical
data are concordant with their chemical structures.
In order to obtain information about hydrogen bonding and self-
assembled structures of triphenylene derivatives, FT-IR spectra were
measured. IR spectra of compound 9, 10d, 10h, 10i were recorded at
room temperature using dry powder samples in KBr. For 10d,
n(N-H) is 3315 cmꢀ1 and n(C¼O) is 1660 cmꢀ1; for 10h n(N-H) is
3315 cmꢀ1 and n(C¼O) is 1651 cmꢀ1; for 10i n(N-H) is 3408 cmꢀ1 and
n(C¼O) is 1663 cmꢀ1; for 9 n(C¼O) is 1768 cmꢀ1. Compared with the
literature reported value [7,31], weak to medium strength intermole-
cular H-bonds exist in the amide containing triphenylenes.
2.2. Mesomorphism
The phase transition temperatures and enthalpy changes of the
synthesized triphenylene derivatives were studied with differential
scanning calorimetry (DSC), and the results are drawn in Figure 2
and summarized in Table 1. The optical textures of the mesophases
were observed and recorded with a heating plate polarized optical
microscopy (POM) and typical photomicrographs showed in Figure 1.
POM studies has revealed that, when powder sample in thin
untreated glasses was first heated to isotropic liquid and then cooled
slowly, compound 9, 10b – 10f formed the typical fan shaped texture
of hexagonal columnar mesophases, compound 10h and 10i formed
the same texture just in cooling run, and for compound 10a and
10g, no mesophase optic texture was observe. These compounds
showed very big domains or homeotropic alignment behaviors, and
are suitable for charge carrier mobility measurement and electronic
devices manufacture.
DSC analysis showed that these triphenylene derivatives have only
one mesophase (Colh phase). The melting points of compound 10a to
10g gradually decreased with the amide tail lengthening at first,
and increased after n > 4. The clearing points showed the reverse
trend. 10d displayed the widest mesophase range, about 88ꢁC, among
these compounds. 10h and 10i had monotropic mesomorphism, and the
mesophase rang only about 27ꢁC. The phase diagram of 10a – 10g are
drawn in Figure 3.
The chemical structure of 10h has polar hydroxyl group at the end
of amide chain, and 10i possesses bulk benzyl group at the terminal of
amide group, it is obvious that the large size and polar substituents
destabilize and disturb the columnar organization of triphenylene
derivatives. It should be the same reason that 10a and 10g did not

65=[807]

66/[808]
Y. F. Bai et al.
FIGURE 1 POM photographs of triphenylene derivatives. All photos taken in
the slowly cooling run from isotropic liquid: (A) 9, 105ꢁC, Colh phase; (B) 10d,
119ꢁC, with shearing; (C) 10d, 132ꢁC, Colh phase; (D) same with (c), two
parallel polarizers.
show mesomorphism, as the amide chain is too short to 10a (methyl
group), and too long to 10g (dodecyl group). These two compounds
showed polymorphism, they have two crystal phases but obviously
not liquid crystal phase under POM. In contrast, the melting points
of all amide containing triphenylene derivatives 10, are higher than
that of 9, which contains ester functional groups. It has reported that
the melting and clearing points increased with the number of amide
containing tail increasing [31,32]. To the triphenylenes, C18H6
(OC6H13)x(OCH2CO NHBu)6-x, melting points increasing is more
obvious than that of clearing points.
2.4. Gelation Test
The gelation tests have been done (see Fig. 4) and results summarized
in Table 2. 10d can form gels in octane, petroleum ether, cyclohexane
and p-xylene, but can not form gels in the solvents such as toluene,
acetone, CHCl3. 10h and 10i with polar and bulky peripheral groups
respectively did not form organogel. This demonstrates that weak to

Synthesis of Amide Group Containing Triphenylene
67/[809]
FIGURE 2 DSC traces of triphenylene derivatives. (A) heating run of 10a –
10 g, 2,7-C18H6(OC6H13)4(OCH2CONHR)2, R ¼ CnH2nþ1; (B) cooling run of 9,
10h, 10i.
medium, not strong H-bonding in the amide group containing
triphenylene derivatives. The IR and gelling test arrives the same
conclusion.
The organogel aggregate structure of 10d can be visualized by SEM
observations. The SEM images of the xerogels obtained from 10d in
cyclohexane and petroleum ether showed very long fibrous ribbons
with 10–20 mm in diameters or sponge-like plates (Fig. 5). The primary
experiments show that the morphology of the supramolecular assem-
bly can be controlled by organic solvent selection or evaporation rate
of organic solvents.
The supramolecular assembly to discotic columns or organic gel by
intra-columnar intermolecular hydrogen bonds of amide groups has
been demonstrated in Figure 6.

68/[810]
Y. F. Bai et al.
FIGURE 3 Phase diagraph of triphenylene discogens 10a – 10g, 2,7-C18H6
(OC6H13)4(OCH2CONHR)2, R ¼ CnH2nþ1
.
FIGURE 4 The photograph of organic gels formed by 10d, 2,7-C18H6
(OC6H13)4(OCH2CONHC4H9)2 in different organic solvents.

Synthesis of Amide Group Containing Triphenylene
69/[811]
TABLE 2 Organic Solvents Tested for Gelation by 10d, 10g, 10h, and 10i
(4 ꢂ 10ꢀ3 mol=L)
hexane petroleum ether cyclo-hexane p-xylene toluene acetone Chloroform
10d
10g
10h
10i
G
G
I
G
G
I
G
PS
I
PG
PS
I
S
S
S
S
S
S
S
S
S
S
S
S
I
I
I
I
PS, poor solution; I, insoluble; S, soluble; G, gelation; PG, partial gelation.
FIGURE 5 Scanning electron micrographs of the xerogel. (A), 10d from
cyclohexane; (B), 10d from petroleum ether.
FIGURE 6 Hydrogen bonds anchor the columnar organization resulted in
more ordered Colh mesophase and organic gel.

70/[812]
Y. F. Bai et al.
3. CONCLUSION
A series of triphenylene derivatives which containing amide groups at
2,7-position has been synthesized. 10a and 10g did not show any
mesomorphism as their two amide peripheral chains too short or too
long, Most of the compounds with alkyl chain exhibit enantiotropic
hexagonal columnar mesophase, and the compound with –C2H4OH
and –CH2Ph just exhibit monotropic mesophase. The melting points
of compound 10a – 10g gradually decrease accompany with the length
of tail group at first, and increase after butyl. The clearing points
showed the reverse trend. As 10d has six almost equal length periph-
eral chains, and therefore better molecular symmetry, it exhibits the
widest mesophase temperature rang among all the compounds, about
88ꢁC. IR spectra, gelation tests have demonstrated the intermolecular
hydrogen bond exists among the triphenylene derivatives. The inves-
tigation for the influence of hydrogen bond interactions on the charged
carrier mobility of functionalized triphenylene discogens is underway.
4. EXPERIMENTAL
Instrumentation
1H NMR (600 MHz) spectra were recorded with Bruker-Avance-600,
using CDCl3 as solvent and Me4Si as internal standard. IR spectra
were obtained with KBr pellets using NICOLETMX-IE FT-IR. The
elemental analysis was performed with Carlo Erba 1106. The high
resolution Mass were recorded on Varian 7.0 T FTICR-MS (MALDI
mode). Melting points, clearing points, phase transition enthalpies
were measured using differential scanning calorimetry (DSC) on
TA-DSC Q100 system, with heating and cooling rate of 10ꢁC minꢀ1
.
Phase transition enthalpies were transferred into kJ molꢀ1, entropy
changes transferred into J molꢀ1 Kꢀ1. The mesophase textures were
observed and recorded using polarizing optical microscopy (POM)
XP-201, with a hot stage XP-201.
Chemicals and Synthesis
All chemicals are commercial products and used without further
purification.
2-Methyloxyphenyl Acetate, 1
Acetyl chloride (49 g, 0.62 mol) was slowly added to the guaiacol
(59.5 g, 0.48 mol) in 30 min, and the mixture was stirred for further
24 h at room temperature. Dichloromethane was added and the

Synthesis of Amide Group Containing Triphenylene
71/[813]
solution was washed with aqueous potassium carbonate until the
aqueous layer was basic. The organic layer was dried with anhydrous
magnesium sulfate, and the organic solution was removed under
vacuum. Distillation of the residue at 110–120ꢁC at 7.6 mmHg
afforded product as light yellow oil (68.5 g, 86%).
2-Methyloxy-5-iodophenyl Acetate, 2
The compound 1 (28.5 g, 171.87 mmol) was added to the mixture of
iodine (17.46 g, 68.75 mmol), HIO3 (7.18 g, 40.8 mmol), glacial acid
(190 ml), chloroform (50 ml), water (65 ml) and concentrated sulfuric
acid (2 ml), the mixture was stirred for 24 h at 40ꢁC. Then 50 mL
chloroform and 30 mL water was added. The mixture was washed with
dilute NaHSO3 solution three times, then by water one time. The
organic layer was dried with magnesium sulfate, and the organic
solvent was removed under vacuum. Recrystallization from ethanol
afforded the product as white crystal (17.06 g, 34%).
2-Methyloxy-5-iodophenol, 3
The compound 2 (15.7 g, 53.77 mmol) was dissolved in the solution
of potassium hydroxide (18.14 g, 0.324 mol) in the mixture of ethanol
(80 mL) and water (60 mL). The mixture was refluxed for 2 h, then
cooled to room temperature, acidified with 10% (V=V) hydrochloric
acid. The mixture was extracted with dichloromethane three times,
and the organic layer was dried with magnesium sulfate, then solvent
was removed under vacuum. Recrystallization from light petroleum
afforded product as white crystal (10.5 g, 78%).
2-Hexyloxy-4-iodoanisole, 4
BrC6H13 (10.3 g, 62.4 mmol) and the compound 3 (13 g, 52 mmol)
were added to the mixture of potassium carbonate (10.76 g, 78 mmol)
in ethane (100 mL), the mixture was refluxed 12 h, then cooled to room
temperature. Dichloromethane (50 mL) was added to the mixture and
solid was filtered off. The filtrate was concentrated under vacuum.
Recrystallization from ethanol afforded product as white crystal
(15.7 g, 90%).
3,30-Bis(hexyloxy)-4,40-dimethoxybiphenyl, 5
10% Pd=C (3.96 g), Zn dust (9.1 g, 140 mmol), the solution of KOH in
water (6 ml, 2 mol Lꢀ1) were added to the mixture of acetone (150 mL)
and water (60 mL), and the suspension was stirred 0.5 h, then the com-
pound 4 (15.6 g, 46.7 mmol) was added. The mixture was refluxed 10 h,
and cooled to room temperature. The solid was filtered and the filtrate
was extracted with dichloromethane. The organic layer was dried with

72/[814]
Y. F. Bai et al.
magnesium sulfate, the solvent was removed under vacuum. Recrys-
tallization from light petroleum afforded product as white crystal
(6.24 g, 64.5%).
1,2-Bis(hexyloxy)benzene, 6
Bromohexane (36.3 g, 0.22 mol), catechol (11 g, 0.1 mol) were added
to the suspension of potassium carbonate (41.4 g, 0.3 mol) and ethanol
(150 mL), and the mixture was refluxed 24 h. The solid was filtered
and the solvent was removed under vacuum. Distillation of the residue
at 152–160ꢁC at 7.6 mmHg afforded the product as yellow liquid
(22.38 g, 80.5%).
2,7-Dimethoxy-3,6,10,11-tetrakis(hexyloxy)triphenylene, 7
The compound 5 (6.21 g, 15 mmol), 6 (16.68 g, 60 mmol), anhydrous
iron (III) chloride (24.38 g, 150 mmol) and concentrated sulfuric acid
(10 drops) were added to dichloromethane (100 mL), and the mixture
was stirred 2 h at 30ꢁC. The reaction mixture was carefully poured
into the methanol (300 mL), and kept it in ice over 2 h. The resulting
solid was filtered off and washed with cold methanol. Separation from
columnar chromatography on silica afforded the triphenylene as white
crystal (7.12 g, 69%, mp: 98ꢁC).
2,7-Dihydroxy-3,6,10,11-tetrakis(hexyloxy)triphenylene, 8
Metal Li (1.07 g, 0.153 mol) was added to the solution of PPh3 (16 g,
0.0612 mol) in dry THF (150 mL), after the mixture was stirred over
1 h, t-BuCl (5.66 g, 0.0612 mol) was added by three times and refluxed
1 h. Compound 7 (7 g, 0.0102 mol) was added under the nitrogen atmo-
sphere, and stirred 2 h at room temperature. Then the reaction mix-
ture was poured carefully into the ice water, and acidified with 10%
HCl solution (100 mL), and extracted with dichloromethane. The
organic layer was dried with magnesium sulfate, and the organic sol-
vent was removed under vacuum. Purification through columnar chro-
matography on silica afforded the product as white crystal (5.83 g,
92%, mp: 186ꢁC).
Compound 9, 2,7-C18H6(OC6H13)4(OCH2COOC2H5)2
2,7-di(ethyloxycarbonylmethyloxy)-3,6,10,11-tetrakis(hexyloxy)tri-
phenylene. BrCH2COOC2H5 (652 mg, 3.9 mmol), compound 8 (858 mg,
1.3 mmol) were added to the suspension of potassium carbonate and
DMF. The mixture was heated at 120ꢁC with stirring for 12 h, poured
onto the ice water, and extracted with dichloromethane. The organic
layer was dried with magnesium sulfate, and the organic solvent was

Synthesis of Amide Group Containing Triphenylene
73/[815]
removed under vacuum. The residue recrystallization from ethanol
afforded the product as white solid (1.08 g, 89%, mp: 56ꢁC).
Compound 10d: 2, 7-C18H6(OC6H13)4(OCH2CONHC4H9)2
2,7-di(butylaminocarbonylmethyloxy)3,6,10,11-tetrakis(hexyloxy)
triphenylene. The compound 9 (83.2 mg, 0.1 mmol) was added to n-
butylamine (1.46 g, 20 mmol), and the mixture was refluxed 12 h.
The excessive n-butylamine was removed by distillation. The residue
recrystallization from ethanol and further purified by column chroma-
tography afforded the product as white solid (73 mg, 82%, mp: 77ꢁC).
1H NMR (CDCl3, TMS, 600 MHz) d: 7.85 (s, 2 H), 7.83 (s, 2 H), 7.76
(s, 2 H), 7.09 (s, 2 H), 4.74 (s, 4 H), 4.26 (t, J ¼ 6.48 Hz, 4 H), 4.23 (t,
J ¼ 6.42 Hz, 4 H), 3.39–3.42 (m, 4 H), 1.93–1.98 (m, 8 H), 1.57–1.62
(m, 8 H), 1.54–1.56 (m, 4 H), 1.38–1.44 (m, 20 H), 0.93–0.96 (m, 18
H). Anal. Calcd for C54H82O8N2: C 73.10 H 9.32 N 3.16; found C
72.97 H 9.38 N 3.18. MALDI-MS: calculated [M]þ (C54H82N2O8þ),
886.6066; found 886.6075.
Compound 10a: 2, 7-C18H6(OC6H13)4(OCH2CONHCH3)2
2,7-di(methylaminocarbonylmethyloxy)-3,6,10,11-tetrakis(hexy-
loxy)triphenylene. This compound was prepared as the method
1
described above (83%, mp: 173ꢁC). H NMR (CDCl3, TMS, 600 MHz)
d: 7.86 (s, 2 H), 7.82 (s, 2 H), 7.76 (s, 2 H), 7.14 (s, 2 H), 4.75 (s, 4
H), 4.26 (t, J ¼ 6.42 Hz, 4 H), 4.23 (t, J ¼ 6.48 Hz, 4H), 2.97 (d,
J ¼ 5.1 Hz, 6 H), 1.93–1.99 (m, 8 H), 1.57–1.62 (m, 8 H), 1.40–1.46
(m, 16 H), 0.93–0.96 (m, 12 H). Anal. Calcd for C48H70O8N2: C 71.79
H 8.79 N 3.49; found C 71.41 H 8.88 N 3.45. MALDI-MS: calculated
[M]þ (C48H70N2O8þ), 802.5127; found 802.5129.
Compound 10b: 2, 7-C18H6(OC6H13)4(OCH2CONHC2H5)2
2,7-di(ethylaminocarbonylmethyloxy)-3,6,10,11-tetrakis(hexyloxy)
triphenylene. This compound was prepared as the method described
above (86%, mp: 144ꢁC). 1H NMR (CDCl3, TMS, 600 MHz) d: 7.86
(s, 2 H), 7.83 (s, 2 H), 7.77 (s, 2 H), 7.09 (s, 2 H), 4.74 (s, 4 H), 4.26
(t, J ¼ 6.36 Hz, 4 H), 4.23 (t, J ¼ 6.6 Hz, 4 H), 3.43–3.47 (m, 4 H),
1.93–1.98 (m, 8 H), 1.59–1.60 (m, 8 H), 1.38–1.46 (m, 16 H),
1.23–1.26 (t, J ¼ 7.20 Hz, 6 H), 0.93–0.96 (m, 12H). Anal. Calcd
for C50H74 O8N2: C 72.26 H 8.07 N 3.37; found C 72.36 H 9.02 N
3.38. MALDI-MS: calculated [M]þ (C50H74N2O8þ), 830.5440; found
830.5444.

74/[816]
Y. F. Bai et al.
Compound 10c: 2, 7-C18H6(OC6H13)4(OCH2CONHC3H7)2
2,7-di(propylaminocarbonylmethyloxy)-3,6,10,11-tetrakis(hexyloxy)
triphenylene. This compound was prepared as the method described
1
above (86%, mp: 100ꢁC). H NMR (CDCl3, TMS, 600 MHz) d: 7.85 (s,
2 H), 7.83 (s, 2 H), 7.76 (s, 2 H), 7.13 (s, 2 H), 4.75 (s, 4 H), 4.26 (t,
J ¼ 6.54 Hz, 4 H), 4.23 (t, J ¼ 6.48 Hz, 4 H), 3.36–3.39 (m, 4 H),
1.93–1.98 (m, 8 H), 1.57–1.66 (m, 12 H), 1.37–1.41 (m, 16 H),
0.97–0.99 (t, J ¼ 7.5 Hz, 6 H), 0.93–0.96 (m, 12 H). Anal. Calcd for
C52H78O8N2: C 72.69 H 9.15 N 3.26; found C 72.25 H 9.19 N 3.28.
MALDI-MS: calculated [M]þ (C52H78N2O8þ), 858.5752; found 858.5759.
Compound 10e: 2,7-C18H6(OC6H13)4(OCH2CONHC6H13)2
2,7-di(hexylaminocarbonylmethyloxy)-3,6,10,11-tetrakis(hexyloxy)
triphenylene. This compound was prepared as the method described
1
above (90%, mp: 85ꢁC). H NMR (CDCl3, TMS, 600 MHz) d: 7.85 (s, 2
H), 7.83 (s, 2 H), 7.77 (s, 2 H), 7.10 (s, 2 H), 4.75 (s, 4 H), 4.26 (t,
J ¼ 6.48 Hz, 4 H), 4.23 (t, J ¼ 6.66 Hz, 4 H), 3.37–3.41 (m, 4 H),
1.93–1.99 (m, 8 H), 1.56–1.61 (m, 12 H), 1.36–1.42 (m, 20 H),
1.28–1.29 (m, 8 H), 0.93–0.96 (m, 12 H), 0.85–0.88 (t, J ¼ 6.84 Hz,
6 H). Anal. Calcd for C58H90O8N2: C 73.58 H 9.62 N 2.97; found C
73.55 H 9.65 N 2.97. MALDI-MS: calculated [M]þ (C58H90N2O8þ),
942.6692; found 942.6697.
Compound 10f: 2,7-C18H6(OC6H13)4(OCH2CONHC8H17)2
2,7-di(octylaminocarbonylmethyloxy)-3,6,10,11-tetrakis(hexyloxy)
triphenylene. This compound was prepared as the method described
1
above (90%, mp: 100ꢁC). H NMR (CDCl3, TMS, 600 MHz) d: 7.85 (s,
2 H), 7.83 (s, 2 H), 7.76 (s, 2 H), 7.09 (s, 2 H), 4.75 (s, 4 H), 4.26 (t,
J ¼ 6.42 Hz, 4 H), 4.23 (t, J ¼ 6.42 Hz, 4 H), 3.37–3.40 (m, 4 H),
1.93–1.98 (m, 8 H), 1.56–1.61 (m, 12 H), 1.39–1.42 (m, 16 H),
1.23–1.36 (m, 20 H), 0.93–0.96 (m, 12 H), 0.85–0.87 (t, J ¼ 6.78 Hz,
6 H). Anal. Calcd for C62H98O8N2: C 74.51 H 9.88 N 2.80; found C
74.67 H 9.96 N 2.78. MALDI-MS: calculated [M]þ (C62H98N2O8þ),
998.7318; found 998.7316.
Compound 10g: 2,7-C18H6(OC6H13)4(OCH2CONHC12H25)2
2,7-di(dodecylaminocarbonylmethyloxy)-3,6,10,11-tetrakis(hexyloxy)
triphenylene. This compound was prepared as the method described
above (72%, mp: 102ꢁC). 1H NMR (CDCl3, TMS, 600 MHz) d: 7.85
(s, 2 H), 7.83 (s, 2 H), 7.76 (s, 2 H), 7.09 (s, 2 H), 4.75 (s, 4 H), 4.26
(t, J ¼ 6.36 Hz, 4 H), 4.23 (t, J ¼ 6.60 Hz, 4 H), 3.37–3.40 (m, 4 H),

Synthesis of Amide Group Containing Triphenylene
75/[817]
1.93–1.99 (m, 8 H), 1.56–1.61 (m, 12 H), 1.39–1.45 (m, 16 H), 1.35–1.37
(m, 4 H), 1.32–1.33 (m, 8 H), 1.28–1.29 (m, 24 H), 0.93–0.96 (m, 12 H),
0.86–0.88 (t, J ¼ 6.96 Hz, 6 H). Anal. Calcd for C70H114O8N2: C 75.63 H
10.34 N 2.52; found C 75.54 H 10.40 N 2.50. MALDI-MS: calculated
[M]þ (C70H114N2Oþ8 ), 1110.8570; found 1110.8574.
Compound 10h: 2,7-C18H6(OC6H13)4(OCH2CONHC2H4OH)2
2,7-di(hydroxyethylaminocarbonylmethyloxy)-3,6,10,11-tetrakis(hex
yloxy)-triphenylene. This compound was prepared as the method
1
described above (88%, mp: 192ꢁC). H NMR (CDCl3, TMS, 600 MHz)
d: 7.75 (s, 2 H), 7.69 (s, 2 H), 7.64 (s, 2 H), 7.75 (s, 2 H), 4.73 (s, 4
H), 4.18–4.22 (m, 8 H), 3.81–3.84 (m, 4 H), 3.57–3.60 (m, 4 H), 2.66
(s, 2 H), 1.93–1.98 (m, 8 H), 1.57–1.63 (m, 8 H), 1.37–1.44 (m, 16 H),
0.94–0.96 (t, J ¼ 7.02 Hz, 12 H). Anal. Calcd for C50H74O10N2: C
69.58 H 8.64 N 3.25; found C 69.11 H 8.72 N 3.22. MALDI-MS: calcu-
lated [M]þ (C50H74N2O1þ0), 862.5337; found 862.5344.
Compound 10i: 2,7-C18H6(OC6H13)4(OCH2CONHCH2Ph)2
2,7-di(benzylaminocarbonylmethyloxy)-3,6,10,11-tetrakis(hexyloxy)-
triphenylene. This compound was prepared as the method described
1
above (83%, mp: 135ꢁC). H NMR (CDCl3, TMS, 600 MHz) d: 7.88 (s,
2 H), 7.76 (s, 4 H), 7.46 (s, 2 H), 7.26–7.31 (m, 10 H), 4.83 (s, 4 H),
4.59 (d, J ¼ 6.06 Hz, 4 H), 4.22 (t, J ¼ 6.48 Hz, 4 H), 4.12 (t, J ¼ 6.42 Hz,
Hz, 4 H), 1.93–1.98 (m, 4 H), 1.75–1.80 (m, 4 H), 1.57–1.62 (m, 4 H),
1.38–1.46 (m, 12 H), 1.30–1.32 (m, 8 H), 0.90–0.95 (m, 12 H). Anal.
Calcd for C60H78O8N2: C 75.44 H 8.23 N 2.93; found C 75.14 H
8.31 N 2.95. MALDI-MS: calculated [M]þ (C60H78N2O8þ), 954.5752;
found 954.5749.
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