Discogens Possessing Aryl Side Groups Synthesized by Suzuki Coupling of Triphenylene Triflates and Their Self-Organization Behavior

Article abstract of DOI:10.1002/ejoc.201600270

Pd-catalyzed Suzuki cross-coupling reactions between arylboronic acids and bromoarenes have been applied widely in the synthesis of liquid-crystalline materials. However, aryl triflate derivatives have been less used despite their high chemical tolerance, reactivity, and chemical accessibility. In this report, three series of discogens have been synthesized in good yields from appropriate triphenylene triflate precursors by Suzuki coupling reactions with various commercial arylboronic acids (e.g., aryl = phenylene, thiophene, naphthalene, triarylamine, carbazole, and fluorene). The synthesized discogens display broad mesophase ranges and high thermal stabilities. Moreover, those bearing triarylamine, carbazole, and fluorene side groups are also blue-light emitters. The availability of the triflate precursors coupled with their highly efficient cross-coupling with commercial arylboronic acids make this strategy extremely versatile and attractive for the design of new functional materials.

Full text of DOI:10.1002/ejoc.201600270

DOI: 10.1002/ejoc.201600270
Full Paper
Liquid Crystals
Discogens Possessing Aryl Side Groups Synthesized by Suzuki
Coupling of Triphenylene Triflates and Their Self-Organization
Behavior
Ke-Qing Zhao,*[a] Yue Gao,[a] Wen-Hao Yu,[a] Ping Hu,[a] Bi-Qin Wang,[a] Benoît Heinrich,[b]
and Bertrand Donnio*[b]
Abstract: Pd-catalyzed Suzuki cross-coupling reactions be- amine, carbazole, and fluorene). The synthesized discogens dis-
tween arylboronic acids and bromoarenes have been applied play broad mesophase ranges and high thermal stabilities.
widely in the synthesis of liquid-crystalline materials. However, Moreover, those bearing triarylamine, carbazole, and fluorene
aryl triflate derivatives have been less used despite their high side groups are also blue-light emitters. The availability of the
chemical tolerance, reactivity, and chemical accessibility. In this triflate precursors coupled with their highly efficient cross-cou-
report, three series of discogens have been synthesized in good pling with commercial arylboronic acids make this strategy ex-
yields from appropriate triphenylene triflate precursors by Suz- tremely versatile and attractive for the design of new functional
uki coupling reactions with various commercial arylboronic materials.
acids (e.g., aryl = phenylene, thiophene, naphthalene, triaryl-
Introduction
tures.[1] In contrast, more sophisticated hexaaryl-substituted tri-
phenylenes, Ar6-TP, and corresponding fused-ring DLCs, pre-
pared from hexabromotriphenylene followed by oxidation reac-
tions, exhibit low solubilities in classical organic solvents but
possess high phase-transition temperatures, high thermal sta-
bilities, and wide mesophase ranges.[26,27] However, they have
been less investigated owing to their unalterable and limited
molecular designs and evident synthetic difficulties.
In recent decades, discotic liquid crystal (DLC) derivatives based
on polycyclic π-conjugated triphenylene (TP) have become the
most important discotic representatives and have attracted
considerable research interest[1–12] because of their exceptional
self-organizational behavior, defect-self-healing character, and
high charge-carrier transportation along the assembled cylin-
drical columns.[13–18] The highly symmetrical TP core is an ideal
scaffold for the development of various discotic functional
materials with interesting electronic properties, and various
molecular systems based on TP have shown a wide range of
commercial applications, including optical compensating
films,[19] organic photovoltaic (OPV) devices,[20,21] organic field-
effect transistors (OFET),[22] and organic light-emitting diodes
(OLEDs).[23,24]
Hexa(alkoxy)triphenylenes (R6-TP, R = OCnH2n+1) and simple
related derivatives are the workhorses of DLCs:[1–4] their synthe-
sis conditions are versatile, and purification methods for large-
scale TP derivatives have been developed.[25] Although, R6-TP
discogens have good solubilities in most organic solvents, they
exhibit hexagonal columnar mesophases (Colhex) over narrow
temperature ranges and with low phase-transition tempera-
Alternatively, it is anticipated that mixed alkoxy/aryltriphen-
ylenes would display physical and chemical properties interme-
diate between those of pure Ar6-TP and those of pure R6-TP, of
interest for the development of new materials for electronic
devices, but such systems have not been investigated
widely.[28,29] The replacement of only one alkyl or alkoxy group
by H in R6-TPs already compromises their mesomorphism.[30–33]
However, the replacement of some of the diverging alkoxy
chains by radial π-conjugated groups (e.g., cyano, ethynyl, or
aromatic) results in mixed TP systems, in which the mesomor-
phism is maintained, with higher clearing temperatures than
those of the parent R6-TP compounds.[31] The extension of the
TP core with π-conjugated groups is also beneficial to meso-
phase induction/formation and the enhancement of the meso-
phase stability.[28,31] To date, bromo-substituted TP deriva-
tives[26,27,30–33] have mostly been used as key intermediates for
the synthesis of such π-extended TPs, mainly by Suzuki cross-
coupling reactions. However, these bromo-TPs are not readily
accessible, as their previously reported synthesis is tedious, low
yielding, and involves hydroxyl activation, catalytic hydrogen-
ation, and aromatic bromination.[30–35] In contrast, aryl triflates
are suitable alternative substrates for the Suzuki cross-coupling
reaction.[36–38] Indeed, their synthesis is shorter and more direct
than that of their bromo-TP homologs, as they can be obtained
[a] College of Chemistry and Material Science, Sichuan Normal University,
Chengdu 610066, P. R. China
E-mail: kqzhao@sicnu.edu.cn
[b] Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS),
CNRS-Université de Strasbourg (UMR 7504),
23 rue du Loess, BP 43, 67034 Strasbourg Cedex 2, France
E-mail: bertrand.donnio@ipcms.unistra.fr
http://www.ipcms.unistra.fr/
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/ejoc.201600270.
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directly in one-step from the corresponding and readily efficient overlap and result in a higher thermal stability of the
available hydroxytriphenylenes[1] by reaction with triflic an- columnar mesophase and faster charge-carrier mobility.[48,49]
hydride.[37] Triphenylenyl triflates and nonaflates have been
With these ideas in mind, we designed a series of TP disco-
used for C–N[39] and C–C bond[40] construction, respectively, in
gens, which contain various aryl moieties with electron-donat-
functional material synthesis. In this context, TP triflate deriva-
tives would seem to be more useful and relevant starting mate-
rials for the synthesis of mixed alkoxy/aryltriphenylenes.
ing and electron-withdrawing groups. We first synthesized tri-
phenylene mono(triflate), bis(triflate), and tris(triflate) deriva-
tives in high yields by the reaction of the appropriate hydroxy-
Functional molecules containing units such as triaryl- triphenylene with triflic anhydride (M0, D0, and T0, respectively;
amine,[41–43] carbazole,[44–46] and fluorene[47] have been investi- Tables 1, 2, and 3). We subsequently applied Suzuki cross-cou-
gated extensively as photoconductors, charge-carrier transport- pling reactions between these TP triflates and various arylbor-
ers, photo- and electroluminescent materials, and photorefract- onic acids to synthesize the corresponding series of mixed alk-
ive materials. They have displayed enormous academic and eco- oxy/aryltriphenylenes (Mn, Dn, and Tn), which possess radial
nomic values. DLCs containing these functional units possess electron-rich or electron-deficient phenylenes, as well as tri-
not only their own dynamics and order but also electron-rich phenylamine, carbazole, and fluorine groups, in good-to-excel-
and light-emitting features, which increase their applicability. It lent yields (Tables 1, 2, and 3). More importantly, these mixed-
may be expected that the enlargement of the π-conjugated side-group triphenylenes have been characterized by differen-
system of the semiconducting discogens will provide a more tial scanning calorimetry (DSC), polarized optical microscopy
Table 1. Molecular structures and synthetic yields of 2,7-diaryltriphenylenes D1–D17.
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Table 2. Molecular structures and synthetic yields of 2-aryltriphenylenes M1–M5.
Table 3. Molecular structures and synthetic yields of 2,6,10-triaryltriphenylenes T1–T4.
(POM), and small-angle X-ray scattering (SAXS), and most of ation, and statistical o-dialkoxybenzene oxidative trimeriza-
them (25/29) exhibit hexagonal columnar mesophases over tion.[1,50] The benzene–biphenyl route possesses a higher se-
large temperature ranges with higher clearing temperatures lectivity than the statistical method, and 2-hydroxy-3,6,7,10,11-
than those of the hexa(hexyloxy)triphenylene parent.
pentakis(hexyloxy)triphenylene and 2,7-di(hydroxy)-3,6,10,11-
tetrakis(hexyloxy)triphenylene were synthesized by this route
(Schemes 1 and 2) and obtained in good yields.[51,52] 2-Meth-
oxy-3,6,7,10,11-pentakis(hexyloxy)triphenylene was prepared
by FeCl3 oxidative coupling between 1-methoxy-2-hexyloxy-
benzene and 3,3′,4,4′-tetra(hexyloxy)biphenyl, followed by se-
lective demethylation with LiPPh2 to produce 2-hydroxy-
3,6,7,10,11-pentakis(hexyloxy)triphenylene (Scheme 1). 3,6,10,11-
Results and Discussion
Synthesis of Aryltriphenylenes from Triphenylenyl Triflates
The synthesis of hydroxytriphenylenes can usually be per- Tetrakis(hexyloxy)-2,7-bis(methyloxy)triphenylene was synthe-
formed by three different methods, namely, o-terphenyl intra- sized by the FeCl3-mediated oxidative cyclodehydrogenation
molecular oxidation, benzene–biphenyl intermolecular oxid- between 1,2-bis(hexyloxy)benzene and 3,3′-bis(hexyloxy)-4,4′-
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dimethoxybiphenyl, followed by selective demethylation with
LiPPh2 (Scheme 2). Finally, 2,6,10-tri(hydroxy)-3,7,11-tris(hexy-
loxy)triphenylene was prepared by the statistical method
(Scheme 3). First, 2,6,10-tris(hexyloxy)-3,7,11-tri(methoxy)tri-
phenylene was synthesized by the FeCl3-mediated oxidative tri-
merization of 1-methoxy-2-hexyloxybenzene, followed by col-
umn chromatographic separation of the unsymmetrical isomer.
Then, selective demethylation with LiPPh2 yielded 2,6,10-tri-
(hydroxy)-3,7,11-tris(hexyloxy)triphenylene.
Scheme 3. Synthesis of 2,6,10-tri(hydroxy)-3,7,11-tris(hexyloxy)triphenylene:
(i) n-C6H13Br, K2CO3, DMF (90 %); (ii) FeCl3, H2SO4, CH2Cl2 (50–60 %), separa-
tion of the isomers by column chromatography; (iii) LiPPh2, THF, tBuCl (80–
90 %).
Suzuki cross-coupling reactions.[36–38] Generally, the TP triflate
and arylboronic acid (1.2 equiv. per triflate group) reacted in
tetrahydrofuran/H2O (THF/H2O, 4:1) with Pd(PPh3)4 (8 mol-%) as
the catalyst and K2CO3 as the base.
The 2,7-diaryltriphenylene derivatives D1–D17 were synthe-
sized in yields of 48 to 87 % (Table 1). Considering the twofold
cross-coupling characteristic of the reaction, the yields are ac-
ceptable. Two major advantages of this cross-coupling reaction
can be emphasized: it (1) possesses a simple catalytic system
and (2) has a large functional-group tolerance; for example,
chloro (D9), cyano (D4), and thiophene (D2) derivatives were
synthesized in good yields. Furthermore, both electron-rich and
electron-deficient arylboronic acids react smoothly, and the
yields are also high, considering their bulkiness. However, the
stereochemistry has a moderate effect on the synthetic yield:
D13–D17 with bulky aryl groups are synthesized in moderate
yields. Monoaryltriphenylenes M1–M5 were synthesized in
yields of 60–94 % (Table 2), and the triaryltriphenylene disco-
gens T1–T4 were obtained in yields of 62–85 % (Table 3) with
a high tolerance to bulky substituents, as for series D1–D17.
Scheme 1. Synthesis of 2-hydroxy-3,6,7,10,11-penta(hexyloxy)triphenylene: (i)
NaOH, H2O2, H20 (91.1 %); (ii) n-C6H13Br, K2CO3, DMF (80–90 %); (iii) 1: Mg,
THF; 2: Ni(PPh3)2Cl2, THF (70 %); (iv) FeCl3, H2SO4, CH2Cl2 (50–60 %); (v) LiPPh2,
THF, tBuCl (80–90 %).
1
All of the synthesized compounds were characterized by H
NMR and IR spectroscopy; the new intermediates and target
compounds were characterized by high-resolution mass spec-
troscopy [Fourier transform ion cyclotron resonance mass spec-
trometry (FTICR-MS) with MALDI or ESI], and the analytical data
are in good agreement with the chemical structures (Fig-
ures S4–S64 in the Supporting Information).
Mesomorphism Investigation by POM, DSC, and SAXS
We first investigated the mesomorphism of these sophisticated
discogens by POM. All but D16, D17, T3, and T4 displayed typi-
cal fan-shaped or pseudo-focal-conical textures, which indicate
the presence of discotic columnar mesophases (Figure 1). The
phase transitions were characterized comprehensively by DSC
(Figure 2), and the transition temperatures and enthalpy
changes are summarized in Table S1 and Figures S1–S3. The
columnar nature of the mesophases of some representative
compounds was further proved by SAXS (Figure 4 and Table 4).
Scheme 2. Synthesis of 2,7-dihydroxy-3,6,10,11-tetrakis(hexyloxy)triphenyl-
ene: (i) m-CPBA, CH2Cl2 (81.7 %); (ii) n-C6H13Br, K2CO3, DMF (88.5 %); (iii) 1:
Mg, THF; 2: Ni(PPh3)2Cl2, THF, HCl (67.2 %); (iv) FeCl3, H2SO4, CH2Cl2 (57.1 %);
(v) LiPPh2, THF, tBuCl (80.9 %).
Triphenylene-2,7-diyl triflate (D0) was synthesized in a yield The synthesized discogens crystallized from organic solvents,
of 91 % through the reaction of triphenylene-2,7-diol with triflic and on the first heating runs they displayed crystal → meso-
anhydride (Table 1).[37] Similarly, M0 and T0 were synthesized phase and mesophase → isotropic (I) liquid transitions. On the
in almost quantitative yields (Tables 2 and 3). The correspond- first cooling run, they displayed isotropic liquid → mesophase
ing mixed alkoxy/aryltriphenylenes were synthesized through transitions, but crystallization is not always observed as the aryl
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groups are larger than the alkyl chains and the target discogens
are highly viscous. However, some discogens showed cold crys-
tallization during the second heating run (Table S1).
Table 4. Small-angle X-ray data for the mesophases of M2, D8, D12, D13,
D14, and T2.
d
meas [Å][a] I (ꢀ, Å)[b] hk/Di/hi[c] calcd. [Å][d] Mesophase parameters[e]
d
M2 20.44
14.1
vs (sh)
m (60)
w (sh)
10
D
11
20.20
11.66
Colhex (T = 25 °C)
a = 23.3 Å; S = 471 Å2 (Z = 1)
11.64
V
mol = (1610 50) Å3
(ρ = 1.01 0.03)
hmol = (3.42 0.14) Å
10.11
7.57
4.4
vw (sh) 20
10.10
7.63
w (sh)
vs (10)
s (80)
21
hch+har
hπ
3.50
D12 22.10
14.6
vs (sh)
m (60)
vw (sh) 20
10
D
21.90
10.95
Colhex (T = 25 °C)
a = 25.35 Å; S = 555 Å2 (Z = 1)
11.02
V
mol = (1850 60) Å3
(ρ = 1.01 0.03)
hmol = (3.33 0.14) Å
8.17
7.25
4.5
3.53
21.85
14.6
10.76
m (sh) 21
vw (sh) 30
vs. (10) hch+har
vs (100) hπ
8.28
7.30
vs (sh)
m (40)
10
D
21.70
10.85
8.20
Colhex (T = 150 °C)
a = 25.05 Å; S = 544 Å2 (Z = 1)
Figure 1. POM images of some representative samples (for a cooling rate of
3 °C/min from isotropic liquid). (A) M1 at 98 °C with homeotropic alignment
behavior (face-on orientation of the discotic columns on the glass surface);
(B) M1 at 96 °C with parallel polarizers, showing sixfold symmetrical domains
of the Colhex mesophase; (C) M4 at 88 °C, the black textures show face-on
orientation of the columns; (D) D12 at 125 °C, the fan-shaped texture shows
the edge-on orientation of the discotic columns; (E) D5 at 90 °C, the texture
shows the homeotropic alignment behavior of the fluorophenyltriphenylene;
(F) T2 at 120 °C, big fan-shaped texture; (G) D14 at 140 °C, small fan-shaped
texture with propeller-like assembly; (H) D14 at 180 °C, the growth of devel-
opable domains from the isotropic liquid.
vw (sh) 20
V
mol = (2020 70) Å3
(ρ = 0.93 0.03)
hmol = (3.71 0.16) Å
8.10
4.5
3.74
w (sh)
vs (10)
vs (40)
vs (sh)
s (40)
21
hch+har
hπ
10
D
T2 23.42
14.6
23.15
11.58
Colhex (T = 25 °C)
a = 26.7 Å; S = 619 Å2 (Z = 1)
11.53
w (sh)
20
V
mol = (2080 60) Å3
(ρ = 1.02 0.03)
hmol = (3.36 0.14) Å
8.64
6.57
m (sh)
vw (sh) 22
21
8.75
6.68
4.4
s (10)
hch+har
3.52
s (100)
m (50)
vs (sh)
m (70)
hπ
D2
10
D
D8 29
18.20
14.4
Colhex (T = 170 °C)
18.20
20.10
a = 21.0 Å; S = 382 Å2 (Z = 1)
V
(ρ = 1.00 0.03)
hmol = (3.86 0.16) Å
mol = (1480 50) Å3
4.4
3.71
D13 20.10
14.3
vs (10)
s (50)
vs (sh)
m (80)
vs (10)
hch+har
hπ
10
Colhex (T = 50 °C)
D
a = 23.2 Å; S = 467 Å2 (Z = 1)
4.4
hch+har
V
mol = (1825 80) Å3
(ρ = 1.02 0.05)
hmol = (3.91 0.20) Å
3.60
D14 20.16
14.0
s (50)
100 (sh) 10
m (100)
w (sh)
hπ
20.18
7.63
Colhex (T = 160 °C)
D
21
a = 23.3 Å; S = 470 Å2 (Z = 1)
7.64
V
mol = (1920 80) Å3
(ρ = 0.96 0.04)
hmol = (4.09 0.20) Å
5.0–4.4
3.64
vs (10)
s (40)
hch+har
hπ
[a] Measured periodicities of reflections from columnar lattice (hk) of scatter-
ing signals from short-range correlated structure Di and from lateral distances
between molecular segments hi. [b] Intensity of reflections and scattering
signals (VS: very strong, S: strong, m: medium, w: weak, vw: very weak) and
associated correlation length ꢀ (sh indicates a sharp reflection). [c] Miller indi-
ces, short-range correlated periodicities D and D2 = 2D, lateral distances be-
tween chains (hch), rigid segments of substituents (har), and face-to-face tri-
phenylene rings (hπ). [d] Calculated spacing from optimized lattice parameter.
[e] Type of mesophase, temperature, lattice parameter (a), lattice area (S),
number of molecule stacks per lattice (Z), calculated molecular volume from
reference data (Vmol), density (ρ), and columnar slice thickness (hmol).
Figure 2. Representative DSC curves depicting the first cooling run and the
second heating run of M2, M4, D3, D6, D8, T1, and T2. The peaks in the
first cooling runs represent isotropic liquid to columnar phase transitions
(I → Colhex); and the peaks in the second heating run show columnar phase
to isotropic liquid transitions (Colhex → I).
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Mesomorphism of 2,7-Diaryl-Substituted Triphenylenes
D1–D17
ter of the substituents and the extension of the columnar meso-
morphism to higher temperature was previously investigated
for close discotic systems.[55,56]
The 2,7-diaryl-substituted triphenylenes contain neutral aryls
(D1–D3), electron-deficient aryls (D4–D9), electron-rich aryls
(D10–D12), and the bulky triphenylamine (D12), carbazole
(D14, D16, and D17), and fluorene (D15) groups (Table 1). Tri-
phenylene-2,7-diyl triflate (D0) displays a columnar (Colhex
phase at 124–179 °C and a plastic columnar (Colx) phase below
124 °C (Figure S1).
Diphenyl-TP (D1) can be regarded as the parent compound
of the 2,7-diaryl-substituted derivatives. Compound D1 exhibits
melting and clearing temperature of 10 and 120 °C, that is 50 °C
below and 20 °C above the respective transition temperatures
of hexakis(hexyloxy)TP (R6-TP, R = OC6H13).[53] The temperature
range of the mesophase is also considerably broader than those
of other disubstituted isomers: the 3,6-isomer displays a colum-
nar phase between 71 and 136 °C, and the 2,3-isomer is non-
mesomorphic with a melting point of 104 °C.[28]
For D2, possessing 3-thiophene substituents, the mesophase
range shifts somewhat to higher temperature (between 68 and
148 °C), consistent with previously reported findings for the 3,6-
isomer (I → Colhex 147 °C, Colhex → glass 55 °C) and 2,3-isomer
(monotropic with a m.p. of 87 °C).[28] This shift is evidently re-
lated to the enhanced interactions between the thiophene
rings, whereas D3 instead demonstrates the effect of a further
molecular extension of the conjugated moieties from phenyl to
2-naphthalenyl substituents. As expected, the extension further
delayed the transition to the isotropic liquid phase (202 °C), and
the melting temperature increased moderately (37 °C), resulting
in much higher mesophase stability than those for D1 and D2.
In D4, the phenyl rings are terminated with electron-withdraw-
ing cyano functions, which are well-known promoters of meso-
morphism through dipolar association.[31,32,54] Logically, the en-
hanced interactions increase both the clearing and the melting
temperature (by 88 and 64 °C, respectively) and enlarge the
mesophase range somewhat. The ratio with other substitution
patterns is similar to that for D1, as the 2,3-isomer is non-meso-
morphic with a melting temperature of 217 °C, and the 3,6-
isomer displays a clearing temperature of 186 °C with a meso-
phase range of 10 °C.[28] Comparing the mesomorphism of 2,7-
diaryl-TPs D1, D2, and D4 with those of their 2,3- and 3,6-iso-
mers, the most influential structural features for the induction
and stabilization of mesomorphism is the larger separation be-
tween both substitution positions rather than the molecular
symmetry alone. For example, the 2,7- and 3,6-isomers, which
favor a more homogeneous distribution of the aliphatic contin-
uum between the columns, are less perturbed than they would
be if the substituents were closer to each other, as in the 2,3-
isomer.[55,56]
The deleterious effect of weakly electron-donating groups
such as alkyl and alkoxy chains was pointed out in the same
report, but the series of substituents involved no longer chains
than a methyl group. On the contrary, D10 and D12 show ex-
tended Colhex ranges owing to their pentyl chains, which insert
into the aliphatic periphery and contribute to isolating the dis-
cogens at the nodes of the lattice. Conversely, the methoxy
chains of D11 are insufficient to screen out interactions be-
tween the substituents of neighboring columns and lead to the
appearance of a broad three-dimensional “plastic Col” meso-
phase followed by a narrow Colhex range. The derivatives with
bulkier electron-rich substituents such as diphenylaminophenyl
(D13) and phenylcarbazole (D14, D16, and D17) are either non-
mesomorphic with crystalline phases that melt at high temper-
ature (D13, D16, and D17) or show a tiny Colhex range above a
three-dimensional mesophase (D14). In the crystalline carb-
azole derivatives, the substituents are attached through the
phenyl rings; therefore, the entire carbazole rings are pendant
from the triphenylene core, and this allows self-association in
regular, crystalline networks. Conversely, mesomorphism per-
sists for the compound with the side-attached carbazole moiety
and is even improved for the dimethylfluorene derivative (D15),
for which side-attachment combines with the space require-
ment of the methyl groups to hamper interactions between the
fluorene rings. This derivative exclusively shows the Colhex
phase in the broadest range of the series, presumably because
the triphenylene columns are surrounded by a swollen periph-
ery of molten chains and disorganized fluorene substituents.
)
Mesomorphism of 2-Aryltriphenylenes M0–M5
The starting compound, triphenylen-2-yl triflate (M0), displays
a Colhex phase from room temperature to 173 °C, that is, to a
much higher temperatures than that for R6-TP. All five synthe-
sized 2-aryltriphenylenes also exhibit Colhex phases over broad
ranges, again up to temperatures well above that of R6-TP (Fig-
ure S2). The transition to the isotropic liquid is indeed delayed
by the molecular extension of the mesogens; thus, the transi-
tions are intermediate between those of the disubstituted ana-
logues and R6-TP (see above and Figure 3). The broadening
of the mesomorphic range actually comes from a significant
decrease of the melting temperature: for instance, M4 melts at
84 °C on first heating, but the D16 analogue melts at 232 °C,
and R6-TP at melts 68 °C. On cooling, none of the monosubsti-
For the electron-deficient aryl systems such as the fluoro- tuted derivatives crystallize, and only two of them (M1 and M3)
phenyl (D5 to D8) and chlorophenyl (D9) derivatives, the bene- give rise to cold crystallization on the second heating. In these
ficial impact of electron-withdrawing substituents on the clear- monosubstituted derivatives, the disorder introduced by the in-
ing temperatures is obvious: D5 to D8 possess one to three sertion of substituents between the aliphatic chains seems to
fluoro groups on the phenyl rings, and their clearing tempera- be the dominant effect, and this explains the suppression of
tures increase from 162–214 °C, and the transition increases to crystalline arrangements. In particular, the proportion of sub-
219 °C for D9 with the even more withdrawing chloro group. stituents appears too low to efficiently promote 3D arrange-
Such a relationship between the electron-withdrawing charac- ments through self-association processes.
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observed for the alkyl-chain-terminated substituents, that is, for
columns extended by aromatic segments that are entirely en-
veloped by the chains. This architecture logically promotes
sharp interfaces with the aliphatic periphery and, thus, the pres-
ence of higher-order reflections. On the contrary, substituents
devoid of terminal chains just insert in the periphery without
contributing to nanosegregation boundaries. Therefore, the in-
terfaces are rather irregular for these systems, and, conse-
quently, no or only one higher-order reflection is detectable in
the SAXS patterns.
Figure 3. Comparative phase diagram of selected compounds of the three
series of TP derivatives bearing the same substituents.
Mesomorphism of 2,6,10-Triaryltriphenylenes T0–T4
The starting compound for the triaryl-TPs, T0, displays a plastic
Col phase (Colx) with a high clearing temperature of 222 °C. In
line with findings for derivatives with fewer alkyl chains, the
transitions to the isotropic liquid phase are further delayed with
regard to those of the disubstituted derivatives (Figure 3). For
the alkyl-chain-terminated derivatives T1 and T2, the Colhex
phase is maintained and even extended to higher clearing tem-
peratures. The derivatives with side-attached phenylcarbazole
and dimethylfluorene moieties, T3 and T4, only show crystalline
phases with very high melting temperatures (271 and 239 °C,
respectively, Figure S3) owing to the self-association of the
macrocycles. Therefore, the proportion of aliphatic segments is
not enough to counterbalance these bulky aryls and allow the
appearance of mesophases. Therefore, in this series, the bulki-
ness of the substituents is very deleterious to mesomorphism
but contrarily helps with the stabilization of the crystalline state.
Characterization of the Mesophases by SAXS
The mesomorphism of a selection of aryl-TP compounds (i.e.,
M2, D8, D12–D14, and T2) was investigated by SAXS. In partic-
ular, the assignments of Colhex mesophases on the basis of the
optical textures were confirmed by the sharp small-angle reflec-
tions and the wide-angle scattering profiles (Figure 4 and
Figure 4. Representative SAXS profiles.
For any substituent, the aromatic segments and the chains
Table 4). In addition to the broad scattering maximum at ca. connected to the triphenylene unit alternate in the column re-
4.5–5 Å owing to the liquidlike lateral distances between mol- gion around the triphenylene cores. This alternation of high-
ten chains (hch) and between the rigid moieties of the substitu- and low-electronic-density segments gives rise to its own scat-
ents (har), the wide-angle region contains a semidiffuse peak at tering signal identified as the broad small-angle peak, D (Fig-
ca. 3.5 Å for the triphenylene rings stacked into columns (hπ). ure 4). The width of the signal implies that the associated struc-
The columns then arrange at the nodes of a hexagonal lattice ture is limited to the local range, and the correlation lengths
with a mixed periphery of chains and aromatic residues, as de- are between three and eight alternations. Consequently, the
finitively demonstrated by the indexation of the small-angle re- cylindrical symmetry of the long-range-correlated arrangement
flections to (10), (11), (20), (21), (30), and (22). However, the of columns is not affected, and the mesophase can still be con-
number of detectable reflections is variable: three or four were sidered as a classical Colhex phase with only an increased rough-
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ness of the nanosegregation interfaces. As previously found for
other closely related discotic systems,[57] the molecular organi-
zation in the mesophase appears to be ruled by the stacking
of the mesogenic units, which prevails over the development
of a regular structure between the substituents.
Nevertheless, substituents without terminal chains (D8) and
especially those with large peripheral macrocycles (D13 and
D14) perturb the columnar stacking, as indicated by the induc-
tion of crystalline phases and the restriction of the mesomor-
phism to small Colhex ranges (or even only monotropic, as for
D13), whereas the ranges are enlarged by the alkyl-chain-termi-
nated substituents in M2, D12, and T2 (see above). Within the
mesomorphic domains, the perturbation of the stacking should
lead to a modified relationship between the stacking distance
at the local range, hπ, and the molecular-slice thickness of the
columns hmol (i.e., the ratio between the molecular volume,
V
mol, calculated from reference data, and the lattice area, S).[58]
Both heights are similar with alkyl-chain termination and are
associated with relatively large correlation lengths; therefore,
the triphenylene rings form rather straight and untilted col-
umns. In addition, the geometrical interface areas per chain are
ca. 21 Å2 at room temperature and 23 Å2 for D12 at 150 °C,
that is, in good agreement with the natural cross-section of the
alkyl chains. This favorable packing geometry is consistent with
the broad Colhex ranges, in contrast to substituents without ter-
minal chains, which show hmol values significantly above hπ and
areas per chain that exceed their space requirement. These find-
ings confirm a perturbed stacking, which is clearly related to
enhanced interactions between the substituents.
Photophysical Properties of Aryltriphenylene Derivatives
Bearing Chromophores – UV/Vis Absorption and
Fluorescent Emission
As some of the discogens contain light-emitting functional
units, we measured the UV/Vis absorption and fluorescent emis-
sion spectra of M3–M5, D13, D15, D16, T3, and T4 in dilute
THF solution (1 × 10–6
M). The spectra are displayed in Figure 5,
and the data are summarized in Table 5. The spectra display
the absorptions of the TP core and the triphenylamine, carbaz-
ole, or fluorene units: all of these compounds have an absorp-
tion peak at λ = 284 nm that originates from the absorption of
the TP core; the other absorption bands at λ = 325–360 nm
are characteristic bands of triarylamine, carbazole, and fluorine
moieties. The absorptions are redshifted compared with that of
pure hexakis(hexyloxy)TP. As the number of aryl substituents
increases from one to three, the absorptions at λ = 300–400 nm
also strengthen accordingly.
Figure 5. UV/Vis and fluorescence spectra of R6-TP and aryl-TPs (in solution
in THF, 1.0 × 10–6
M): (a) diphenylaminophenyl-TP, (b) carbazoylphenyl-TP, (c)
dimethylfluorenyl-TP.
In solution, the maximum emissions occur in the λ = 350– With a few exceptions (Table 5 and Supporting Information), no
500 nm range with a peak at λ ≈ 425 nm, and the fluorescence great differences could be observed between the fluorescence
intensities are enhanced with the increasing number of aryl properties of the films and solutions. Indeed, almost identical
groups; T3 displays the strongest absorption and emission (Fig- spectral features were observed for the triarylamine- and carb-
ure 5). The broad fluorescence emission bands of the target azole-substituted TP compounds, whereas the largest diver-
compounds at λ = 375–500 nm demonstrate that these com- gence was recorded for the carbazole-2,7-distubstituted TP
pounds emit blue light and can be used as light-emitting dis- (D16), for which the emission was redshifted by ca. 20 nm. The
cotic materials. To complete this investigation, the fluorescence films of all of the fluorene derivatives (M5, D15, and T4) show
of films of the corresponding compounds was also recorded. redshifted emissions compared with the solution emissions
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Table 5. Summary of the UV/Vis absorption and fluorescence spectroscopic Experimental Section
properties of discogens in solutions and films.
Instruments: High-resolution mass spectra were measured with an
λabs
ε
λex/λem [nm] λex/λem
Quantum efficiency
IonSpec (now Varian) FTICR mass spectrometer (7.0 T) with MALDI
[nm] [L mol–1 cm–1
]
(intensity)[a]
[nm][b]
(λex, nm)[c]
1
or ESI. The H NMR (400 MHz) spectra were recorded with a Varian
R6-TP 278
308
1.3 × 105
2.6 × 104
1.3 × 105
5.5 × 104
1.1 × 105
5.5 × 104
1.3 × 105
1.3 × 105
1.3 × 105
6.1 × 104
1.5 × 105
4.4 × 104
8.9 × 104
4.0 × 104
8.7 × 104
5.7 × 104
1.5 × 105
1.2 × 105
278/383
–
–
UNITY INOVA-400 spectrometer, CDCl3 and C6D6 were used as the
solvents, and tetramethylsilane (TMS) was used as the internal stan-
dard. The phase transitions and enthalpy changes were measured
by DSC with a TA-DSC Q100 instrument at heating and cooling
rates of 10 °C/min under a N2 atmosphere. Liquid-crystalline optical
textures were observed with an OLYMPUS BX41 polarizing optical
microscope installed with a HCS302-GXY heating plate and an
INSTEC STC200 temperature controller. The SAXS patterns were re-
corded with a Rigaku Smartlab (3) X-ray diffractometer with a TCU
110 temperature controller ( 1 K) and a Cu-K radiation source (λ =
0.154 nm) operated at 40 kV with a scanning speed of 10 K/min.
The fluorescence was measured with a HORIBA Fluoromax-4p spec-
trometer, and the quantum efficiencies were measured with a
HORIBA-F-3029 integrating sphere.
(8.4 × 105)
340/412
M3
282
347
340/402, 418 0.47 (340)
(4.1 × 106)
362/425
D13 296
362/426
345/410
340/406
343/427
340/418
340/452
0.50 (362)
0.67 (345)
0.30 (340)
0.42 (340)
0.38 (340)
0.24 (340)
0.22 (345)
346
(9.5 × 106)
348/411
T3
286
349
283
341
(11.9 × 106)
340/408
M4
(1.6 × 106)
343/408
D16 286
342
(1.6 × 106)
340/405
M5
288
340
(1.7 × 106)
340/422
D15 290
348
(1.7 × 106)
T4
316
340
344/388, 404 345/418
Chemicals: The intermediate 2-hydroxy-3,6,7,10,11-pentakis(hexy-
loxy)triphenylene[51] and 2,6,10-tri(hydroxy)-3,7,11-tris(hexyloxy)tri-
phenylene[52] were prepared according to our previously reported
methods (Schemes 1 and 3). All chemicals, including the arylboronic
acids and solvents, were commercial products, which were used
directly without further purification.
(5.7 × 106,
5.8 × 106)
[a] Solution fluorescence with excitation and emission peaks. [b] Film fluores-
cence with excitation and emission peaks. [c] The fluorescence absolute
quantum efficiency was measured for THF solutions of the samples at a con-
centration of 1 × 10–6 mol/L.
5-Bromo-2-methoxyphenol:[59] 5-Bromo-2-methoxybenzaldehyde
(10 g, 50.5 mmol) in dichloromethane (30 mL) was cooled to 0 °C.
Then, a solution of 3-chloroperoxybenzoic acid (m-CPBA, 11.9 g,
69.0 mmol, 85 %) in dichloromethane (100 mL) was added dropwise
with stirring at this temperature, and the mixture was stirred at
ambient temperature for 72 h. The white solid was removed by
(10–30 nm), probably because of the possible aggregation of
the molecules. This aggregation has also been indicated by the
decreased fluorescence quantum efficiencies caused by aggre-
gation quenching (Table 5).
filtration, Na2S2O3 solution (40 mL, 2 M) was added, and stirring was
continued for another 2 h. The CH2Cl2 was removed with a rotary
evaporator, and the residue was dissolved in diethyl ether and
Conclusions
washed with Na2SO3 solution (3 × 10 mL, 1
NaHCO3 (3 × 10 mL); the organic phase was extracted with NaOH
solution (3 × 20 mL, 2 ). The pH of the aqueous phase was ad-
M) and a solution of
Three new series of DLCs, namely, 2-aryl-, 2,7-diaryl-, and 2,6,10-
triaryl/alkoxytriphenylenes, have been designed and synthe-
sized. The first application of Suzuki cross-coupling reactions
between the readily accessible triflate derivatives 2-TfO-TP, 2,7-
(TfO)2-TP, and 2,6,10-(TfO)3-TP (M0, D0, and T0) and various aryl-
boronic acids resulted in the synthesis of the target discogens
in good-to-excellent yields. The three precursory TP triflates
(M0, D0, and T0) display Colhex mesophases or plastic Colx pha-
ses with high clearing temperatures. Among the 26 synthesized
M
justed to 3–4 and it was extracted with diethyl ether (3 × 20 mL),
dried with MgSO4, and filtered. The solvent was removed by distilla-
tion, and the compound was purified by column chromatography
(light petroleum/CH2Cl2 1:1) to yield a white solid (7.12 g, 81.7 %).
1H NMR (CDCl3, 400 MHz): δ = 7.06 (d, J = 2.40 Hz, 1 H, ArH), 6.96
(dd, J = 2.40, J = 8.40 Hz, 1 H, ArH), 6.71 (d, J = 8.40 Hz, 1 H, ArH),
5.67 (s, 1 H, OH), 3.87 (s, 3 H, OCH3) ppm.
4-Bromo-2-hexyloxy-1-methoxybenzene: A mixture of 5-bromo-
2-methoxyphenol (2 g, 10.8 mmol), K2CO3 (4.5 g, 32.3 mmol), and 1-
bromohexane (1.94 g, 12.9 mmol) in N,N-dimethylformamide (DMF,
45 mL) was stirred at 80 °C for 24 h. The inorganic compounds were
removed by filtration, the solvent was removed by distillation, and
the product was collected by reduced pressure distillation to yield
the product as a pale liquid (3.1 g, 88.5 %).
aryl-substituted triphenylene discogens, 22 exhibit
a
Colhex mesophase. The clearing temperatures increase with the
increased number of aryl substituents. On cooling from the iso-
tropic liquids, the discogens exhibit Colhex phases in broad tem-
perature ranges down to room temperature. We have demon-
strated for the first time that both electron-rich and electron-
deficient aryl substituents on the TP core enhance the meso-
phase formation and stability. The successful combination of
one, two, and three triarylamine, carbazole, and fluorene units
to the central triphenylene core has resulted in functional DLCs,
which have potential applications in the field of mesophase
semiconducting materials with high charge-carrier transport.
Furthermore, we expect that aryl triflates, as equivalent
bromoarene synthons, will be used more widely as substrates
for Pd-catalyzed cross-coupling reactions in the synthesis of liq-
uid crystals or even other functional molecular materials.
3,3′-Di(hexyloxy)-4,4′-bis(methyloxy)biphenyl: To magnesium
chips (420 mg, 17.4 mmol) was slowly added a solution of 4-bromo-
1-methoxy-2-(hexyloxy)benzene (9.5 g, 33.0 mmol) in THF (10 mL)
under N2. The mixture was stirred under reflux until the magnesium
chips disappeared. Then, it was cooled to room temperature, and
Ni(PPh3)2Cl2 (140.2 mg, 0.28 mmol) was added. The mixture was
stirred at 45 °C for 12 h. Diluted hydrochloric acid was added drop-
wise until the mixture was acidic. The organic phase was extracted
with ethyl acetate and dried with anhydrous MgSO4. The solvent
was evaporated under reduced pressure to afford the crude prod-
uct, which was recrystallized from methanol to afford the biphenyl
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as a white solid, yield 3.9 g (67.2 %). 1H NMR (CDCl3, TMS, 400 MHz): series, D2–D17, were all prepared accordingly. 1H NMR (CDCl3, TMS,
δ = 7.01 (dd, J = 0.80, 2.00 Hz, 1 H, ArH), 6.99 (dd, J = 0.80, 2.00 Hz,
400 MHz): δ = 8.39 (s, 2 H, ArH), 7.99 (s, 2 H, ArH), 7.93 (s, 2 H, ArH),
1 H, ArH), 6.98 (s, 1 H, ArH), 6.97 (s, 1 H, ArH), 3.97 (t, J = 6.80 Hz, 4
7.74 (d, J = 8.00 Hz, 4 H), 7.51 (t, J = 7.60 Hz, 4 H), 7.42 (t, J =
H, OCH2), 3.83 (d, J = 0.80 Hz, 6 H, OCH3), 1.87–1.80 (m, 4 H, CH2), 7.20 Hz, 2 H), 4.21 (dd, J = 6.40, J = 15.60 Hz, 8 H, OCH2), 1.95–1.80
1.47–1.41 (m, 4 H, CH2), 1.37–1.31 (m, 8 H, CH2), 0.92–0.88 (m, 6 H,
CH3) ppm.
(m, 8 H, CH2), 1.51–1.47 (m, 8 H, CH2), 1.39–1.32 (m, 18 H, CH2),
0.93–0.89 (m, 12 H, CH3) ppm. HRMS (ESI): calcd. for C54H68O4 [M]+
780.51; found 780.5115.
2,7-Bis(methyloxy)-3,7,10,11-tetrakis(hexyloxy)triphenylene: To
a
mixture of 4,4′-bis(methyloxy)-3,3′-bis(hexyloxy)-1,1′-biphenyl
D2: The coupling of D0 (100 mg, 0.11 mmol) with (thiophen-3-
yl)boronic acid (33.4 mg, 0.262 mmol) resulted in D2 (67.1 mg,
76.9 %). H NMR (CDCl3, TMS, 400 MHz): δ = 8.53 (s, 2 H, ArH), 7.94
(s, 2 H, ArH), 7.93 (s, 2 H, ArH), 7.80 (d, J = 4.00 Hz, 2 H), 7.65 (d, J =
8.00 Hz, 2 H), 7.44 (dd, J = 2.80, 2.00 Hz, 2 H), 4.27–4.21 (m, 8 H,
OCH2), 1.97–1.90 (m, 8 H, CH2), 1.61–1.52 (m, 8 H, CH2), 1.41–1.37
(m, 16 H, CH2), 0.93 (t, J = 8.00 Hz, 12 H, OCH3) ppm. HRMS (ESI):
calcd. for C50H64O4S2 [M]+ 792.42; found 792.4246.
(10.0 g, 24.1 mmol) and 1,2-bis(hexyloxy)benzene (26.9 g,
96.6 mmol) in CH2Cl2 (100 mL), FeCl3 (30.6 g, 188.3 mmol) and a
catalytic amount of H2SO4 were added, and the mixture was stirred
at room temperature for 2 h. Then, the mixture was quenched with
cold methanol, and water was added. The organic layer was ex-
tracted and dried with anhydrous MgSO4. The mixture was purified
by chromatography to yield the dimethoxytriphenylene derivative
as a white solid, yield 9.51 g (57.1 %). 1H NMR (CDCl3, TMS,
400 MHz): δ = 7.85 (s, 4 H, ArH), 7.80 (s, 2 H, ArH), 4.24 (t, J =
6.40 Hz, 8 H, OCH2), 4.12 (s, 6 H, OCH3), 1.98–1.91 (m, 8 H, CH2),
1.62–1.54 (m, 8 H, CH2), 1.45–1.34 (m, 16 H, CH2), 0.94 (dd, J = 1.60,
7.20 Hz, 12 H, CH3) ppm.
1
D3: The coupling of D0 (50 mg, 0.054 mmol) with (naphthalen-2-
yl)boronic acid (22.53 mg, 0.131 mmol) resulted in D3 (27.9 mg,
1
58.3 %). H NMR (CDCl3, TMS, 400 MHz): δ = 8.50 (s, 2 H, ArH), 8.18
(s, 2 H, ArH), 8.05 (s, 2 H, ArH), 7.97–7.92 (m, 8 H, ArH), 7.90 (s, 1 H,
ArH), 7.88 (s, 1 H, ArH), 7.54 (t, J = 4.00 Hz, 4 H, ArH), 4.25–4.19 (m,
8 H, OCH2), 1.94–1.80 (m, 8 H, CH2), 1.55–1.46 (m, 8 H, CH2), 1.36–
1.30 (m, 16 H, CH2), 0.91–0.86 (m, 12 H, CH3) ppm. HRMS (ESI): calcd.
for C62H72O4 [M]+ 880.54; found 880.5428.
2,7-Dihydroxy-3,6,10,11-tetrakis(hexyloxy)triphenylene: Lith-
ium (small particles, 3.1 g, 435.5 mmol) was added to a solution of
PPh3 (45.73 g, 174.2 mmol) in dry THF (100 mL). The mixture was
stirred for 1 h, and the Li disappeared; tBuCl (16.13 g, 174.2 mmol)
was added in three portions, and the mixture was heated under
reflux for 1 h. 2,7-Dimethoxy-3,6,10,11-tetrakis(hexyloxy)triphenyl-
ene (12 g, 17.42 mmol) was added under a nitrogen atmosphere,
and the mixture was stirred for 12 h at 70 °C. Then, the mixture
was poured carefully into ice water, acidified with 10 % HCl solution
(100 mL),and extracted with diethyl ether. The organic layer was
dried with magnesium sulfate and filtered, and the organic solvent
was removed under vacuum. Purification through silica gel column
chromatography afforded the product as a white solid, yield 9.32 g
(80.9 %). 1H NMR (CDCl3, TMS, 400 MHz): δ = 7.96 (s, 2 H, ArH), 7.81
(s, 2 H, ArH), 7.73 (s, 1 H, ArH), 7.71 (s, 1 H, ArH), 5.89 (s, 2 H, OH),
4.28 (dd, J = 6.40, 12.80 Hz, 4 H, OCH2), 4.20 (t, J = 6.40 Hz, 4 H,
OCH2), 1.97–1.90 (m, 8 H, CH2), 1.58–1.52 (m, 8 H, CH2), 1.42–1.38
(m, 16 H, CH2), 0.96–0.92 (m, 12 H, CH3) ppm.
D4: The coupling of D0 (50 mg, 0.054 mmol) with (4-cyanophe-
nyl)boronic acid (19.2 mg, 0.131 mmol) resulted in D4 (33.5 mg,
1
74.6 %). H NMR (CDCl3, TMS, 400 MHz): δ = 8.35 (s, 2 H, ArH), 7.98
(s, 2 H, ArH), 7.90 (s, 2 H, ArH), 7.85 (d, J = 8.40 Hz, 4 H, ArH), 7.80
(d, J = 8.40 Hz, 4 H, ArH), 4.25–4.19 (m, 8 H, OCH2), 1.96–1.81 (m, 8
H, CH2), 1.56–1.43 (m, 8 H, CH2), 1.38–1.33 (m, 16 H, CH2), 0.93–0.89
(m, 8 H, CH3) ppm. HRMS (ESI): calcd. for C56H66N2O4 [M]+ 830.50;
found 830.5018.
D5: The coupling of D0 (50 mg, 0.054 mmol) with (4-fluoro-
phenyl)boronic acid (18.33 mg, 0.131 mmol) resulted in D5
1
(28.5 mg, 64.2 %). H NMR (CDCl3, TMS, 400 MHz): δ = 8.34 (s, 2 H,
ArH), 7.96 (s, 2 H, ArH), 7.92 (s, 2 H, ArH), 7.69 (dd, J = 5.60, 2.80 Hz,
4 H, ArH), 7.19 (t, J = 8.80 Hz, 4 H, ArH), 4.22–4.20 (m, 8 H, OCH2),
1.95–1.80 (m, 8 H, CH2), 1.57–1.47 (m, 8 H, CH2), 1.38–1.33 (m, 16
H, CH2), 0.93–0.89 (m, 12 H, CH3) ppm. HRMS (ESI): calcd. for
C54H66F2O4 [M]+ 816.49; found 816.4928.
3,6,10,11-Tetra(hexyloxy)triphenylene-2,7-diyl Triflate (D0): To
a stirred solution of 2,7-dihydroxy-3,6,10,11-tetra(hexyloxy)triphen-
ylene (1.0 g, 1.51 mmol) in CH2Cl2 (50 mL) was added triethylamine
(1.28 mL, 12.1 mmol) at room temperature under an argon atmos-
phere. The mixture was cooled to –40 °C, and Tf2O (1.28 mL,
3.02 mmol) was added. The mixture was warmed to room tempera-
ture and stirred for 6 h. The reaction mixture was filtered, and the
filtrate was concentrated in vacuo. The residue was purified by silica
column chromatography (dichloromethane/petroleum ether 1:2) to
yield D0 as a gray solid (1.26 g, 90.6 %). 1H NMR (CDCl3, TMS,
400 MHz): δ = 8.21 (s, 2 H, ArH), 7.88 (s, 2 H, ArH), 7.68 (s, 2 H, ArH),
4.28 (t, J = 6.4 Hz, 4 H, OCH2), 4.23 (t, J = 6.4 Hz, 4 H, OCH2), 1.99–
1.93 (m, 8 H, CH2), 1.62–1.56 (m, 8 H, CH2), 1.45–1.37 (m, 16 H),
0.96–0.93 (m, 12 H, CH3) ppm. HRMS (ESI): calcd. for C44H58F6O10S2
[M]+ 924.34; found 924.3375.
D6: The coupling of D0 (50 mg, 0.054 mmol) with (3,4-difluorophe-
nyl)boronic acid (20.69 mg, 0.131 mmol) resulted in D6 (39.2 mg,
1
84.6 %). H NMR (CDCl3, TMS, 400 MHz): δ = 8.34 (s, 2 H, ArH), 7.94
(s, 2 H, ArH), 7.90 (s, 2 H, ArH), 7.30–7.27 (m, 2 H, ArH), 7.24 (s, 2 H,
ArH), 6.89–6.84 (m, 2 H, ArH), 4.23 (t, J = 6.40 Hz, 8 H, OCH2), 1.97–
1.83 (m, 8 H, CH2), 1.61–1.51 (m, 8 H, CH2), 1.40–1.34 (m, 16 H, CH2),
0.94–0.89 (m, 12 H, CH3) ppm. HRMS (ESI): calcd. for C54H64F4O4
[M]+ 852.47; found 852.4738.
D7: The coupling of D0 (50 mg, 0.054 mmol) with (3,5-difluorophe-
nyl)boronic acid (20.69 mg, 0.131 mmol) resulted in D7 (40.5 mg,
1
87.4 %). H NMR (CDCl3, TMS, 400 MHz): δ = 8.32 (s, 2 H, ArH), 7.95
(s, 2 H, ArH), 7.90 (s, 2 H, ArH), 7.60–7.54 (m, 2 H, ArH), 7.44–7.41
(m, 2 H, ArH), 7.31–7.25 (m, 2 H, ArH), 4.24–4.21 (m, 8 H, OCH2),
1.96–1.82 (m, 8 H, CH2), 1.55–1.46 (m, 8 H, ArH), 1.39–1.34 (m, 16 H,
CH2), 0.94–0.89 (m, 12 H, CH3) ppm. HRMS (ESI): calcd. for
C54H64F4O4 [M]+ 852.47; found 852.4739.
D1: Under argon, D0 (100 mg, 0.11 mmol), phenylboronic acid
(30.8 mg, 0.262 mmol), K2CO3 (354.0 mg, 2.67 mmol), and Pd(PPh3)4
(15.8 mg, 0.01 mmol) were added to a reaction tube. Degassed
water (3 mL) and THF (10 mL) were injected into the reaction mix-
ture. The mixture was stirred at 80 °C for 24 h. Then, it was cooled, D8: The coupling of D0 (50 mg, 0.054 mmol) with (3,4,5-trifluoro-
extracted with EtOAc and dried with MgSO4. The organic solvent
was removed by distillation, and the residue was purified by silica
gel column chromatography (light petroleum/CH2Cl2 1:1) to yield
D1 as a white solid (68.5 mg, 80.7 %). The other compounds of the
phenyl)boronic acid (23.8 mg, 0.131 mmol) resulted in D8 (41.1 mg,
85.1 %). H NMR (CDCl3, TMS, 400 MHz): δ = 8.29 (s, 2 H, ArH), 7.93
(s, 2 H, ArH), 7.88 (s, 2 H, ArH), 7.36 (t, J = 7.20 Hz, 2 H, ArH), 4.23
(t, J = 6.40 Hz, 8 H, OCH2), 1.96–1.85 (m, 8 H, CH2), 1.56–1.49 (m, 8
1
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H, CH2), 1.40–1.36 (m, 16 H, CH2), 0.92 (t, J = 6.40 Hz, 12 H, CH3)
J = 7.6 Hz, 2 H, ArH), 7.79 (d, J = 8.0 Hz, 2 H, ArH), 7.67 (d, J =
6.8 Hz, 2 H, ArH), 7.30 (d, J = 7.6 Hz, 2 H, ArH), 7.24 (t, J = 6.8 Hz, 4
H, ArH), 4.10 (t, J = 6.0 Hz, 4 H, OCH2), 3.93 (t, J = 6.0 Hz, 4 H, OCH2),
1.78–1.65 (m, 8 H, CH2), 1.54 (s, 12 H, CH3), 1.51–1.36 (m, 8 H, CH2),
1.31–1.17 (m, 16 H, CH2), 0.89 (t, J = 6.4 Hz, 6 H, CH3), 0.84 (t, J =
6.4 Hz, 6 H, CH3) ppm. HRMS (ESI): calcd. for C72H84O4 [M]+ 1012.64;
found 1012.6372.
ppm. HRMS (ESI): calcd. for C54H62F6O4 [M]+ 888.46; found 888.4548.
D9: The coupling of D0 (100 mg, 0.11 mmol) with (3,4-dichloro-
phenyl)boronic acid (50.4 mg, 0.261 mmol) resulted in D9 (66.4 mg,
1
66.7 %). H NMR (CDCl3, TMS, 400 MHz): δ = 8.31 (s, 2 H, ArH), 7.92
(s, 2 H, ArH), 7.89 (s, 2 H, ArH), 7.84 (s, 2 H, ArH), 7.55 (t, J = 8.00 Hz,
4 H, ArH), 4.21 (t, J = 6.40 Hz, 8 H, OCH2), 1.96–1.82 (m, 8 H, CH2),
1.60–1.51 (m, 8 H, CH2), 1.39–1.35 (m, 16 H, CH2), 0.92 (t, J = 6.80 Hz,
12 H, CH3) ppm. HRMS (ESI): calcd. for C54H64Cl4O4 [M]+ 916.36;
found 916.3556.
D16: The coupling of D0 (100 mg, 0.11 mmol) with [4-(9H-carbazol-
9-yl)phenyl]boronic acid (74.9 mg, 0.261 mmol) resulted in D16
1
(81.2 mg, 66.4 %). H NMR (CDCl3, TMS, 400 MHz): δ = 8.54 (s, 2 H,
ArH), 8.21 (d, J = 7.60 Hz, 4 H, ArH), 8.08 (s, 2 H, ArH), 8.04 (s, 2 H,
ArH), 8.01 (d, J = 2.00 Hz, 2 H, ArH), 7.99 (d, J = 2.00 Hz, 2 H, ArH),
7.73 (d, J = 2.00 Hz, 2 H, ArH), 7.72 (d, J = 2.00 Hz, 2 H, ArH), 7.60
(d, J = 8.00 Hz, 4 H, ArH),7.47 (t, J = 8.00 Hz, 4 H, ArH), 7.34 (t, 4 H,
ArH), 4.35–4.26 (m, 8 H, OCH2), 2.00–1.91 (m, 8 H, CH2), 1.60–1.53
(m, 8 H, CH2), 1.45–1.35 (m, 16 H, CH2), 0.94–0.91 (m, 12 H, CH3)
ppm. HRMS (ESI): calcd. for C78H82N2O4 [M]+ 1110.63; found
1110.6273.
D10: The coupling of D0 (30 mg, 0.033 mmol) with (4-pentyl-
phenyl)boronic acid (15.0 mg, 0.078 mmol) resulted in D10
(23.5 mg, 77.3 %). H NMR (CDCl3, TMS, 400 MHz): δ = 8.39 (s, 2 H,
ArH), 7.97 (s, 2 H, ArH), 7.93 (s, 2 H, ArH), 7.66 (d, J = 8.00 Hz, 4 H,
ArH), 7.33 (d, J = 8.00 Hz, 4 H, ArH), 4.20 (d, J = 4.00, 8 Hz, OCH2),
2.71 (t, J = 8.00 Hz, 4 H,CH2), 1.53–1.48 (m, 12 H,CH2), 1.41–1.34 (m,
24 H, CH2), 0.95–0.90 (m, 18 H, CH3) ppm. HRMS (ESI): calcd. for
C64H88O4 [M]+ 920.67; found 920.6679.
1
D17: The coupling of D0 (100 mg, 0.11 mmol) with [3-(9H-carbazol-
9-yl)phenyl]boronic acid (74.9 mg, 0.261 mmol) resulted in D17
(59.6 mg, 48.8 %). H NMR (CDCl3, TMS, 400 MHz): δ = 8.47 (s, 2 H,
D11: The coupling of D0 (50 mg, 0.054 mmol) with (3,4-dimethoxy-
phenyl)boronic acid (23.9 mg, 0.131 mmol) resulted in D11
(38.7 mg, 79.1 %). H NMR (CDCl3, TMS, 400 MHz): δ = 8.38 (s, 2 H,
ArH), 7.98 (s, 2 H, ArH), 7.94 (s, 2 H, ArH), 7.34 (d, J = 2.00 Hz, 2 H,
ArH), 7.28 (d, J = 4.00 Hz, 1 H, ArH), 7.26 (d, J = 2.00 Hz, 1 H, ArH),
7.04 (s, 1 H, ArH), 7.02 (s, 1 H, ArH), 4.23–4.18 (m, 8 H, OCH2), 3.98
(d, J = 5.2.0 Hz, 12 H, OCH3), 1.94–1.84 (m, 8 H, CH2), 1.58–1.49 (m,
8 H, CH2), 1.38–1.33 (m, 16 H, CH2), 0.93–0.88 (m, 12 H, CH3) ppm.
HRMS (ESI): calcd. for C58H76O8 [M]+ 900.55; found 900.5538.
1
1
ArH), 8.18 (d, J = 7.60 Hz, 4 H, ArH), 8.00 (t, J = 2.00 Hz, 4 H, ArH),
7.94 (s, 2 H, ArH), 7.83 (s, 1 H, ArH), 7.81 (s, 1 H, ArH), 7.74 (d, J =
8.00 Hz, 2 H, ArH), 7.60 (t, J = 8.00 Hz, 4 H, ArH), 7.56 (s, 2 H, ArH),
7.43 (t, J = 8.00 Hz, 4 H, ArH), 7.31 (t, J = 7.60 Hz, 4 H, ArH), 4.28–
4.20 (m, 8 H, OCH2), 1.95–1.85 (m, 8 H, CH2), 1.45–1.36 (m, 16 H,
CH2), 1.29–1.17 (m, 8 H, CH2), 0.90 (t, J = 7.20 Hz, 6 H, CH3), 0.82 (t,
J = 7.20 Hz, 6 H, CH3) ppm. HRMS (ESI): calcd. for C78H82N2O4 [M]+
1110.63; found 1110.6272.
D12: The coupling of D0 (50 mg, 0.054 mmol) with [3,4-bis(pentyl-
oxy)phenyl]boronic acid (38.34 mg, 0.131 mmol) resulted in D12
3,6,7,10,11-Pentakis(hexyloxy)triphenylen-2-yl Triflate (M0): To
a solution of triphenylen-2-ol (2.0 g, 2.68 mmol) in CH2Cl2 (60 mL)
was added triethylamine (2.23 mL) at room temperature under ar-
gon. The mixture was stirred for 10 min, and Tf2O (2.3 mL,
13.4 mmol) was added at –40 °C. The mixture was warmed to room
temperature and stirred for 6 h. The reaction mixture was filtered,
and the filtrate was concentrated in vacuo. The residue was purified
by column chromatography (light petroleum/CH2Cl2 1:1) to afford
1
(40.5 mg, 87.4 %). H NMR (CDCl3, TMS, 400 MHz): δ = 8.37 (s, 2 H,
ArH), 7.96 (s, 2 H, ArH), 7.93 (s, 2 H, ArH), 7.34 (d, J = 4.00 Hz, 2 H,
ArH), 7.25 (d, J = 4.00 Hz, 1 H, ArH), 7.23 (d, J = 4.00 Hz, 1 H, ArH),
7.03 (s, 1 H, ArH), 7.01 (s, 2 H, ArH), 4.20 (dd, J = 8.00, 4.00 Hz, 8 H,
OCH2), 4.11–4.07 (m, 8 H, OCH2), 1.95–1.82 (m, 16 H, CH2), 1.55–
1.33 (m, 40 H, CH2), 0.98–0.90 (m, 24 H, CH3) ppm. HRMS (ESI): calcd.
for C74H108O8 [M]+ 1124.80; found 1124.8045.
1
D13: The coupling of D0 (50 mg, 0.054 mmol) with [4-(diphenyl-
amino)phenyl]boronic acid (37.9 mg, 0.131 mmol) resulted in D13
(37 mg, 61.1 %). 1H NMR (C6D6, TMS, 400 MHz): δ = 8.43 (s, 2 H,
ArH), 7.82 (s, 2 H, ArH), 7.77 (s, 2 H, ArH), 7.41 (d, J = 2.00 Hz, 2 H,
ArH), 7.39 (d, J = 2.00 Hz, 2 H, ArH), 6.88 (d, J = 2.00 Hz, 2 H, ArH),
6.87 (d, J = 2.00 Hz, 2 H, ArH), 6.77 (dd, J = 1.20, 8.80 Hz, 8 H, ArH),
6.66 (t, J = 7.20 Hz, 8 H, ArH), 6.46 (t, J = 7.20 Hz, 4 H, ArH), 3.62 (t,
J = 6.40 Hz, 4 H, OCH2), 3.45 (t, J = 6.40 Hz, 4 H, OCH2), 1.35–1.23
(m, 8 H, CH2), 1.12–1.06 (m, 4 H, CH2), 1.04–0.96 (m, 4 H, CH2), 0.94–
0.79 (m, 16 H, CH2), 0.52–0.46 (m, 12 H, CH3) ppm. HRMS (ESI): calcd.
for C78H86N2O4 [M]+ 1114.66; found 1114.6588.
the triphenylen-2-yl triflate as a gray solid, yield 1.96 g (83.4 %). H
NMR (CDCl3, TMS, 400 MHz): δ = 8.18 (s, 1 H, ArH), 7.85 (s, 1 H, ArH),
7.80 (s, 1 H, ArH), 7.79 (s, 2 H, ArH), 7.69 (s, 1 H, ArH), 4.28–4.21 (m,
10 H, OCH2), 1.99–1.91 (m, 10 H, CH2), 1.60–1.59 (m, 10 H, CH2),
1.45–1.37 (m, 20 H, CH2), 0.94 (t, J = 6.8 Hz, 15 H, CH3) ppm. HRMS:
calcd. for C49H71F3O8S [M]+ 876.48; found 876.4819.
M1: Under argon, M0 (150 mg, 0.171 mmol), (4-pentylphenyl)-
boronic acid (39.4 mg, 0.205 mmol), K2CO3 (354.0 mg, 2.67 mmol),
and Pd(PPh3)4 (15.8 mg, 0.0574 mmol) were added to a reaction
tube. Degassed water (3 mL) and THF (10 mL) were injected into
the reaction mixture. The mixture was stirred at 80 °C for 24 h,
cooled, extracted with EtOAc, and dried with MgSO4. The organic
solvent was removed by distillation, and the residue was purified
by silica gel column chromatography (light petroleum/CH2Cl2 1:1)
to afford M1 as a white solid (140.3 mg, 93.6 %). The other com-
pounds of the series, M2–M5, were all prepared accordingly. 1H
NMR (CDCl3, TMS, 400 MHz): δ = 8.37 (s, 1 H, ArH), 7.93 (s, 2 H, ArH),
7.84 (s, 3 H, ArH), 7.65 (d, J = 8 Hz, 1 H, ArH), 7.32 (d, J = 8 Hz, 2 H,
ArH), 4.25–4.19 (m, 10 H, OCH2), 2.70 (t, J = 7.6 Hz, 2 H, CH2), 1.99–
1.90 (m, 8 H, CH2), 1.87–1.80 (m, 2 H, CH2), 1.75–1.67 (m, 2 H, CH2),
1.63–11.47 (m, 10 H, CH2), 1.41–1.25 (m, 26 H, CH2), 0.96–0.87 (m,
18 H, CH2) ppm. HRMS (ESI): calcd. for C59H86O5 [M]+ 874.65; found
874.6420.
D14: The coupling of D0 (100 mg, 0.11 mmol) with (9-phenyl-9H-
carbazol-3-yl)boronic acid (74.9 mg, 0.261 mmol) resulted in D14
1
(65.9 mg, 58.7 %). H NMR (CDCl3, TMS, 400 MHz): δ = 8.53 (s, 2 H,
ArH), 8.21 (s, 2 H, ArH), 8.19 (s, 2 H, ArH), 8.08 (s, 2 H, ArH), 8.01 (t,
J = 9.60 Hz, 6 H, ArH), 7.73 (d, J = 8.40 Hz, 4 H, ArH), 7.59 (t, J =
8.40 Hz, 4 H, ArH), 7.49–7.45 (m, 4 H, ArH), 7.33 (t, J = 7.20 Hz, 4 H,
ArH), 4.34–4.26 (m, 8 H, OCH2), 1.99–1.90 (m, 8 H, CH2), 1.59–1.54
(m, 8 H, CH2), 1.43–1.37 (m, 16 H, CH2), 0.92 (t, J = 7.20 Hz, 12 H,
CH3) ppm. HRMS (ESI): calcd. for C78H82N2O4 [M]+ 1110.63; found
1110.6275.
D15: The coupling of D0 (100 mg, 0.11 mmol) with (9,9-dimethyl-
9H-fluoren-2-yl)boronic acid (74.9 mg, 0.261 mmol) resulted in D15
1
(53.5 mg, 48.4 %). H NMR (C6D6, TMS, 400 MHz): δ = 8.92 (s, 2 H,
M2: The coupling of M0 (150 mg, 0.171 mmol) with [3,4-bis(pentyl-
oxy)phenyl]boronic acid (60.3 mg, 0.205 mmol) resulted in M2
ArH), 8.39 (s, 2 H, ArH), 8.23 (s, 2 H, ArH), 8.09 (s, 2 H, ArH), 7.89 (d,
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1
(152.1 mg, 91 %). H NMR (CDCl3, TMS, 400 MHz): δ = 8.35 (s, 1 H,
J = 15.2 Hz, 18 H, CH3) ppm. HRMS (ESI): calcd. for C69H90O3 [M]+
ArH), 7.93 (s, 2 H, ArH), 7.86 (d, J = 8 Hz, 3 H, ArH), 7.32 (d, J = 2, 966.69; found 966.6888.
0.5 Hz), 7.21 (dd, J = 1.6, J = 8.4 Hz, 1 H, ArH), 7.02 (d, J = 8.4 Hz, 1
T2: The coupling of T0 (50 mg, 0.054 mmol) with [3,4-bis(pentyl-
H, ArH), 4.27–4.17 (m, 10 H, OCH2), 4.11–4.06 (m, 4 H, OCH2), 1.99–
1.81 (m, 16 H, CH2), 1.63–1.32 (m, 45 H, CH2), 0.98–0.86 (m, 21 H,
CH2) ppm. HRMS (ESI): calcd. for C64H96O7 [M]+ 976.72; found
976.7035.
oxy)phenyl]boronic acid (57.2 mg, 0.194 mmol) resulted in T2
1
(46.1 mg, 67.1 %). H NMR (CDCl3, TMS, 400 MHz): δ = 8.45 (s, 3 H,
ArH), 7.98 (s, 3 H, ArH), 7.34 (s, 3 H, ArH), 7.25 (d, J = 8.4 Hz, 3 H,
ArH), 7.04 (d, J = 8.4 Hz, 3 H, ArH), 4.18 (t, J = 6.4 Hz, OCH2), 4.10
(dd, J = 6.4, J = 4.4 Hz, 12 H, OCH2), 1.93–1.80 (m, 18 H, CH2), 1.57–
1.38 (m, 34 H, CH2), 1.33–1.32 (m, 12 H, CH2), 0.98–0.89 (m, 27 H,
CH3) ppm. HRMS (ESI): calcd. for C84H120O9 [M]+ 1272.89; found
1272.8929.
M3: The coupling of M0 (50 mg, 0.057 mmol) with [4-(diphenyl-
amino)phenyl]boronic acid (19.8 mg, 0.068 mmol) resulted in M3
(36.8 mg, 72 %). 1H NMR (CDCl3, TMS, 400 MHz): δ = 8.38 (s, 1 H,
ArH), 7.95 (s, 1 H, ArH), 7.93 (s, 1 H, ArH), 7.87 (s, 1 H, ArH), 7.84 (s,
2 H, ArH), 7.64 (d, J = 8.4 Hz, 2 H, ArH), 7.29 (t, J = 7.6 Hz, 4 H, ArH),
7.20 (d, J = 8.0 Hz, 6 H, ArH), 7.05 (t, J = 7.2 Hz, 2 H, ArH), 4.23 (dd,
J = 7.6, J = 14.4 Hz, 10 H, OCH2), 1.98–1.82 (m, 10 H, CH2), 1.63–
1.48 (m, 10 H, CH2), 1.41–1.33 (m, 20 H, CH2), 0.96–0.88 (m, 15 H,
CH2) ppm. HRMS (ESI): calcd. for C66H85NO5 [M]+ 971.64; found
971.6428.
T3: The coupling of T0 (100 mg, 0.18 mmol) with [4-(diphenyl-
amino)phenyl]boronic acid (112.4 mg, 0.389 mmol) resulted in T3
(114.9 mg, 84.5 %). 1H NMR (CDCl3, TMS, 400 MHz): δ = 8.52 (s, 3 H,
ArH), 7.80 (s, 3 H, ArH), 7.43 (d, J = 8.4 Hz, 6 H, ArH), 8.91 (d, J =
8.8 Hz, 6 H, ArH), 6.79 (d, J = 5.6 Hz, 12 H, ArH), 6.68 (t, J = 7.6 Hz,
12 H, ArH), 6.48 (t, J = 7.2 Hz, 6 H, ArH), 3.37 (t, J = 6.00 Hz, OCH2),
1.21–1.14 (m, 6 H, CH2), 1.00–0.91 (m, 6 H, CH2), 0.91–0.80 (m, 12
H, CH2), 0.51 (t, J = 7.2 Hz, 9 H, CH3) ppm. HRMS (ESI): calcd. for
C90H87N3O3 [M]+ 1257.67; found 1257.6748.
M4: The coupling of M0 (150 mg, 0.171 mmol) with [4-(9H-carbazol-
9-yl)phenyl]boronic acid (58.9 mg, 0.205 mmol) resulted in M4
1
(142.5 mg, 93.1 %). H NMR (C6D6, TMS, 400 MHz): δ = 8.48 (s, 1 H,
ArH), 8.20 (s, 1 H, ArH), 8.18 (s, 1 H, ArH), 8.00 (s, 1 H, ArH), 7.96 (d,
J = 1.2 Hz, 2 H, ArH), 7.95 (d, J = 5.6 Hz, 2 H, ArH), 7.87 (s, 2 H, ArH),
7.70 (d, J = 4.4 Hz, 2 H, ArH), 7.58 (d, J = 8.0 Hz, 2 H, ArH), 7.46 (t,
J = 8.0 Hz, 2 H, ArH), 7.32 (t, J = 7.6 Hz, 2 H, ArH), 4.29–4.24 (m, 10
H, OCH2), 2.01–1.87 (m, 10 H, CH2), 1.64–1.51 (m, 10 H, CH2), 1.47–
1.34 (m, 20 H, CH2), 0.97–0.89 (m, 15 H, CH3) ppm. HRMS (ESI): calcd.
for C66H83NO5 [M]+ 969.63; found 969.6268.
T4: The coupling of T0 (50 mg, 0.054 mmol) with (9,9-dimethyl-
9H-fluoren-2-yl)boronic acid (55.7 mg, 0.194 mmol) resulted in T4
(36.9 mg, 61.9 %). H NMR (C6D6, TMS, 400 MHz): δ = 8.99 (s, 3 H,
ArH), 8.27 (s, 3 H, ArH), 8.11 (s, 3 H, ArH), 7.90 (d, J = 8.0 Hz, 3 H,
ArH), 7.79 (d, J = 7.6 Hz, 3 H, ArH), 7.65 (d, J = 7.6 Hz, 3 H, ArH),
7.30 (d, J = 6.8 Hz, 3 H, ArH), 7.24 (dd, J = 6.8, J = 2.0 Hz, 6 H, ArH),
3.90 (t, J = 6.0 Hz, 6 H, OCH2), 1.63–1.57 (m, 6 H, CH2), 1.54 (s, 18
H, CH3), 1.37–1.30 (m, 6 H, CH2), 1.24–1.11 (m, 12 H, CH2), 0.82 (t,
J = 6.8 Hz, 9 H, CH3) ppm. HRMS (ESI): calcd. for C81H84O3 [M]+
1104.64; found 1104.6418.
1
M5: The coupling of M0 (50 mg, 0.057 mmol) with (9,9-dimethyl-
9H-fluoren-2-yl)boronic acid (16.3 mg, 0.068 mmol) resulted in M5
1
(31.6 mg, 60.1 %). H NMR (C6D6, TMS, 400 MHz): δ = 8.90 (s, 1 H,
ArH), 8.35 (s, 1 H, ArH), 8.25 (d, J = 3.6 Hz, 2 H, ArH), 8.20 (d, J =
4.0 Hz, 2 H, ArH), 8.08 (s, 1 H, ArH), 7.89 (d, J = 8.0 Hz, 1 H, ArH),
7.79 (d, J = 7.6 Hz, 1 H, ArH), 7.67 (d, J = 7.6 Hz, 1 H, ArH), 7.29–
7.21 (m, 3 H, ArH), 4.18 (t, J = 6.4 Hz, 2 H, OCH2), 4.14–4.08 (m, 4 H,
OCH2), 4.02 (t, J = 6.4 Hz, 2 H, OCH2), 3.93 (t, J = 6.4 Hz, 2 H, OCH2),
1.90–1.80 (m, 6 H, CH2), 1.79–1.72 (m, 2 H, CH2), 1.68–1.63 (m, 2 H,
CH2), 1.59–1.56 (m, 2 H, CH2), 1.53 (s, 6 H, CH3), 1.49–1.42 (m, 4 H,
CH2), 1.40–1.16 (m, 24 H, CH2), 0.91 (dd, J = 12, 5.6 Hz, 12 H, CH3),
0.83 (t, J = 6.4 Hz, 3 H, CH3) ppm. HRMS (ESI): calcd. for C63H84O5
[M]+ 920.63; found 920.6318.
Supporting Information (see footnote on the first page of this
article): Phase diagrams; summary of thermotropic behavior; 1H
NMR, HRMS, and emission spectra.
Acknowledgments
This work was financially supported by the National Natural Sci-
ence Foundation of China (NSFC) (grant numbers 51443004,
51273133). B. D. and B. H. thank the Centre National de la Re-
cherche Scientifique (CNRS) and the Université de Strasbourg,
France for support.
3,7,11-Tris(hexyloxy)triphenylene-2,6,10-triyl Triflate (T0): To a
solution of TP-2,6,10-triol (600 mg, 1.04 mmol) in CH2Cl2 (30 mL)
was added triethylamine (0.86 mL, 8.32 mmol) at room temperature
under an argon atmosphere. The mixture was stirred for 10 min,
and Tf2O (2.63 mL, 15.6 mmol) was added at –40 °C. The mixture
was warmed to room temperature and stirred for 6 h. The reaction
mixture was filtered, and the filtrate was concentrated in vacuum.
The residue was purified by column chromatography (light petro-
leum/CH2Cl2 1:3) to yield the product T0 as a white solid, yield
Keywords: Self-assembly · Liquid crystals · Mesophases ·
Cross-coupling · Polycycles
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739.
900.4 mg (93.3 %). H NMR (CDCl3, TMS, 400 MHz): δ = 8.01 (t, J =
5.6 Hz, 3 H, ArH), 7.52 (t, J = 7.00 Hz, 3 H, ArH), 4.24 (t, J = 6.4 Hz,
6 H, OCH2), 2.01–1.93 (m, 6 H, CH2), 1.62–1.54 (m, 8 H, CH2), 1.44–
1.40 (m, 12 H, CH2), 0.96 (t, J = 7.2 Hz, 9 H, CH3) ppm.
T1: The coupling of TP-2,6,10-triyl triflate (50 mg, 0.054 mmol) with
(4-pentylphenyl)boronic acid (37.3 mg, 0.194 mmol) resulted in T1
(40.8 mg, 78.2 %). The other compounds of the series, T2–T4, were
prepared accordingly. 1H NMR (CDCl3, TMS, 400 MHz): δ = 8.46 (s,
3 H, ArH), 7.97 (s, 3 H, ArH), 7.67 (d, J = 7.6 Hz, 6 H, ArH), 7.33 (d,
J = 8.00 Hz, 6 H, ArH), 4.17 (t, J = 6.4 Hz, 6 H, OCH2), 2.70 (t, J =
7.6 Hz, 6 H, CH2), 1.86–1.79 (m, 6 H, CH2), 1.75–1.68 (m, 6 H, CH2),
1.42–1.39 (m, 12 H, CH2), 1.34–1.31 (m, 10 H, CH2), 0.92 (dd, J = 8.4,
[11] B. R. Kaafarani, Chem. Mater. 2011, 23, 378–396.
Eur. J. Org. Chem. 2016, 2802–2814
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© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

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Received: March 8, 2016
Published Online: April 13, 2016
Eur. J. Org. Chem. 2016, 2802–2814
www.eurjoc.org
2814
© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim