Mesomorphic phase transition behavior of novel triphenylene compounds possessing fluoroalkylated side chains

Article abstract of DOI:10.1016/j.jfluchem.2006.04.011

This report discusses the effect of fluoroalkyl chain on the mesomorphism. Several homologues of novel triphenylene compounds possessing fluoroalkylated side chains were synthesized. Studies of X-ray diffraction, DSC and texture observations by polarized

Full text of DOI:10.1016/j.jfluchem.2006.04.011

Journal of Fluorine Chemistry 127 (2006) 954–961
www.elsevier.com/locate/fluor
Mesomorphic phase transition behavior of novel triphenylene
compounds possessing fluoroalkylated side chains
a
b
Naohiro Terasawa a, , Hirosato Monobe , Kenji Kiyohara
*
a Research Institute for Ubiquitous Energy Devices, National Institute of Advanced Industrial Science and Technology (AIST),
KANSAI, Midorigaoka 1-8-31, Ikeda, Osaka 563-8577, Japan
b Research Institute for Cell Engineering, National Institute of Advanced Industrial Science and Technology (AIST),
KANSAI, Midorigaoka 1-8-31, Ikeda, Osaka 563-8577, Japan
Received 28 February 2006; received in revised form 12 April 2006; accepted 18 April 2006
Available online 2 May 2006
Abstract
This report discusses the effect of fluoroalkyl chain on the mesomorphism. Several homologues of novel triphenylene compounds possessing
fluoroalkylated side chains were synthesized. Studies of X-ray diffraction, DSC and texture observations by polarized microscope revealed that
these homologues show hexagonal columnar (Colh) mesophase. These homologues made columnar mesophase stabilize and the melting point
increase, as compared with corresponding alkyloxytriphenylenes. In the case of fluoroalkyloxytriphenylenes possessing fluoromethylene side
chains, the increase of the fluoromethylene chain length stabilized columnar mesophase, made the phase transition enthalpy (Colh-Iso) and entropy
(Colh-Iso) increase. It is considered that these results are due to the fluorophilic interaction, and that the fluorophilic interaction is important for
stabilizing columnar mesophase.
# 2006 Elsevier B.V. All rights reserved.
Keywords: Phase transition behavior; Novel triphenylene; Fluoroalkylated side chain; Hexagonal columnar (Colh) mesophase; Fluorophilic interaction
1. Introduction
As for rod-like liquid crystals, a large number of liquid-
crystalline materials incorporating fluoroalkyl chains have been
synthesized. Among the important applications of liquid
crystals is the electrooptical display. The advantages of fluoro
substitution in low-molecular-weight liquid crystals have been
studied [1]. The argument for introducing fluorine into the
molecules centered on its high electronegativity, or strong
electron-withdrawing inductive effect, in relation to its small
size, fairy close to that of hydrogen. Therefore its presence
could be expected to exert a large influence on permittivity,
while causing minimum change in molecular shape. In general,
terminal fluoro-, trifluoromethyl-, and trifluoromethoxy-sub-
stituted mesogenic molecules have been shown to be useful by
themselves, or as additives for formulated practical mixtures
with other more conventional cyano-terminated mesogens,
because they are chemically stable and possess moderate
positive dielectric anisotropy with lower viscosity [1]. It was
reported that the fluorophilic and fluorophobic interactions
around fluoroalkyl chains enhance the mesophase thermal
stability and facilitates the formations of the smectic phase [5–
20]. Furthermore, it was reported that the combination of the
Fluorinated materials play a significant role in a variety of
fields such as polymer, plastic, coating material, surfactant,
pharmaceutical and agrochemical due to their unique properties
[1,2]. The substitution of hydrogen atom by fluorine atom
increases chemical and oxidative stability, weatherability and
melting point, while it decreases flammability, adhesion,
dielectric constant and refractive index [1], because of the
property of fluorine atom and unique physical property of C–F
bond. It is well known that the fluorinated alkanes are more
rigid than the corresponding hydrogenated alkanes, and that the
fluorophilic and fluorophobic interactions work around
fluoroalkyl and alkyl chains [1–4]. These intermolecular
interactions of fluoroalkyl chains are interesting not only for
mesophase formation but also for its functionality.
* Corresponding author. Tel.: +81 727 51 7914; fax: +81 727 51 9628.
E-mail address: terasawa-naohiro@aist.go.jp (N. Terasawa).
0022-1139/$ – see front matter # 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2006.04.011

N. Terasawa et al. / Journal of Fluorine Chemistry 127 (2006) 954–961
955
suitable length of aliphatic chain and the ratio of the
perfluorinated alkane segment to the perhydrogenated one in
the chain relates to the microsegregation at the molecular level
[21–28]. For example, (perfluorodecyl)decane shows smectic B
liquid-crystalline phase between 38 and 61 8C due to the
amphiphilic character of the molecules [23] and the bilayer of
glutamate-based amphiphiles having fluoroalkylchain shows a
lyotropic mesophase in water [27]. These strongly indicate that
fluorophilic and fluorophobic interactions are responsible for
the formation of the thermotropic and lyotropic mesophases.
On the other hand, several reports were also published on
columnar liquid crystals possessing fluoroalkyl side chains [29–
40]. For example, it was reported that all tapered building
blocks, and the self-assembly polymers (perfluorinated
methylenic groups of their alkyl tails) into tubular super-
molecular architectures show an enantiotropic hexagonal
columnar mesophase. Semifluorination of all model com-
pounds and polymers decreases the melting temperature of the
supramolecular assembly and enhances the thermal stability of
hexagonal columnar (Colh) mesophase. A further increase of
fluoromethylene chain number (from 4–8) increases both the
isotropization temperature of the Colh phase and the melting
temperature. A parallel increase of the diameter of the
supramolecular columns with the increase of fluoromethylene
chain number is observed. A mechanism for this dramatic
increase in the self-assembly process via microsegregation of
the perfluorinated and perhydrogenated parts of tapered groups
due to the fluorophobic effect has been proposed [30].
Furthermore, as for discotic liquid crystals possessing
fluoroalkyl side chains, two reports, triphenylene liquid crystal
and hexabenzocoronene liquid crystal, have been published, in
which the effect of fluoroalkyl chain on the mesomorphic
behavior is discussed [39]. In triphenylene liquid crystal report,
they showed that the temperature range of the mesophase is
strongly affected by fluorinated side chains. Substituting of one
aliphatic chain with a partially fluorinated side chain in
triphenylene mesogens with six long chains decreases the
clearing temperature, while substituting of all aliphatic chains
broadens the mesophase range. However, systematic studies
have not been shown so far for the fluorinated effect on discotic
mesomorphism.
Since the discovery of fast electronic carrier transport in
columnar mesophase, liquid crystals have been recognized as a
new class of organic semiconductor [41–45]. For example,
Haarer et al. [41] found a fast mobility (10ꢀ1 cm2 Vꢀ1 sꢀ1) of
holes in the helical columnar phase of 2,3,6,7,10,11-hexahex-
ylthiotriphenylene for discotic liquid crystals, and Hanna et al.
[42] found a fast mobility (10ꢀ2 cm2 Vꢀ1 sꢀ1) of holes and
electrons in the smectic E phase of 2-phenylbenzothiazole
derivatives for rod-like liquid crystals. In fact, recent studies on
electronic properties of columnar mesophase have revealed fast
one-dimensional transport of charged carriers [41,46,47] which
exceeds the values of magnitude for amorphous polymers such
as poly(N-vinylcarbazole) by two to three orders, which has
been applied to xerography and laser-printer as photoimaging
materials. Thus, the liquid crystals are recognized as a new
class of organic semiconductor that exhibits self-organization
and fluidity [48] and are expected to be used for electronic
devices. This characteristic property of mesophase is poten-
tially applicable in the areas of EL devices, information storage,
sensors and high-resolution xerography. The improvement of
carrier mobility due to the stabilization of columnar structure
could be expected if the triphenylene side chains are modified
by fluoroalkyl chains.
Recently, two homologues of novel triphenylene derivatives
possessing fluoroalkyl chains (2,3,6,7,10,11 hexakis(1H,1H,2H
,2H,3H,3H-perfluorobutyloxy)-triphenylene (F1) and 2,3,6,7,
10,11-hexakis(1H,1H,2H,2H,3H,3H-perfluorononyloxy)triphe-
nylene (F6) in Scheme 1) were synthesized and they showed the
hexagonal columnar (Colh) mesophase. Those fluoroalkyloxy-
triphenylenes have stabilized the columnar mesophase and
increased the melting point, compared with corresponding
alkyloxytriphenylenes. The mesomorphic behavior is obviously
different from those of the corresponding hydrocarbon homo-
logues (H1 and H6 in Scheme 1). Interestingly, it was found that
F1showsadisorderedColh phase, thoughH1formsonlyaplastic
hexagonal columnar (Colhp) mesophase [49].
In this work, novel triphenylene compounds possessing
fluoroalkylchains (Fn in Scheme 1) were synthesized and
investigated on their mesomorphism in order to discuss the
difference of mesomorphism to the corresponding hydrocarbon
mesogens (Schemes 2 and 3).
Scheme 1. Structures of triphenylene compounds possessing fluoroalkylated side chains (n = 1, 2, 3, 4, 6) and alkyl side chains.

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N. Terasawa et al. / Journal of Fluorine Chemistry 127 (2006) 954–961
Scheme 2. Synthesis of triphenylene compound possessing fluoroalkylated side chains (n = 1).
Scheme 3. Synthesis of triphenylene compounds possessing fluoroalkylated side chains (n = 2, 3, 4, 6).
2. Results and discussion
The phase transition behavior of fluoroalkyloxytripheny-
lenes (Fn) and alkyloxytriphenylenes (Hn) are given in Table 1.
All fluoroalkyloxytriphenylenes stabilized columnar meso-
phase and made the melting point increase, as compared with
corresponding alkyloxytriphenylenes. The increase of the
fluoromethylene chain length stabilized the columnar meso-
phase in the same way as the case of rod-like liquid crystals
possessing fluoroalkyl chains, because of the fluorophilic
interaction around the fluoromethylene chain [17]. While, the
increase of the methylene chain length did not stabilize the
columnar mesophase, it was suggested fluorophilic interaction
did not work around the methylene chain and was important for
stabilizing for the columnar mesophase. In the case of
fluoroalkyloxytriphenylenes possessing fluoromethylene side
chains (F2–F6), the thermal stability of columnar mesophase
for the fluoromethylene side chains showed the opposite
tendency for the methylene side chains (Table 1).
A typical texture observed by microscope under crossed
polarizer for these homologues is shown in Fig. 1. This texture
(F2) is very similar to the known texture (focal conic texture)
for Colh mesophase.
Phase transition parameters of fluoroalkyloxytriphenylenes
(Fn) and alkyloxytriphenylenes (Hn) were shown in Table 1.
Fn showed enatiotropic mesopahse.
The phase transition enthalpies (Colh-Iso) of Fn and Hn are
given in Table 1. In the case of F2–F6, the increase of the
fluoromethylene chain length made the phase transition enthalpy
(Colh-Iso) increase in the same way as the case of rod-like liquid
crystalspossessingfluoroalkylchains, becauseofthefluorophilic
interaction around the fluoromethylene chain. While, the
increase of the methylene chain length made the phase transition
enthalpy (Colh-Iso) decrease, it was supported that fluorophilic
Fig. 1. Textures of fluoroalkyloxytriphenylenes (F2) (120 8C).

N. Terasawa et al. / Journal of Fluorine Chemistry 127 (2006) 954–961
957
Table 1
Phase transition parameters of fluoroalkyloxytriphenylenes (Fn) and alkylox-
ytriphenylenes (Hn)
Compound
Transition
Temperature
DH
(kJ molꢀ1
DS
(J molꢀ1 Kꢀ1
)
(8C)
)
F1
C ! Colh
132
171
22.1
4.7
54.5
10.6
Colh ! Iso
H1a
F2
C ! Colhp
87
24.7
20.5
68.6
49.1
Colhp ! Iso
144
C ! Colh
126
150
44.4
3.4
111.2
8.0
Colh ! Iso
H2
C ! Colh
66
35.4
9.6
104.4
23.7
Colh ! Iso
122
F3
C ! Colh
130
149
48.0
3.7
119.2
8.8
Colh ! Iso
Fig. 2. X-ray diffraction pattern of fluoroalkyloxytriphenylene (F1).
H3
C ! Colh
67
99
39.2
5.5
115.3
14.8
Colh ! Iso
interaction did not work around the methylene chain and was
important for making the phase transition enthalpy (Colh-Iso)
increase. The phase transition enthalpy (Colh-Iso) for the
fluoromethylene side chains showed the opposite tendency for
the methylene side chains. This indicates that motion of
triphenylene side chains restricts on columnar mesophase
because of the fluorophilic interaction around the fluoromethy-
lene chain. On the other hand, the trifluoromethyl groupmadethe
phase transition enthalpy (Colh-Iso) decrease (F1) from that of
methyl group. This indicates that compound H1 forms a so-
called plastic hexagonal columnar phase (Colhp) [50]; while
compound F1 cannot form Colhp because of introducing
trifluoromethyl group in triphenylene side chain.
F4
C ! Colh
116
157
55.1
4.0
141.5
9.4
Colh ! Iso
H4
C ! Colh
64
89
56.5
4.4
167.6
12.1
Colh ! Iso
F6
C ! Colh
89
55.2
5.2
152.6
11.4
Colh ! Iso
183
H6
C ! Colh
56
77
72.9
2.7
221.5
7.7
Colh ! Iso
a
Colhp: plastic hexagonal columnar phase.
Fig. 3. X-ray diffraction patterns of fluoroalkyloxytriphenylenes (Fn) and alkyloxytriphenylenes (Hn).

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N. Terasawa et al. / Journal of Fluorine Chemistry 127 (2006) 954–961
The phase transition entropies (Colh-Iso) of Fn and Hn are
patterns are shown in Fig. 2 and Fig. 3. The assignments of
reflections are given in Table 2. In the low-angle region, three or
four sharp peaks are seen and the d-spacings are in the ratio of
given in Table 1. The phase transition entropy shows the same
tendency as the case of the phase transition enthalpy.
The X-ray diffraction measurements for fluoroalkyloxytri-
phenylenes (Fn) were carried out. The X-ray diffraction
pffiffiffi
pffiffi
pffiffi
d1 0 0 : d1 1 0 : d2 0 0 : d2 1 0 ¼ 1 : 1= 3 : 1= 4 : 1= 7. This is a
typical set of reflection for hexagonal arrangement of
molecules. In the wide-angle region of F2–F6, two diffused
Table 2
˚
reflections are seen, centered at ca. 4.1–4.2 A, which
corresponds to the liquid-like order of the hydrocarbon
The assignments of X-ray diffractions of fluoroalkyloxytriphenylenes (Fn) and
alkyloxytriphenylenes (Hn)
˚
aliphatic chains [51] and at ca. 5.2–5.3 A, which corresponds
˚
ahex (A)
˚
dh k l (A)
Compound
h k l
to the disordered perfluoroalkyl chains [21–23,30]. This
indicates that intracolumnar order exists for fluoroalkyl chains
which are close to each other. This considers to supports that the
increase of the fluoromethylene chain length stabilizes
columnar mesophase, makes the phase transition enthalpy
(Colh-Iso) and entropy (Colh-Iso) increase for the fluorophilic
interaction. While, in the case of F1, only one broad reflection
F1 (125 8C)
18.2
1 0 0
1 1 0
2 0 0
15.8
9.1
7.9
4.1 (broad)
F2 (110 8C)
F3 (180 8C)
F4 (140 8C)
20.1
1 0 0
1 1 0
2 0 0
17.4
10.0
8.6
˚
centered at ca. 4.1 A, which corresponds to the liquid-like order
5.3 (broad)
4.2 (broad)
of the hydrocarbon aliphatic chains [51]. There is no observed
distinct order of trifluoromethyl group in spite of introducing
trifluoromethyl group in triphenylene side chain.
21.5
23.7
1 0 0
1 1 0
2 0 0
18.6
10.6
The X-ray diffraction measurements for alkyloxytripheny-
lenes (Hn) were carried out. In the case of H2–H6, in the low-
angle region, three or four sharp peaks are seen and the d-
spacings are in the ratio of d1 0 0 : d1 1 0 : d2 0 0 : d2 1 0
9.3
5.3 (broad)
4.2 (broad)
1 0 0
1 1 0
2 0 0
2 1 0
20.6
pffiffi
pffiffiffi
pffiffi
11.8
¼ 1 : 1= 3 : 1= 4 : 1= 7. This is a typical set of reflection
for hexagonal arrangement of molecules. While, in the case of
compound H1, as in previous report, the X-ray reflections
pattern showed the formation of a so-called plastic hexagonal
columnar phase (Colhp) and the three-dimensional crystal-like
registry of ordered columns in a hexagonal lattice formed [50].
In the case of F1, it is not allowed because of introducing
trifluoromethyl group in triphenylene side chain. In the wide-
angle region of H2–H6, H2 showed broad and sharp
10.1
7.6
5.3 (broad)
4.2 (broad)
F6 (80 8C)
26.1
19.2
1 0 0
1 1 0
2 0 0
2 1 0
22.6
13.0
11.4
8.5
5.2(broad)
4.1(broad)
˚
reflections, one broad reflection centered at ca. 4.2 A
corresponding to the liquid-like order of the aliphatic
hydrocarbon chains [51] and another sharp reflection centered
H1 (115 8C)
1 0 0
16.6
9.5
1 1 0
2 0 0
8.2
˚
at ca. 3.6 A corresponding to the stacking periodicity of the
2 1 0
6.3
core part [52], but the three-dimensional crystal-like registry of
ordered columns in a hexagonal lattice could not form
differently from H1. While, F2 did not show sharp reflection
centered at ca. 3.6 A. This indicates that hexagonal ordered
columns are not allowed because of introducing fluoroalkyl
2 2 0/2 1 1
4.7
4.2(broad)
3.5
0 0 2
1 0 2
3.4
˚
H2 (100 8C)
20.6
1 0 0
2 0 0
2 1 0
17.8
8.9
chain of triphenylene side chains. H3–H6 showed only one
˚
broad reflection centered at ca. 4.2 A, which corresponded to
6.7
4.2(broad)
3.6(broad)
the liquid-like order of the hydrocarbon aliphatic chains [51],
different from the case of two broad reflections of F3–F6.
Scheme of Colh phase of F2–F6 is indicated in Fig. 4. As
H3 (80 8C)
H4 (75 8C)
H6 (45 8C)
22.0
23.0
25.2
1 0 0
1 1 0
2 0 0
19.0
10.9
˚
F2–F6 centers at ca. 5.2–5.3 A, which corresponds to the
9.4
4.2(broad)
disordered perfluoroalkyl chains [21–23,30], it is suggested that
that F2–F6 are the packing of peripheral fluoroalkyl chain.
Therefore, it is suggested that fluorophilic interaction works
around the fluoromethylene chain. And as F2–F6 does not show
1 0 0
1 1 0
2 0 0
19.8
11.5
9.8
4.2(broad)
˚
sharp reflection centered at ca. 3.6 A corresponding to the
1 0 0
1 1 0
2 0 0
21.9
stacking periodicity of the core part [52], it is suggested that
hexagonal ordered columns is not allowed because of
introducing fluoroalkyl chain of triphenylene side chains.
12.6
10.8
4.2(broad)
˚
While, as for F1, there is no reflection of ca. 5.2–5.3 A in spite

N. Terasawa et al. / Journal of Fluorine Chemistry 127 (2006) 954–961
959
chain length (n) are shown in Fig. 5. The lattice constant ahex of
Fn showed similar values corresponding to those of Hn. In the
case of Fn, it was found that the increase of lattice constant is
˚
proportional to the increase of chain length (n) (ca. 1.6 A/n).
But this increase in column diameter is not sufficient to account
˚
for ca. 3.2 A increase of fluoromethylene chain length (n)
˚
(–CF2CF2– bond length: 1.58 A). The increase rate of diameter
˚
˚
of Fn (ca. 1.6 A/n) is bigger than that of Hn (ca. 1.2 A/n).
The difference of increase rate is considered as due to the longer
˚
–CF2CF2– bond length (1.58 A) compared to the –CH2CH2–
˚
bond length (1.54 A). Another factor, such as the increased
rigidity of fluroalkyl segments can be considered to contribute
as well.
3. Conclusions
Novel triphenylene compounds possessing fluoroalkylated
side chains were synthesized. The X-ray diffraction, DSC
measurements and the texture observations by polarized
microscope showed that these homologues are thermotropic
liquid crystals with hexagonal columnar (Colh) mesophase. All
fluoroalkyloxytriphenylenes stabilize columnar mesophase and
make the melting point increase, compared with corresponding
alkyloxytriphenylenes. In the case of fluoroalkyloxytripheny-
lenes possessing fluoromethylene side chains, the thermal
stability of columnar mesophase, the phase transition enthalpy
(Colh-Iso) and entropy (Colh-Iso) for the fluromethylene side
chains show the opposite tendency for the methylene side
chains. The fluorophilic interaction around the fluoromethylene
chain plays a significant role for the thermal stability of
columnar mesophase.
Fig. 4. Scheme of Colh phase of fluoroalkyloxytriphenylenes (Fn).
of introducing trifluoromethyl group in triphenylene side chain
˚
and there is no reflection of ca. 3.6 A. There is only reflection,
˚
centered at ca. 4.1 A corresponding to the liquid-like order of
the aliphatic hydrocarbon chains [52].
Dependence of the lattice constant for Fn and Hn on the
number of fluoromethylene chain length (n) and methylene
4. Experimental
4.1. General methods
As for the identification of compounds, 1H NMR
(500.0 MHz) and 19F NMR (376.1 MHz) spectra were obtained
on JEOL ALPHA-500 and JEOL JNM-AL400 FT-NMR
spectrometers, respectively. MALDI-TOF mass spectra were
also measured on a Applied Biosystems/Voyager TM DE STR-
D1 spectrometer. IR spectra were obtained for KBr pellets by a
Perkin–Elmer Paragon 1000 FT-IR spectrometer. UV–vis
spectra were recorded on a Shimadzu UV-2500PC spectrometer.
The phase transitions and enthalpies were detected by a
differential scanning calorimeter (TA Instrument, 2920 MDSC)
and the textures of mesophase were observed by a polarizing
microscope (Olympus, BH-2) equipped with a hot stage
(Mettler, FP82HT). X-ray diffraction studies were carried out
by a Rigaku Geigerflex X-ray diffractometer (Cu Ka) with a
hand-made ho stage.
4.2. Synthesis
All materials used are commercially available and were used
without further purification. The syntheses of compounds F2–
F6 were carried out by the method in the literature [53].
Fig. 5. Dependence of the lattice constant for fluoroalkyloxytriphenylenes (Fn)
and alkyloxytriphenylenes (Hn) on the number of fluoromethylene chain length
(n) and methylene chain length (n).

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N. Terasawa et al. / Journal of Fluorine Chemistry 127 (2006) 954–961
4.2.1. 2,3,6,7,10,11-hexakis(1H,1H,2H,2H,3H,3H-
perfluorobutyloxy)triphenylene (F1)
4.2.4. 2,3,6,7,10,11-hexakis(1H,1H,2H,2H,3H,3H-
perfluoroheptyloxy)triphenylene (F4) (0.84 g, 22.3%)
1H NMR (CDCl3, TMS, 500.0 MHz) d 2.21–2.28 (m, 12H),
A
mixture of 2,3,6,7,10,11-hexahydroxytriphenylene
(0.648 g, 2.0 mmol), 1-bromo-4,4,4-trifluorobutane (3.82 g,
20 mmol), K2CO3 (2.76 g, 20 mmol) and EtOH (50 ml) was
refluxed for 19 h. The solvent was evaporated in vacuo and the
residue was resolved with CH2Cl2. The organic layer was
separated and the solvent was evaporated in vacuo. The crude
product was purified by column chromatography (silica gel, n-
hexane: ethyl acetate = 8:2, Rf = 0.20) and the recrystallization
from EtOH gave the product (0.85 g, 43.2%).
2.37–2.51 (m, 12H), 4.31 (t, J = 5.8 Hz, 12H), 7.82 (s, 6H); 19
F
NMR (CDCl3, CFCl3, 376.1 MHz) d ꢀ81.7 (t, J = 9.2 Hz, 18F),
ꢀ115.0 to ꢀ115.2 (m, 12F), ꢀ125.0 (s, 12F), ꢀ125.6 (t,
J = 12.2 Hz, 12F); MS m/z = 1884.6 (calcd. 1884.2 for
C60H42F54O6); FTIR (KBr, cmꢀ1) 1520, 1442, 1269, 1226,
1176, 1134, 1032, 722; UV–vis (CHCl3) lmax, nm (emax
,
l molꢀ1 cmꢀ1) 345 (3800), 307 (26,900), 278 (115,000), 269
(79,200); Anal Calcd. for C60H42F54O6: C,38.23; H, 2.25; F,
54.43; Found: C, 37.98; H, 2.16; F, 54.53.
1H NMR (CDCl3, TMS, 500.0 MHz) d 2.17–2.24 (m, 12H),
2.38–2.50 (m, 12H), 4.29 (t, J = 6.0 Hz, 12H), 7.81 (s, 6H); 19
F
NMR (CDCl3, CFCl3, 376.1 MHz) d ꢀ66.8 (t, J = 10.7 Hz,
18F); MS m/z = 984.7 (calcd. 984.3 for C42H42F18O6); FTIR
(KBr, cmꢀ1) 1520, 1439, 1386, 1341, 1255, 1231, 1175,
4.2.5. 2,3,6,7,10,11-hexakis(1H,1H,2H,2H,3H,3H-
perfluorononyloxy)triphenylene (F6) (0.74 g, 30.6%)
1H NMR (CDCl3, TMS, 500.0 MHz) d 2.20–2.28 (m, 12H),
1154, 1133, 1062, 1030; UV–vis (CHCl3) lmax, nm (emax
,
2.36–2.50 (m, 12H), 4.30(t, J = 5.8 Hz, 12H), 7.81 (s, 6H); 19
F
l molꢀ1 cmꢀ1) 345 (3600), 306 (25,700), 278 (111,000), 269
(76,600); Anal Calcd. for C42H42F18O6: C,51.23; H, 4.30; F,
34.73; Found: C, 51.16; H, 4.28; F, 34.53.
NMR (CDCl3, CFCl3, 376.1 MHz) d ꢀ81.4 (t, J = 10.0 Hz,
18F), ꢀ114.8 to ꢀ115.2 (m, 12F), ꢀ122.5 (s, 12F), ꢀ123.5 (s,
12F), ꢀ124.0 (s, 12F), ꢀ126.6 to ꢀ126.9 (m, 12F); MS m/
z = 2484.4 (calcd. 2484.2 for C72H42F78O6); FTIR (KBr, cmꢀ1
)
1520, 1442, 1266, 1236, 1191, 1146, 1034, 698; UV–vis
(CHCl3) lmax, nm (emax, l molꢀ1 cmꢀ1) 345.0 (3900), 306.5
(26,300), 278.0 (112,000), 268.5 (77,600); Anal Calcd. for
C72H42F78O6: C, 34.80; H, 1.70; F, 59.63; Found: C, 34.62; H,
1.53; F, 59.39.
4.2.2. 2,3,6,7,10,11-hexakis(1H,1H,2H,2H,3H,3H-
perfluoropentyloxy)triphenylene (F2)
2,3,6,7,10,11-hexahydroxytriphenylene (0.648 g, 2.0 mmol)
was added to a suspension of sodium hydride (0.576 g,
24.0 mmol) in dry DMF (30 ml) at room temperature. After
stirring for 1.5 h, 1H,1H,2H,2H,3H,3H-perfluoropentyl-p-
toluenesulphonate [54] (4.65 g, 14.0 mmol) was added. The
mixture was then heated to 130 8C and stirred for 17 h. After
cooled to room temperature, water was added into the reaction
mixture. The product was extracted by ether and the organic
layer was washed by 0.5N-HCl aq. and brine. The crude
product was purified by column chromatography (silica gel, n-
hexane: ethyl acetate = 85:15, Rf = 0.22). The recrystallization
from n-hexane gave the product. (0.54 g, 21.0%)
Acknowledgements
We thank Dr. T. Nakamura and Dr. N. Yumoto for measuring
MALDI-TOF mass spectra.
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