Synthesis and characterization of triphenylene-dione half-disc mesogens

Article abstract of DOI:10.1080/15421400490435396

Novel half-disc mesogens of general structure 6,7,10,11-tetrakis(alkoxy) triphenylene-1,4-dione wem synthesized and their phases characterized by polarized microscopy, differential scanning calorimetry and X-ray diffraction. These compounds were found to

Full text of DOI:10.1080/15421400490435396

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Synthesis and Characterization
of Triphenylene-Dione Half-Disc
Mesogens
Alexander Paraskos a , Yutaka Nishiyama a & Timothy
Swager a
a Department of Chemistry and Center for Materials
Science and Engineering , Massachusetts Institute of
Technology , Cambridge, MA, USA
Published online: 18 Oct 2010.
To cite this article: Alexander Paraskos , Yutaka Nishiyama & Timothy Swager (2004)
Synthesis and Characterization of Triphenylene-Dione Half-Disc Mesogens, Molecular
Crystals and Liquid Crystals, 411:1, 363-375, DOI: 10.1080/15421400490435396
To link to this article: http://dx.doi.org/10.1080/15421400490435396
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Mol. Cryst. Liq. Cryst., Vol. 411, pp. 363=[1405]–375=[1417], 2004
Copyright # Taylor & Francis Inc.
ISSN: 1542-1406 print=1563-5287 online
DOI: 10.1080=15421400490435396
SYNTHESIS AND CHARACTERIZATION OF
TRIPHENYLENE-DIONE HALF-DISC MESOGENS
Alexander J. Paraskos, Yutaka Nishiyama, and Timothy M. Swager
Department of Chemistry and Center for Materials Science and
Engineering, Massachusetts Institute of Technology, Cambridge,
MA 02139, USA
Novel half-disc mesogens of general structure 6,7,10,11-tetrakis(alkoxy)triphe-
nylene-1,4-dione were synthesized and their phases characterized by polar-
ized microscopy, differential scanning calorimetry and X-ray diffraction.
These compounds were found to form hexagonal columnar mesophases upon
heating, despite their half-disc molecular shapes. X-ray diffraction suggests
that within the mesophases a dimeric mesogenic subunit exists, driven by
dipolar forces, in which the molecules are oriented antiparallel to one another.
Such a dimer is approximately disc-shaped, and may explain the formation of
columnar phases by these half-disc molecules.
INTRODUCTION
With the discovery that disc-shaped molecules can stack and form colum-
nar mesophases a new paradigm was born for the rational design of novel
liquid crystals [1]. This discovery highlights the importance of considering
shape anisotropy and structure-property relationships when creating novel
mesogens that might potentially display new mesophases.
Since then, it has been shown that many non-discoid molecules are
capable of forming columnar mesophases as well. For example, polycatenar
mesogens frequently display columnar mesophases arising through the for-
mation of aggregates [2] or dimers [3] of molecules within the columns. The
design of metallomesogens in which half-disc subunits are brought together
covalently through a central metal atom(s) to form disc-shaped [4], propel-
ler-shaped [5], butterfly-shaped [6] and rod=half-disc shaped [7] mesogenic
We are grateful for the generous financial support from the National Science Foundation
and the Japanese Society for the Promotion of Science.
Address correspondence to Timothy M. Swager Department of Chemistry and Center for
Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA
02139, USA.
363=[1405]

364=[1406]
A. J. Paraskos et al.
units has demonstrated that unfavorably-shaped subunits can be strategi-
cally combined to form molecules which are mesogenic. The assembly of
mesogenic units through non-covalent forces such as hydrogen-bonding
[8], coordination polymers [9], microphase segregation [10] and dipole-
dipole interactions [11] has also proven effective.
Herein we describe the synthesis and phase behavior of a series of meso-
gens of general structure 6,7,10,11-tetrakis(alkoxy)triphenylene-1,4-dione.
These deep-red coloured organic dyes have been found to display hexag-
onal columnar mesophases due to a correlated organization of their shapes.
RESULTS AND DISCUSSION
Synthesis
A number of triphenylene-based quinones were synthesized and studied
(Scheme 3). The synthesis of compound 18 and has been previously de-
scribed by our group [12], and a similar synthetic route was followed for
the synthesis of compounds 14–17. Williamson ether synthesis of the
appropriate alkyl bromide with catechol affords the corresponding 1,2-
dialkoxybenzene, which is iodinated with periodic acid and iodine yielding
the 3,4-dialkoxy-1-iodobenzene [13]. Ullman coupling of the 3,4-
dialkoxybenzenes is carried out neat with copper (220ꢀC) yielding the
corresponding 3,30,4,40-tetraalkoxybiphenyl cleanly in 70–75% yield after
precipitation from CHCl3=MeOH (Scheme 1). Alternatively, etherification
of 5-iodo-2-methoxyphenol, synthesized by the previously reported method
[14], with 1-bromo-2-ethylhexane provides 2-(2-ethylhexyloxy)-4-iodo-
1-methoxybenzene in good yield after distillation. Biphenyl 7 can then be
synthesized via a zinc=palladium (0) coupling in good yields (Scheme 2).
Cyclization of the resulting biphenyl compounds with p-dimethoxybenzene
and iron (III) chloride in DCM yields the parent triphenylenes 8–13, which
are then oxidatively demethylated with cerium ammonium nitrate yielding
the desired mesogenic quinones 14–19 (Scheme 3).
Phase Behaviour
The phase behaviour of the mesogens 14–19 is listed in Table 1. Despite
their half-disc shapes, compounds 14, 15 and 16, possessing n-hexyloxy,
n-octyloxy and n-decyloxy sidechains, respectively, all exhibit enantiotro-
pic Colh mesophases as identified by polarized microscopy and X-ray
diffraction. When viewed by polarized microscopy these compounds exhibit
petal-like textures possessing features that are clearly hexagonal in nature
(Fig. 1). Compound 17, with n-dodecyloxy sidechains, exhibits a relatively

Synthesis and Characterization of Triphenylene-Dione
365=[1407]
SCHEME 1 Synthesis of 3,304,40-tetrakis(n-alkoxy)biphenyls.
narrow monotropic Colh mesophase, as does the bis(2-ethylhexyl)dimethyl
triphenylene quinone 19, which represents an unusual example of a colum-
nar phase exhibited by a triphenylene-type compound possessing only two
alkoxy sidechains. Quinone 18, possessing four 2-ethylhexyl sidechains,
exhibits a Colh mesophase at room temperature. In stark contrast to the
quinone compounds, none of the parent triphenylenes 8–13 are liquid-
crystalline, presumably as a consequence of their half-disc shapes.
XRD Studies
Variable temperature X-ray diffraction studies were performed for the
columnar phases exhibited by each of the quinones, with the exception
SCHEME 2 Synthesis of 3,30-bis(2-ethylhexyloxy)-4,4-dimethoxybiphenyl.

366=[1408]
A. J. Paraskos et al.
SCHEME 3 Synthesis of mesogenic triphenylene quinones.
of compound 16 (Table 2). The ColH phases of these compounds are all
characterized by the observation of sharp (100) peaks in the low angle re-
gion. The diffraction patterns of compounds 15 and 17 also exhibit sharp
(110) and (200) peaks, confirming the hexagonal nature of the phases.
The wide-angle regions of the diffraction patterns all display broad halos
˚
at approximately 3.5 A, corresponding to the distance between neighboring
˚
mesogens within individual columns. In addition, broad halos at 4.6 A cor-
respond to the distance between liquid-like sidechains, confirming that the
phases are indeed liquid crystalline as opposed to crystal or plastic phases.
Further analysis of the wide-angle region of compound 19 suggests an anti-
parallel (dimerized) packing of the molecules within the columns, as evi-
denced by the appearance of an additional diffuse scattering peak
˚
centered at approximately 6.9 A. (Fig. 2) This behaviour has been observed
repeatedly by our group and other groups for mesogens in which packing
and dipolar forces combine to cause an antiparallel dimer association of
molecules within both columnar [14] and lamellar phases [15]. Such dimer-
ization, most likely driven by dipole-dipole interactions (AM1 calculations
on a model compound suggest a molecular dipole of 1.27D) in combination
with the half-disc shape may explain the relative stability of the columnar
phases of these half-disc mesogens. This would also explain the lack of
mesogenicity observed for the parent triphenylenes, as these molecules
lack a significant dipole and so most likely would not possess a driving force
to organize in this fashion.
SUMMARY
A variety of triphenylene quinones were prepared and shown to exhibit
Colh mesophases. Their ability to form columnar phases despite their
half-disc shape may be explained by the formation of an antiparallel dimers

Synthesis and Characterization of Triphenylene-Dione
TABLE 1 Phase Behaviour of Triphenylene Quinones
367=[1409]
Transition temperatures (ꢀC) and enthalpies (in parentheses, kJ/mol) were determined by
DSC (10ꢀC/min) and are given above and below the arrows.
of molecules within the liquid crystal phases, which have been observed by
X-ray diffraction studies. Such a correlated organization of molecules, dri-
ven by dipole-dipole interactions, results in the formation of mesogenic
units that are roughly disc-shaped. Further supporting this idea is the fact

368=[1410]
A. J. Paraskos et al.
FIGURE 1 Polarized microscopy of the Colh phase of 15 at 111ꢀC (top) and 109ꢀC
(bottom) (both 100 Â magnification). (See COLOR PLATE XI)
that the parent triphenylene compounds, whose dipoles are apparently not
significant enough to drive an antiparallel association of molecules, are not
liquid crystalline.
EXPERIMENTAL SECTION
General
Dichloromethane was dried by passing through activated alumina columns.
Anhydrous methanol was purchased from Aldrich (sure-seal) and stored
over activated molecular sieves before use. All other chemicals were

Synthesis and Characterization of Triphenylene-Dione
TABLE 2 XRD for Compounds 14–15 and 17–19
Lattice Spacing
369=[1411]
Miller
Halos
obsd
˚
constant (A)
˚
A (calcd)
Compd
Mesophase
obsd
indices
14
Colh at 75ꢀC
19.1
20.4
24.4
20.2
17.0
16.5
100
110
200
100
110
200
100
110
200
100
110
200
100
110
200
3.5
4.5
9.5
8.3
15
17
18
19
Colh at 92ꢀC
Colh at 76ꢀC
Colh at 90ꢀC
Colh at 100ꢀC
17.7
10.3
8.9
3.5
4.6
(10.2)
(8.8)
21.1
12.2
10.6
17.5
3.7
4.6
(12.2)
(10.6)
3.7
4.6
(10.1)
(8.8)
14.7
3.5
4.6
6.9
(8.5)
(7.4)
of reagent grade and were used without further purification. 1,2-Dihexyloxy-,
1,2-dioctyloxy, 1,2-didecyloxy, 1,2-didodecyloxy and 1,2-di(2-ethylhexy-
loxy) benzenes were prepared by the alkylation of catechol with alkyl
bromide. Air and water sensitive reactions employed standard Schlenk
techniques under argon atmosphere. NMR spectra were obtained on
FIGURE 2 Proposed antiparallel stacking of mesogenic quinones in the columnar
phase.

370=[1412]
A. J. Paraskos et al.
Varian Mercury-300, Bruker DPX-400 or Varian Inova-500 spectrometers.
All chemical shifts are referenced to residual CHCl3 (7.27 ppm for 1H,
77.0 ppm for 13C). Multiplicities are indicated as s (singlet), d (doublet),
t (triplet), and m (multiplet). High resolution mass spectra were obtained
at the MIT Department of Chemistry Instrumentation facility (DCIF) on a
Finnigan MAT 8200 or on
a
Bruker Daltonics Apex II 3T
FT-ICR MS. Infrared spectra were recorded on a Nicolet Impact 410 in
KBr pellets. DSC investigations were carried out on a Perkin-Elmer
DSC-7. Optical microscopy was carried out on a Leica polarizing micro-
scope in combination with a Linkam LTS350 hotstage. X-ray diffraction
studies were carried out on samples in capillary tubes with an INEL dif-
fractometer with a 2 kW CU Ka X-ray source fitted with an INEL CPS-120
position-sensitive detector. The detectors were calibrated using a silver
behenate standard produced by Eastman Kodak.
2-(2-ethylhexyloxy)-4-iodo-1-methoxybenzene (6)
5-Iodo-2-methoxyphenol (30 g, 120 mmol) and K2CO3 (33.2 g,
240 mmol) were successively added to ethanol (150 mL) and stirred at rt.
for 0.5 h, after which 1-bromo-2-ethylhexane (23.2 g, 120 mmol) was added
to the solution and vigorously stirred at 85ꢀC for 96 h. Additional K2CO3
(8.3 g, 60 mmol) was added to the solution after stirring for 24, 48 and
72 h. Upon cooling the reaction mixture was diluted with diethyl ether
(100 mL), filtered and the remaining solids were washed with diethyl ether
(50 ml). The solvent was removed under reduced pressure; the residual
yellow oil was dissolved in hexane (200 mL) and washed with 1 M NaOH
solution (100 mL ꢁ 2) and H2O (150 ml), respectively. After drying over
MgSO4, the organic layer was concentrated under reduced pressure and
1
the residue was distilled to afford 6 as a colorless oil (37.0 g, 85%). H
NMR (CDCl3, d): 0.91 (t, J ¼ 6.3 Hz, 3H), 0.94 (t, J ¼ 6.3 Hz, 3H), (m,
J ¼ 6.3 Hz, 1H), 1.80 1.58–1.30 (m, 8H), 3.83 (s, 3H), 3.84 (d, J ¼ 6.3 Hz,
2H), 6.62 (d, J ¼ 8.7 Hz, 1H), 7.14 (d, J ¼ 2.1 Hz, 1H), 7.21(dd, J ¼ 2.1,
8.7 Hz, 1H). 13C NMR (CDCl3, d): 11.26, 14.40, 23.31, 24.00, 29.21, 30.60,
39.34, 56.35, 72.17, 82.64, 114.03, 122.10, 129.65, 149.75, 149.99.
3,30-Di(2-ethylhexyloxy)-4,40-dimethoxybiphenyl (7)
10% Pd-C (15.7 g) and Zn dust (15.7 g, 240 mmol) were added to a
mixture of acetone=H2O (1=1 800 mL), and the resulting suspension was
stirred at room temperature for 1 h after which 2-(2-ethylhexyloxy)-4-
iodo-1-methoxybenzene was added dropwise and stirred at for 48 h.
Hexane (150 ml) was added to the resulting solution and the solution
was filtered through Celit pad. The organic layer was separated, then aque-
ous layer was extracted with diethyl ether (100 mL). The combined organic
layers were washed with saturated brine (100 mL ꢁ 2), dried over MgSO4,

Synthesis and Characterization of Triphenylene-Dione
371=[1413]
and then concentrated under reduced pressure leaving a light yellow oil.
Purification by reduced distillation afforded 7 as a clear oil (16.2 g,
1
86%). H NMR (CDCl3, d): 0.92 (t, J ¼ 7.5 Hz, 6H), 0.96 (t, J ¼ 7.5 Hz,
6H), 1.27–1.51 (m, 16H), 1.85 (m, J ¼ 6.0 Hz, 2H), 3.90 (s, 6H), 3.97 (d,
J ¼ 6.0 Hz, 4H), 6.94 (d, J ¼ 9.0 Hz, 2H), 7.08 (s, 2H), 7.09 (d, J ¼ 9.0 Hz,
Hz, 2H). 13C (CDCl3, d): 11.23, 14.32, 23.29, 23.98, 29.22, 30.64, 39.43,
56.53, 72.28, 112.61, 112.73, 119.28, 134.55, 149.14, 149.34.
1,4-Dimethoxy-6,7,10,11-tetrakis(hexyloxy)triphenylene (8)
To a suspension solution of FeCl3 (1.36 g, 8 mmol) in CHCl3 (50 mL) was
added tetra(hexyloxy)biphenyl (1 mmol) dropwise added to at 0ꢀC. 1,4-
Dimethoxybenzene (0.56 g, 4 mmol) was then added and stirred at rt. for
5 h. The reaction mixture was quenched with anhydrous MeOH (30 mL)
and then stirred at r.t for 0.5 h. The solvent was removed under reduced
pressure and the residue solid was dissolved in diethyl ether (100 mL)
and H2O (70 mL). After separating of the organic layer, aqueous layer
was extracted with diethyl ether (50 mL ꢁ 2). The combined organic layers
were washed with saturated brine (100 mL ꢁ 2), dried over MgSO4 and con-
centrated under reduced pressure. The crude product was purified by col-
umn chromatography on silica gel (hexanes=CH2Cl2 2:1 eluent) to afford a
light brown solid. The solid was further purified by recrystallization from
MeOH=CHCl3 yielding 8 as white plates.1H NMR (CDCl3, d): 0.89–0.93
(m, 12 H), 1.32–1.43 (m, 16H), 1.32–1.51 (m, 8H), 1.82–1.99 (m, 8H),
3.91 (s, 6H), 4.12 (t, J ¼ 6.6 Hz, 4H), 4.17 (t, J ¼ 6.6 Hz, 4H), 7.00 (s,
2H), 7.73 (s, 2H), 9.06 (s, 2H). 13C NMR (CDCl3, d): 14.39, 22.97, 26.12,
26.15, 29.53, 29.63, 31.98, 57.43, 69.17, 69.67, 106.60, 110.50, 112.97,
122.46, 123.22, 125.48, 147.68, 148.71, 152.55. HRMS-ESI (m=z):
(M þ H)þ calcd for C44H64O6 689.4776, found 689.4760.
1,4-Dimethoxy-6,7,10,11-tetrakis(octyloxy)triphenylene (9)
1
Preparation same as for 8. H NMR (CDCl3, d): 0.89–0.93 (m, 12H),
1.32–1.42 (32H), 1.56–1.59 (m, 8H), 1.94–1.96 (m, 8H), 3.99 (s, 6H),
4.21–4.25 (m, 8H), 7.09 (s, 2H), 7.82 (s, 2H), 9.16 (s, 2H). 13C NMR
(CDCl3, d): 14.10, 14.12, 22.68, 22.69, 26.13, 29.07, 29.15, 29.31, 29.44,
31.82, 68.72, 69.00, 103.83, 109.37, 122.17, 126.60, 128.80, 137.67,
150.58, 151.05, 189.48.
1,4-Dimethoxy-6,7,10,11-tetrakis(decyloxy)triphenylene
(10)
1
Preparation same as for 8. H NMR (CDCl3, d): 0.87–0.91 (m, 12H),
1.29–1.44 (m, 48), 1.45–1.64 (m, 8H), 1.85–2.01 (m, 8H), 4.00 (s, 6H),
4.18–4.27 (m, 8H), 7.10 (s, 2H), 7.81 (s, 2H), 9.15, (s, 2H). (13C NMR

372=[1414]
A. J. Paraskos et al.
(CDCl3, d): 14.34, 22.92, 26.41, 29.51, 29.60, 29.77, 29.85, 29.92, 32.15,
57.34, 57.51, 69.20, 69.70, 106.66, 110.47, 113.05, 122.56, 123.31, 125.58,
147.82, 148.86, 152.70. HRMS-EI (m=z): (M þ H))þ calcd for C60H96O6
912.7207, found 912.7207.
1,4-Dimethoxy-6,7,10,11-tetrakis(dodecyloxy)triphenylene
(11)
1
Preparation same as for 8. H NMR (CDCl3, d): 0.89–0.93 (m, 12H),
1.28–1.56 (m, 80H), 1.94–1.96 (m, 8H), 4.00 (s, 6H), 4.21 (t, J ¼ 6.6 Hz,
4H), 4.25 (t, J ¼ 6.6 Hz, 4H), 7.10 (s, 2H), 7.81 (s, 2H), 9.15 (s, 2H). 13C
NMR (CDCl3, d): 14.45, 23.01, 26.50, 29.58, 29.69, 29.82, 29.85, 29.98,
30.04, 32.23, 57.42, 69.19, 69.69, 106.62, 110.49, 113.00, 122.47, 123.23,
125.49, 147.68, 148.73, 152.56. HRMS-ESI (m=z): (M þ Na)þ calcd for
C68H112O6 1047.8351, found 1047.8315.
1,4-Dimethoxy-6,7,10,11-tetrakis(2-ethylhexyloxy)tripheny-
lene (12)
Synthesis and characterization previously described. [11]
1,4,6,10-Tetramethoxy-7,11-di(2-ethylhexyloxy)tripheny-
lene (13)
1H NMR (CDCl3, d): 0.94 (t, J ¼ 7.2 Hz, 6H), 1.03 (t, J ¼ 7.2 Hz, 6H),
1.37–1.66 (m, 16H), 1.98 (m, J ¼ 6.0 Hz, 2H), 4.02 (s, 6H), 4.05 (s, 6H),
4.17 (d, J ¼ 6.0 Hz, 4H), 7.11 (s, 2H), 9.19 (s, 2H), 7.83 (s, 2H). 13C
NMR (CDCl3, d): 11.49, 14.44, 23.41, 24.13, 29.32, 30.87, 39.41, 56.17,
57.40, 72.23, 105.88, 110.43, 111.49, 122.39, 123.06, 125.45, 148.19,
148.60, 152.53. HRMS-ESI (m=z): (M þ H)þ calcd for C38H52O6
605.3837, found 605.3822.
6,7,10,11-Tetra(hexyloxy)triphenylene-1,4-dione (14)
To a stirred THF (60 mL) solution of 8 (1.69 g, 2.45 mmol) an H2O
solution (15 mL) of cerium (IV) ammonium nitrate (2.82 g, 5.13 mmol)
was added dropwise and stirred at room temperature for 2 h. The result-
ing solution was poured into diethyl ether (500 mL) and washed with
saturated NaHCO3 solution (100 ml ꢁ 2) followed by water (100 mL
ꢁ 3), then dried over MgSO4. The solvent was removed under the
reduced pressure, and the crude product was subsequently purified by
column chromatography on silica gel (1:1 hexanes=CH2Cl2 eluent) fol-
lowed by precipitation from CH2Cl2=MeOH yielding 14 (11.21 g,
1.83 mmol, 75%) as a deep red solid. 1H NMR (CDCl3, d): 0.89–0.93
(m, 12H), 1.38–1.43 (m, 16H), 1.49–1.60 (m, 8H), 1.95 (m, 8H), 4.22–
4.26 (m, 8H), 6.84 (s, 2H), 7.72 (s, 2H), 8.93 (s, 2H). 13C NMR (CDCl3):

Synthesis and Characterization of Triphenylene-Dione
373=[1415]
14.37, 22.95, 26.10, 29.33, 29.40, 31.93, 68.99, 69.28, 104.07, 109.58,
122.38, 126.87, 129.00, 137.87, 150.73, 151.21, 189.59. IR (KBr): 2954,
2928, 2856, 1647, 1614, 1531, 1510, 1461, 1438, 1382, 1265, 1160,
1086. HRMS-ESI (m=z): (M þ H)þ calcd for C42H58O6 659.4306, found
659.4331.
6,7,10,11-Tetra(octyloxy)triphenylene-1,4-dione (15)
1
Preparation same as for 14. H NMR (CDCl3, d): 0.89–0.93 (m, 12H),
1.32–1.43 (m, 32H), 1.49–1.62 (8H), 1.95–1.98(8H), 4.22– 4.25 (8H),
6.82 (s, 2H), 7.68 (s, 2H), 8.91 (s, 2H). 13C NMR (CDCl3, d): 14.11,
14.12, 22.68, 22.69, 26.13, 29.07, 29.15, 29.32, 29.45, 31.83, 31.84, 68.71,
68.99, 103.81, 109.35, 122.17, 126.60, 128.80, 137.67, 150.57, 151.04,
189.48. IR (KBr): 2953, 2923, 2851, 1653, 1613, 1528, 1510, 1463, 1382,
1266, 1186, 1158, 1083, 872, 823.
6,7,10,11-Tetra(decyloxy)triphenylene-1,4-dione (16)
1
Preparation same as for 14. H NMR (CDCl3, d): 0.89–0.93 (m, 12H),
1.32–1.43 (m, 48H), 1.49–1.62 (8H), 1.95–1.98(8H), 4.22–4.25 (8H), 6.82
(s, 2H), 7.68 (s, 2H), 8.91 (s, 2H). 13C NMR (CDCl3, d): 14.33, 14.34,
22.92, 26.36, 26.37, 29.31, 29.40, 29.60, 29.71, 29.73, 29.77, 29.83, 29.89,
32.15, 32.16, 69.01, 69.31, 104.22, 109.73, 122.46, 126.93, 129.09, 137.94,
150.88, 151.35, 189.72. IR (KBr): 2953, 2971, 2850, 1645, 1613, 1509,
1465, 1437, 1383, 1264, 1158, 1082, 863, 824. HRMS-EI (m=z): (M þ H)þ
calcd for C58H90O6 882.6737, found 882.6738.
6,7,10,11-Tetra(dodecyloxy)triphenylene-1,4-dione (17)
1
Preparation same as for 14. H NMR (CDCl3, d): 0.90 (t, J ¼ 6.6 Hz,
12H), 1.28–1.61 (m, 80H), 1.98 (m, 8H), 4.24 (t, J ¼ 6.6 Hz, 4H), 4.28 (t,
J ¼ 6.6 Hz, 4H), 6.87 (s, 2H), 7.76 (s, 2H), 8.96 (s, 2H). 13C NMR (CDCl3,
d): 14.46, 23.01, 26.46, 29.37, 29.46, 29.69, 29.79, 29.81, 29.99, 30.04,
32.23, 69.01, 69.31, 104.12, 109.62, 122.38, 126.87, 129.01, 137.88,
150.75, 151.22, 189.58. IR (KBr): 2953, 2920, 2849, 1653, 1612, 1508,
1466, 1438, 1382, 1266, 1164, 1083. HRMS-ESI (m=z): (M þ H)þ calcd
for C66H106O6 995.8062, found 995.8104.
6,7,10,11-Tetra(2-ethylhexyl)triphenylene-1,4-dione (18)
Synthesis and characterization previously described. [12]
6,10-Dimethoxy-7,11-bis(2-ethylhexaloxy)triphenylene-1,4-
dione (19)
Preparation same as for 14. 1H NMR (CDCl3, d): 0.92 (t, J ¼ 7.2 Hz, 6H),
1.02 (t, J ¼ 7.2 Hz, 6H), 1.25–1.66 (m, 16H), 1.98 (m, J ¼ 6.0 Hz, 2H), 4.07

374=[1416]
A. J. Paraskos et al.
(s, 6H), 4.18 (d, J ¼ 6.0 Hz, 4H), 6.87 (s, 2H), 7.75 (s, 2H), 8.97 (s, 2H).
13C NMR (CDCl3, d):11.54, 14.41, 23.36, 24.12, 29.32, 30.90, 39.27, 56.14,
71.89, 103.57, 108.59, 122.23, 126.68, 129.01, 137.80, 151.08, 151.21,
189.48. IR (KBr): 2958, 2930, 2872, 2861, 1638, 1615, 1522, 1508, 1463,
1421, 1382, 1263, 1151, 1081, 868. HRMS-ESI (m=z): (M þ H)þ calcd for
C36H46O6 575.3367, found 575.3388.
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Synthesis and Characterization of Triphenylene-Dione
375=[1417]
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