New functionalised derivatives of hexaalkoxytriphenylene

Article abstract of DOI:10.1080/15421400490435288

We report our latent results on the development of functional triphenylene derivatives. Functionality can be introduced directly into the nucleus by, for example, nitration. Analysis of our recently determined single crystal x-ray structure of 1-nitro-2,3,6,7,10,11-hexaethoxytnphenylene (HAT2-NO₂) suggests that the introduced dipole contributes significantly to the stability of the columnar structure. Synthesis of selectively hydroxylated alkoxytriphenylenes allows the functionalisation of one or more side-chains and we show examples of this in which the functional side-chain is: ethyleneoxy or ester or the side chain carries moieties such as: TTF, anthracene, ferrocene, fuller-one or crown-ether. The final section details new findings on croum-ether terminated hexaalkoxytriphenylene derivatives, which form lyotropic lamellar phases.

Full text of DOI:10.1080/15421400490435288

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New Functionalised Derivatives
of Hexaalkoxytriphenylene
Richard Bushby a , Quanying Liu a , Owen Lozman a ,
Zhibao Lu a & Sholto Mclaren a
a SOMS Centre, University of Leeds, Leeds, United
Kingdom
Version of record first published: 18 Oct 2010.
To cite this article: Richard Bushby , Quanying Liu , Owen Lozman , Zhibao Lu &
Sholto Mclaren (2004): New Functionalised Derivatives of Hexaalkoxytriphenylene,
Molecular Crystals and Liquid Crystals, 411:1, 293-304
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Mol. Cryst. Liq. Cryst., Vol. 411, pp. 293=[1335]–304=[1346], 2004
Copyright # Taylor & Francis Inc.
ISSN: 1542-1406 print=1563-5287 online
DOI: 10.1080/15421400490435288
NEW FUNCTIONALISED DERIVATIVES
OF HEXAALKOXYTRIPHENYLENE
Richard J. Bushbyꢀ, Quanying Liu, Owen R. Lozman, Zhibao Lu,
and Sholto R. McLaren
SOMS Centre, University of Leeds, Leeds LS2 9JT,
United Kingdom
We report our latest results on the development of functional triphenylene
derivatives. Functionality can be introduced directly into the nucleus by, for
example, nitration. Analysis of our recently determined single crystal x-ray
structure
of
1-nitro-2,3,6,7,10,11-hexaethoxytriphenylene
(HAT2-NO2)
suggests that the introduced dipole contributes significantly to the stability
of the columnar structure. Synthesis of selectively hydroxylated alkoxytripheny-
lenes allows the functionalisation of one or more side-chains and we show
examples of this in which the functional side-chain is: ethyleneoxy or ester
or the side chain carries moieties such as: TTF, anthracene, ferrocene, fuller-
ene or crown-ether. The final section details new findings on crown-ether ter-
minated hexaalkoxytriphenylene derivatives, which form lyotropic lamellar
phases.
Keywords: discotic liquid crystals; functional materials; substituted triphenylenes; synthesis
INTRODUCTION
Hexaalkoxy derivatives of triphenylene constitute the most important
group of discotic liquid crystals [1]. The triphenylene-based discotics have
relatively low toxicity and have alignment and charge conduction proper-
ties that make them ideal candidates for a range of applications [2]. The
synthetic routes required to prepare these triphenylene derivatives are
now well established and include routes which enable the synthesis of poly-
mers and functional molecules [3]. The two main ways of achieving this are
by electrophilic substitution of the aromatic core or via replacement of one
of the side-chains for a functional moiety.
We thank the EPSRC and NEDO for funding.
ꢀCorresponding author. E-mail: richardb@chem.leeds.ac.uk
293=[1335]

294=[1336]
R. J. Bushby et al.
SCHEME 1 Synthesis of HATn-NO2 from HATn (R ¼ CnH2n þ 1).
RESULTS AND DISCUSSION
Electrophilic Aromatic Substitution
Electrophilic aromatic substitution has proved a valuable way of modulat-
ing the properties of hexasubstituted triphenylene ethers [4]. At the most
basic level a strong lateral dipole can be introduced by nitration at the
a-position (Scheme 1). This introduces a helical twist into the nucleus and
FIGURE 1 The phase transition temperatures of triphenylenes (HATn) and
1-nitrotriphenylenes (HATn-NO2) as a function of the chain-length (n).

New Functionalised Derivatives
295=[1337]
FIGURE 2 An enantiomeric pair or super-disk of HAT2-NO2 molecules viewed
along the crystallographic b (left) and c (right) axes. The dipole moment vectors
calculated using DFT [17] (5.96 Debye) are shown by the arrows. This corresponds
to an attractive dipole-dipole interaction of ꢁ5 kJ molꢂ1 (in a medium with e0 ꢁ 4).
results in liquid crystals with enhanced mesophase ranges (Fig. 1). The
enhanced mesophase range is almost certainly due to strong antiferroelec-
tric dipole-dipole interactions which stabilise the columnar stack. The
single crystal X-ray structure of HAT2-NO2 shows dipole pairing similar to
that in cyanobiphenyls and responsible for the re-entrant phases (Fig. 2) [5].
Replacement of a Side-chain
An alternative, more flexible route to functionalised triphenylene-based
discotic liquid crystals is to functionally transform one of the alkoxy side
chains via the key intermediate mono-hydroxy pentaalkoxytriphenylene 22.
Although there are several routes to this molecule reported in the
literature they suffer from poor yields and=or protracted purification proce-
dures [6,7]. We have recently published an improved strategy for the
production of selectively hydroxylated alkoxytriphenylenes involving a
variant of the phenyl=biphenyl coupling in which an isopropyl moiety is
used as a labile blocking or masking group [8]. In the example shown in
Scheme 2 the monohydroxy derivative is obtained in 70% yield.
It is important to note that the same product cannot be obtained using a
mixture of 2-methoxyphenol and the biphenyl and it is assumed that the
isopropyl group is removed in the workup stage of the reaction. With a
readily available supply of high purity mono-hydroxy pentaalkoxytripheny-
lene it is then relatively simple to introduce side chains such as ethyle-

296=[1338]
R. J. Bushby et al.
SCHEME 2 The synthesis of mono-hydroxy pentaalkoxytriphenylene 22.
neoxy (1-3) [9] or ester-linked (4-9) [7]; and side chains bearing terminal
groups such as anthraquinone (10-13), [10] TTF (14), [11] ferrocene
(15-18, where 10-18 electro-active), [12] fullerene (19, potential photo-
conductor), [13] and crown ethers (20-21, potentially responsive to metal
ions). Fullerenes [14] and crown ethers [15] covalently linked to calamitic
mesogens have been shown to exhibit a rich mesomorphism. In this paper
we describe in detail our new results for the crown ether terminated
hexahexyloxytriphenylene.
Crown-ether Functionalised Hexaalkoxytriphenylene
(20 and 21)
The HAT6-1-aza-15-crown-5 (20) and HAT6-1-aza-18-crown-6 (21)
derivatives were synthesised as shown in Scheme 3. The key step was
the preparation of the activated N-hydroxysuccinimidyl ester (25).
Differential scanning calorimetry, optical polarising microscopy and
X-ray diffraction experiments were performed on the compounds (20)
and (21), their mixtures with excess water ðð20ÞH O and ð21ÞH OÞ and with
2
2
excess 1 M aqueous solutions of LiCl, NaCl, KCl and NH4Cl. As prepared
the anhydrous compounds (20) and (21) exhibit no mesophase. Upon
addition of water or one of the aforementioned salt solutions a new material
is formed which is mesogenic between ꢁ8 and ꢁ40ꢃC (Table 1). Polari-
sing optical microscopy reveals a grainy, birefringent texture with little long
range order and simple shear experiments confirm that the phase has a
high viscosity. Thermal analysis shows no difference between the mixtures
containing different cations. This suggests that water alone promotes the
formation of a mesophase and that the metal ions have little effect.
Water-drop penetration experiments reveal the presence of no other
phases.
In the mesophase, the low angle x-ray diffraction patterns of ð20ÞH O and
2
ð21ÞH O show broad, diffuse reflections (Tables 2 and 3). The diffraction
2
patterns of ð20ÞH O and ð21ÞH O in the mesophase comprise comparable
2
2

New Functionalised Derivatives
297=[1339]
SCHEME 3 Synthesis of the crown-5 (20) and crown-6 (21) functionalised triphe-
nylene ethers. i, Br(CH2)5COOEt, K2CO3, EtOH, reflux. ii, NaOH, H2O, EtOH,
reflux, iii, Et3N, N,N0-disuccinimidyl carbonate, DCM. iv, Et3N, 1-aza-18-crown-6,
DCM, v, Et3N, 1-aza-15-crown-5, DCM.
maxima, although the peaks are much broader for the crown-5 containing
ð20ÞH O. Both sets of data are consistent with diffraction from a columnar
2
structure with intercolumnar and intracolumnar separations of ꢁ18.5
˚
and 3.7 A respectively. In both cases there are reflections from alkyl chain
TABLE 1 Phase Behaviour of the Crown-ether Derivatives and Their Mixtures with
Excess Water as Determined by DSC and Optical Polarising Microscopy
ꢃ
ꢃ
1st cool C (J=g)
Material
2nd heat C (J=g)
(20)
(21)
Cr 20.4 (17.9) I
Cr 22.2 (24.0) I
I ꢂ 8.6 (ꢂ17.7) Cr
I ꢂ 6.8 (ꢂ19.9) Cr
(20)H O
(21)H O
Cr 8.4 (138.7) M 39.7 (11.2) I
Cr 8.7 (140.3) M 44.3 (3.0) I
I 19.8 (ꢂ5.0) M ꢂ 17.7 (ꢂ76.9) Cr
I 28.3 (ꢂ5.3) M ꢂ 15.0 (ꢂ124.0) Cr
2
2

298=[1340]
R. J. Bushby et al.
FIGURE 3 Structures of some recently synthesised functional triphenylene
derivatives.

New Functionalised Derivatives
299=[1341]
TABLE 2 Assignment of the X-ray Powder Diffraction Data for a Sample of HAT6-
ꢃ
˚
Crown-5 (20) with Excess Water at 35 C (d-spacing Measured in A)
Miller
index
dmeas
dcalc for orthohombic
a ¼ 28.5, b ¼ 18.4, c ¼ 3.7
˚
(ꢄ0.5 A)
100
010
27–30ꢀ
18.4
9.3
28.5
18.4
9.2
020
040
4.5
4.0
4.6
Chain-chain
001
ꢁ4
3.7
3.7
ꢀVery broad, diffuse reflection.
˚
(and water) interactions at ꢁ4.0 A. In ð20ÞH O there is evidence of a weak
2
˚
and very broad reflection at ꢁ27–30 A possibly due to reflection from
lamellae of solvated crown ether (Fig. 3). This lamellar arrangement is
strongly visible in ð21ÞH O where higher order reflections are consistent
2
˚
with an orthorhombic lattice a ¼ 27.5, b ¼ 18.0, c ¼ 3.7 A.
An alternative way to view this structure is to consider the molecules
(20) and (21) as conventional hydrophilic head, hydrophobic tail, amphi-
philes with additional columnar ordering in the hydrophobic regions. The
prominence of higher order reflections from the intercolumnar repeat show
that in both cases there is strong coupling between adjacent columns. In
unsolvated (20) and (21) the volume fractions of crown ether are esti-
mated to be 0.16 and 0.19 respectively and no mesophase is observed. In
the solvated materials the volume fraction of the crown ether and its asso-
ciated water would rise to ꢁ0.25 and ꢁ0.30 for ð20ÞH O and ð21ÞH O with 8
2
2
and 10 water molecules respectively. It seems likely that upon increasing
TABLE 3 Assignment of the X-ray Powder Diffraction Data for a Sample of HAT6-
ꢃ
˚
crown-6 (21) with Excess Water at 40 C (d-spacing measured in A)
Miller
index
dmeas
dcalc for orthorhombic
a ¼ 27.5, b ¼ 18.0, c ¼ 3.7
˚
(ꢄ0.5 A)
100
010
27.5
18.4
14.7
13.8
9.0
27.5
18.0
15.1
13.8
9.0
110
200
020
040
4.5
4.0
4.5
ꢁ 4
3.7
Chain-chain
001
3.7

300=[1342]
R. J. Bushby et al.
FIGURE 4 Representation of the columnar lamellar structure formed by the HAT6-
crown-n derivatives (20) and (21) when mixed with water.
the volume fraction of crown-ether (by terminating two or more chains
with crown-ethers) one would reach a critical value of surface curvature
to generate a range of lyotropic phases. In this case one would expect
the addition of ions to have a marked effect on the structure and bulk
properties of the mesophase [16].
EXPERIMENTAL
General Procedures and Instrumentation
DSC measurements were performed on Perkin-Elmer DSC-7 system (3–
5 mg in sealed Al pans under a nitrogen atmosphere, block temperature
ꢂ40ꢃC, cooling and heating rate 10ꢃC=min). X-ray diffraction patterns were
collected on film using a pinhole camera consisting of a Phillips
˚
generator and tubes, nickel-filtered Cu Ka radiation of k ¼ 1.54 A, and a
Lindemann sample tube (1.5 mm inner diameter) to plate distance of
135.5 mm. Nuclear magnetic resonance spectra were recorded on a Bruker
DPX300 spectrometer. Chemical shifts are expressed in parts per million
(ppm) downfield of tetramethylsilane for 1H resonance’s. Mass spectra
were recorded on a VG Autospec mass spectrometer. Microanalyses were
carried out at Leeds University Microanalytical Laboratory. All C, H, and N
analytical figures are percentage values. Thin layer chromatography
was carried out using pre-coated plastic backed silica plates which were

New Functionalised Derivatives
301=[1343]
visualised under ultraviolet. Flash chromatography signifies column chro-
matography on Merck silica gel (230–400). Petroleum ether refers to the
petroleum fraction with boiling range 40–60ꢃC.
2-(60-Carboxypentyloxy)-3,6,7,10,11-pentahexyloxytriphenylene (24)
2-Hydroxy-3,6,7,10,11-pentahexyloxytriphenylene (22) [9] (1.39 g, 1.85
mmol), ethyl-6-bromohexanoate (0.53 g, 2.30 mmol) and potassium
carbonate (0.59 g, 4.28 mmol) were refluxed in ethanol (50 ml) for 2
days. The inorganic salts were removed by filtration and washed with
DCM. Solvent was removed in vacuo and the product (23) purified
via column chromatography on silica gel using 2:1 petroleum ether:
DCM as eluant. Intermediate (23) was refluxed overnight in ethanol
(20 ml) and water (5 ml), with one pellet of sodium hydroxide. After
cooling the mixture was cautiously poured into 1 M HCl (50 ml),
extracted with DCM, and the solvents removed in vacuo. The product
(24) (0.98 g, 61%) was purified by column chromatography on silica
gel using 1:1 DCM:ethyl acetate as eluant. The title compound (24)
was obtained as white powder. Subsequent analytical data were in
accordance with the literature values [3].
N-hydroxysuccinimidyl ester of 2-(60-Carboxypentyloxy)-
3,6,7,10,11-pentahexyloxytriphenylene (25)
2-(60-Carboxypentyloxy)-3,6,7,10,11-pentahexyloxytriphenylene (24) (0.50 g,
0.58 mmol), N,N0-disuccinimidyl carbonate (0.22 g, 0.87 mmol) and triethy-
lamine (0.23 g, 2.32 mmol) were stirred in DCM (50 ml) overnight. The
solventwasremovedinvacuoandthereactionmixturefilteredthroughsilica
using DCM as eluant to give the crude product (25) which was used in the
next step of reaction without further purification. dH(300 MHz, CDCl3) 7.83
(6 H, m, ArH), 4.23 (12 H, t, J 6.6, OCH2), 2.83 (4 H, s, CH2 on succini-
mide), 2.69 (2 H, t, J 7.4, CH2CO), 1.96 ꢂ 1.89 (14 H, m, CH2CH2O,
CH2CH2CO), 1.79 ꢂ .35 (32 H, m, CH2), 0.93 (15 H, t, J 6.8, CH3).
HAT6-1-aza-15-crown-5 derivative (20)
N-hydroxysuccinimidyl ester of 2-(60-Carboxypentyloxy)-3,6,7,10,11-
pentahexyloxytriphenylene (25, 0.20 g, 0.21 mmol), 1-aza-15-crown-5
(0.11 g, 0.52 mmol) and triethyl amine (0.11 g, 1.05 mmol) were stirred in
DCM (50 ml) for 8 hours. The solvent was removed in vacuo and the
product (20) purified by column chromatography on silica gel, eluting with

302=[1344]
R. J. Bushby et al.
ethyl acetate to yield 0.20 g, 0.19 mmol, 92%. C64H101NO11 requires: C,
72.5; H, 9.60; N, 1.32. Found: C, 72.65; H, 9.40, N, 1.50. dH(300 MHz,
CDCl3) 7.83 (6 H, m, ArH), 4.23 (12 H, t, J 6.6, OCH2), 3.80 (2 H, t, J
7.0, CH2N), 3.66 ꢂ 3.53 (18 H, m, CH2O, CH2N of crown ether), 2.42
(2H, t, J 6.7, CH2CON), 1.96 ꢂ 1.89 (12 H, m, CH2CH2O), 1.79 ꢂ 1.72
(2H, m, CH2CH2CON), 1.65 ꢂ 1.55 (10 H, m, CH2), 1.48 ꢂ 1.35 (22 H, m,
CH2), 0.93 (15 H, t, J 6.8, CH3). MS (ESI) 1083 (100%, [M þ Na]þ ).
HAT6-1-aza-18-crown-6 derivative (21)
N-hydroxysuccinimidyl ester of 2-(60-Carboxypentyloxy)-3,6,7,10,11-
pentahexyloxytriphenylene (25, 0.25 g, 0.26 mmol), 1-aza-18-crown-6
(0.10 g, 0.39 mmol) and triethyl amine (0.13 g, 1.30 mmol) were stirred in
DCM (50 ml) for 8 hours. The solvent was removed in vacuo and the pro-
duct (21) purified by column chromatography on silica gel, eluting with
ethyl acetate to yield 0.26 g, 0.23 mmol, 90%. C66H105NO12 requires: C,
71.77; H, 9.58; N, 1.27. Found: C, 71.5; H, 9.85, N, 1.20dH(300 MHz, CDCl3)
7.83 (6 H, m, ArH), 4.23 (12 H, t, J 6.6, OCH2), 3.69 ꢂ 3.59 (24 H, m, CH2O,
CH2N of crown ether), 2.43 (2H, t, J 7.2, CH2CON), 2.01 ꢂ 1.92 (12 H, m,
CH2CH2O), 1.84 ꢂ 1.73 (2H, m, CH2CH2CON), 1.68 ꢂ 1.52 (10 H, m, CH2),
1.48 ꢂ 1.35 (22 H, m, CH2), 0.94 (15 H, t, J 6.9, CH3). MS (ESI) 1127
(100%, [M þ Na]þ ).
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