Board-like Fused-Thiophene Liquid Crystals and their Benzene Analogs: Facile Synthesis, Self-Assembly, p-Type Semiconductivity, and Photoluminescence

Article abstract of DOI:10.1002/asia.201801483

Fused-thiophene discotic liquid crystals were designed and easily synthesized by Suzuki coupling and FeCl₃ oxidized tandem cyclodehydrogenation reactions, including homo- and cross-coupling reactions. The resulting hexagonal and rectangular columnar mesomorphic supramolecular structures formed were characterized by polarizing optical microscopy, differential scanning calorimetry, and small-angle X-ray scattering. The charge carrier transport properties in the mesophases of two of the synthesized fused-thiophene discogens were measured by transient photocurrent time-of-flight (TOF) technique, revealing fast hole transport values in the range of 10^?3 to 10^?2 cm² V^?1 s^?1, thus demonstrating potential applications in electronic devices. The luminescent sanidic mesogens, with different extended π-conjugated systems, also emit blue, green, or red light, with absolute photoluminescent quantum yields as high as 18 %.

Full text of DOI:10.1002/asia.201801483

CHEMISTRY
AN ASIAN JOURNAL
www.chemasianj.org
Accepted Article
Title: Board-like Fused-Thiophene Liquid Crystals and Their
Benzene Analogues: Facile Synthesis, Self-assembly, p-Type
Semiconductivity, and Photoluminescence
Authors: Bertrand Donnio, Kai Chun Zhao, Jun Qi Du, Hai Feng Wang,
Ke Qing Zhao, Ping Hu, Bi Qin Wang, Hirosato Monobe, and
Benoît Heinrich
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To be cited as: Chem. Asian J. 10.1002/asia.201801483
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Chemistry - An Asian Journal
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FULL PAPER
Board-like Fused-Thiophene Liquid Crystals and Their Benzene
Analogues: Facile Synthesis, Self-assembly, p-Type
Semiconductivity, and Photoluminescence
[
a]
[a]
[a]
[a]
[a]
[a]
Kai-Chun Zhao, Jun-Qi Du, Hai-Feng Wang, Ke-Qing Zhao,* Ping Hu, Bi-Qin Wang, Hirosato
[b]
[c]
[c]
Monobe,* Benoît Heinrich, and Bertrand Donnio*
Abstract: Novel fused-thiophene discotic liquid crystals were
polymer and plays a key role in plastic electronics,[5] while poly-
designed and easily synthesized by Suzuki coupling and FeCl
3
3-hexylthiophene (P3HT) as a p-type organic semiconductors
when paired with the n-type C60 fullerene derivatives exhibits
superior performance in organic photovoltaic solar cells.[6]
oxidized tandem cyclo-dehydrogenation reactions, including homo-
and cross-coupling reactions. The resulting hexagonal and
rectangular columnar mesomorphic supramolecular structures
formed were characterized by polarizing optical microscopy,
differential scanning calorimetry, and small-angle X-ray scattering.
Charge carrier transport properties in the mesophases of two of the
synthesized fused-thiophene discogens were measured by transient
photocurrent time-of-flight (TOF) technique, revealing fast hole
Oligothiophene derivatives end-capped with alkyl chains, show
liquid crystalline properties,[7-20] and prefer to self-organize into
supramolecular ordered layered structures: they display two-
dimensional charge transport mobility comparable to inorganic
semiconductors of amorphous and polycrystalline silicon, and
have been investigated as active materials in organic field-effect
transistors (OFET).[21-25] Discotic liquid crystals (DLCs) [26-29]
which contain a fused-thiophene unit [30-46] are also attractive
candidates as novel organic semiconductors due to their
advantageous combination of the highly applicable and promising
electronic properties of the thiophene moiety and the propensity
of DLCs to self-organize into columnar mesophase for one-
dimensional charge transport pathways.[26] However, the
number of thiophene-containing DLCs is still limited compared to
the numerous rod-like liquid crystals incorporating a thiophene
unit. We report here the design and synthesis of such discotic
systems by combined Suzuki and Scholl coupling reactions.
Novel molecular design, supported by facile and efficient
synthetic strategies for the construction of thiophene-fused DLCs
are highly desirable for the discovery of new materials and for
modulating the applicable physical properties. Here, a simple,
direct and highly efficient synthetic route for the preparation of
-
3
-2
2
-1 -1
transport values in the range of 10 to 10 cm V s , thus
demonstrating potential applications in electronic devices. The
luminescent sanidic mesogens, having different extended -
conjugated systems, also emit blue, green or red light, with absolute
photoluminescent quantum yields as high as 18%.
Introduction
Thiophene-containing -conjugated aromatics [1,2] and
polythiophene derivatives [3,4] are important basic molecular
components of organic semiconductors. Polythiophenes as
polymeric semiconductors become electrical conductors when
doped: poly(3,4-ethylenedioxythiophene) (PEDOT) doped with
polystyrene sulfuric acid becomes conjugated conducting
novel
fused-thiophene
DLCs
by
(cross)
oxidative
cyclodehydrogenation is reported (5-8, Scheme 1). This route
was used in parallel for the preparation of the benzene and
biphenylene analogues (9-10, Scheme 2). The mesomorphism
and thermal behavior of all the compounds were characterized by
polarizing optical microscopy (POM), differential scanning
calorimetry (DSC), and small-angle X-ray scattering (SAXS), and
the self-organizational behavior of the two series of dumbbell-
shaped discotic compounds, with half-disc-like mesogens either
rigidly joined by fused rings (compounds 5, 7 and 9), or connected
by a sigma bond through fused ring extenders (compounds 6, 8
and 10) was compared. The molecular structure-mesomorphism
relationship is discussed and the unique effect of thiophene on
the mesomorphism is stressed. Furthermore, this synthetic
strategy was successfully extended to the synthesis of a novel
unsymmetrical discogen 11, and is also described (Scheme 3).
Semiconductive property measured by photocurrent time-of-flight
technique are also reported for two representative compounds,
namely a discotic columnar mesogen (5) and a discotic dimer (6),
revealing rather high, one-dimensional charge carrier mobility in
[
[
[
a]
b]
b]
Mr K.-C. Zhao, Mr J.-Q. Du, Mr H.-F. Wang, Prof K.-Q. Zhao*, Prof
P. Hu and Prof B.-Q. Wang
College of Chemistry and Materials Science,
Sichuan Normal University
Chengdu 610066, China
E-mail: kqzhao@sicnu.edu.cn
Prof H. Monobe*
Inorganic Functional Materials Research Institute
National Institute of Advanced Industrial Science and Technology
(AIST)
Ikeda, Osaka 563-8577, Japan
E-mail: monobe-hirosato@aist.go.jp
Dr B. Heinrich and Dr B. Donnio*
Institut de Physique et Chimie des Matériaux de Strasbourg
(
IPCMS)
CNRS-University de Strasbourg (UMR 7504)
3 rue du Loess, BP43 67034 Strasbourg, Cedex 2, France
2
E-mail: bertrand.donnio@ipcms.unistra.fr
Supporting information for this article is given via a link at the end of
the document.
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the range of 10 ~10 cm V s-1. These sanidic mesogens are
also luminescent and emit blue, green or red light, with absolute
photoluminescent quantum yields as high as 18%.
-
3
-2
2
-1
Scheme 1. Synthesis of fused-thiophene and dimeric discogens 5-8: i) Br2,
CH
2 2 3 4 2 3 2 3 2 2 2
Cl , 0°C; ii) Pd(PPh ) , K CO , H O/THF, 80°C; iii) FeCl , MeNO /CH Cl ,
RT.
Results and Discussion
Synthesis and characterization. The key compound for this
synthesis is 2-bromo-3',4,4',5-tetrakis(pentyloxy)-1,1'-biphenyl (2,
Schemes 1 and 2), which is readily obtained in good yield (> 85%)
from the bromination of 3,3’,4,4’-tetrakis(pentyloxy)-1,1’-biphenyl,
1, in one step, as already reported previously.[47] Running the
reaction above -5°C or using excess liquid bromine resulted in
dibromination of the biphenyl, reducing substantially the yield of 2
and making purification by column chromatography more difficult.
Palladium-catalyzed Suzuki cross-coupling reaction of various
arylboronic acids (e.g. thiophene-3-boronic acid, thieno[3,2-
b]thiophene-2-boronic acid, 1,4-phenyldiboronic acid, 4,4’-
biphenylboronic acid) with 2 was first applied to produce the
corresponding mono-substituted compounds 3a-d in yields of 70-
Scheme 2. Synthesis of π-extended discogen 9 and triphenylene dimer 10: ii)
Pd(PPh , K CO , H O/THF, 80°C; iii) FeCl , MeNO /CH Cl , RT.
)
3 4
2
3
2
3
2
2
2
9
0 % (Schemes 1 and 2, respectively).
Then, oxidative cyclodehydrogenation of 3a-d was followed, for
which the amount of oxidizing agent, FeCl , was found to crucially
affect the reaction yields. The amount of FeCl used was actually
The intermediates 4a and 4b were prepared by the intramolecular
Scholl reaction of 3a and 3b with 2 equiv. of FeCl at room
3
3
3
temperature, in yields of 77 % and 81 %, respectively, along with
the formation of small amounts of dimeric products, 6 and 8
determined by the number of C-C bond formed and hydrogen
atoms eliminated: for each C-C bond formation, two H-atoms
(
3
Scheme 1). Excess FeCl or running the reaction longer time
were eliminated, and two equiv. FeCl
FeCl (50 mg) in CH NO (0.5 mL) was prepared before use, and
the substrates were dissolved in CHCl or CH Cl . The reactions,
3
were used. The solution of
resulted in decreased yields. Intermolecular oxidative cross-
coupling reactions of 4a and 4b in the presence of the biphenyl
derivative 1 produced 5 and 7, respectively. In this reaction, the
substrate ratio of fused-thiophene (4a and 4b) with biphenyl 1 was
3
3
2
3
2
2
monitored by thin-layer chromatography, were completed in 1h at
room temperature.
3
1:1, and four equiv. of FeCl were used. Production of dimeric
compounds 6 and 8 was also observed, both oxidative cross-
coupling and homo-coupling reactions being in competition as the
α-position of the (fused) thiophene is also more reactive. As the
homo-coupled products 6 and 8 are less soluble than the cross-
coupled products 5 and 7, increasing the solvent was found to
favor the formation of the former (5 and 7). When the amount of
FeCl
was promoted over the intermolecular coupling, and compounds
and 7 were obtained with yields of 40% and 45%, respectively,
3
was lowered, the oxidative dimerization products 6 and 8
5
whereas dimers 6 and 8 were formed simultaneously with similar
yields of 45% and 43%, respectively. Thus, the overall
transformations of 4a and 4b are higher than 80%. Note that the
direct coupling of 3a and 3b with biphenyl 1 also produced 5 and
7
, but in yields lower than 5%, whereas when more than 6 equiv.
of FeCl were used, 6 and 8 were obtained as the major products.
Compounds 6 and 8 were synthesized by the direct oxidative
homo-coupling of 4a and 4b with 2 equiv. of FeCl in 65% and
5% yields, respectively. The most efficient transformation of 3a
3
3
5
and 3b to 6 and 8 (66% and 58%, respectively) was achieved by
tandem intra- and inter-molecular coupling reactions with 4 equiv.
of FeCl
Similarly, compounds 9 and 10 were directly prepared by the
FeCl (4 equiv.) oxidative cyclodehydrogenation of 3c and 3d,
3
.
3
respectively. After the reaction was finished, 9 and 10 precipitated
from the solution as white powders, due to the decreased
solubility in organic solvents as compared to the starting
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compounds 3c and 3d. Pure regioisomers 9 and 10 were isolated
in good yields (80 and 90%, respectively) after filtration and
abundant washing with water, de-coloring by active carbon and
recrystallization.
aromatic cores into a twin extended structure which can easily
stack, whereas 5, although possesses a fused aromatic core, but
due to the presence of the meta alkoxy chains pointing towards
the cavity, has a non-planar, twisted core and therefore presents
weaker - intermolecular interactions. The most stable
molecular conformations of 5 ~ 8 calculated by density functional
theory (B3LYP-D3/6-311++**), shown in Tables S1-2, further
support these experimental results. The DFT calculated
molecular structures show that the single aromatic core of 5 is
indeed not flat, while for dimers 6 and 8, the two aromatic cores
connected through a sigma-bond, are in contrast planar. Although
the dimeric molecules may not be planar, the flexibility of the
sigma bond allows stacking of the constitutive flat cores in solution
due to the favourable face-to-face - interactions. The shift and
The strategy used for the preparation of 5 suggested the
possibility to also prepare related unsymmetrical discogenic
compounds, with two edges of different chemical natures. We
successfully tested this possibility by reacting 4a with another
biphenylene derivative (1F, Scheme 3) through the tandem
intramolecular and intermolecular Scholl reaction. Without
optimizing the synthetic conditions, compound 11 was prepared
in moderate yields, ca. 34%, showing the great potential of this
tandem reaction to be exploited for the design of a large range of
novel types of Janus compounds, with modified and adapted
properties, such as solubility, wettability, self-organization, phase
1
broadening of their H NMR signals is likely the signature of the
transition temperatures, of both fundamental and applied interests. aggregation of 6 and 8 in solution, as observed frequently for
other polycyclic aromatic hydrocarbons (PAHs).
Scheme 3. One-pot synthesis of low-symmetry discogen 11 by tandem
intramolecular and intermolecular Scholl reaction. i) FeCl , CH Cl , MeNO .
3 2 2 2
All the intermediates, and the target compounds have been fully
characterized by NMR (Figures S1-14) and HRMS (Figures S15-
21), and the results are in good agreement of the chemical
structures. No positional isomers were observed, otherwise
different from the reported phenomena.[48]
Molecular conformation and aggregation in organic solvents.
Polycyclic aromatic hydrocarbons usually tend to aggregate in
organic solvents due to strong intermolecular interactions, which
depend essentially on the size and planarity of the aromatic core.
The synthesized fused thiophene discotic compounds described
here possess these features and therefore were expected to
strongly aggregate in solution.
The aggregation behavior in solution of compounds 5, 6 and 8,
has been examined by 1H NMR, and their concentration-
dependent spectra are shown in Figure 1 (and Figure S22). The
strong tendency for the aggregation behavior is evidenced in
spectra of compounds 6 and 8: as the concentration of 6 or 8 in
6 6
C D increases (from 5 to 15 mg/mL), the chemical shift values of
the aromatic protons move to upper field with lower value of
chemical shift value; for 8 this tendency is even stronger, as the
proton signals become broadened and unresolved (Figure S22).
In contrast, compound 5 in CDCl
3
shows no aggregation behavior
1
in solution, as evidenced by the invariance of the H NMR spectra
aromatic signals with increasing of the concentration (Figure 1).
These observations are in agreement with the molecular
structures of the compounds: 6 and 8 both have a similar structure
that consists of a sigma-bond connecting two discotic fused flat
Figure 1. Aromatic region of the 1H NMR spectra at different concentrations of
compound: (a) 5 in CDCl , (b) 6 in C
3
6 6
D .
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Figure 2. POM images of the discotic liquid crystals on slow cooling from the
isotropic liquid: (a) 5 at 121°C, (b) 6 at 230°C, (c) 7 at 258°C, (d) 8 at 265°C, (e)
Thermal behavior by DSC and POM. The liquid crystalline
properties of the final compounds (5-11) were investigated first by
POM (Figures 2 and S23) and DSC (Figure S24, DSC data
gathered in Table 1). All samples were observed under optical
polarizing microscope with a heating-stage, and when slowly
cooled from their isotropic liquid states, exhibited fluid and
birefringent optical textures reminiscent of columnar liquid-
crystalline phases (Figure 2): fan-shaped textures typical of
columnar textures with strong homeotropic alignment were
observed for 5-7 and 9-11. 8 behaved differently, and first showed
a schlieren texture characteristic of a nematic phase, which
changed to columnar-like texture with edge-on orientation on
further cooling. Consistently with the extended -conjugated,
overall sanidic-like structures of the compounds, the
mesomorphism in this series is a priori dominated by the
formation of columnar phases. Except compounds 5 and 11 that
possess a distorted non-planar structure (Table S1) and melt at
8
at 229°C, (f) 9 at 262°C, (g) 10 at 165°C, (h) and (i) 11 at 104 and 90°C, fan-
shaped textures with homeotropic domains for columnar phase, and schlieren
texture for the nematic phase (Additional POM images are shown in Figure S23).
Table 1. Phase transition temperatures (°C) and enthalpy changes (H, kJ
-
1
mol )of board-like mesogenic compounds (measured by DSC at 10°C/min
heating/cooling rate).[
a]
2nd Heating
1st Cooling
5
6
7
8
Cr 68.4 (-33.4) Cr’ 102.4 (7.7) Cr”
Iso 133.9 (-9.3) Colhex 69.1 (-3.4)
Cr
114.2 (52.2) Colhex 134.4 (9.3)
Iso
Cr 22.4 (3.1) Cr’ 95.5 (9.5) Cr”
119.4 (8.1) Cr”’ 189.2 (34.3)
Colrec 232.7 (4.7) Iso
Iso 231.4 (-4.4) Colrec 182.1 (-
28.8) Cr”’ 165.6 (-5.5) Cr” 107.4
(-7.3) Cr’ 11.7 (-2.1) Cr
1
10-117°C, all the other mesogens possess rather high transition
temperatures, with melting in the range between ca. 180 and
20°C. Mesogens 7 and 9, which have the most co-planar
2
Cr 114.8 (4.2) Cr’ 146.2 (-)[b] Cr”
Iso 306.7 (-6.4) Colhex 162.0 (-
23.7) Cr’ 92.7 (-10.9) Cr
aromatic core structure, and likely stronger - intermolecular
interactions, exhibit the highest clearing (ca. 310 and 280°C,
respectively) and the largest mesomorphic temperature range
[b]
177.4 (24.6) Cr”’ 188.4 (-)
Colhex 307.2 (8.5) Iso
Cr 206.7 (49.7) Cr’ 213.3 (4.4)
Colrec 263.9 (4.7) N 268.8 (0.9)
Iso
Iso 268.8 (-1.0) N 262.3 (-4.9)
Colrec 152.0 (-47.5) Cr
(
120 and 60°C, respectively). The -bridge between both the two
protomesogenic units in dimers 8 and 6, results in the reduction
of the clearing temperature, concomitantly to that of the
mesomorphic range (55 and 43°C, respectively), whereas the
less hindered rotation in dimer 10 results in the complete
9
1
1
Cr 145.5 (20.9) Cr’ 222.1 (49.2)
Colhex 281.0 (9.2) Iso
Iso 280.8 (-9.1) Colhex 215.9 (-
52.4) Cr’ 135.1 (-17.3) Cr
destabilization of the mesomorphism, yielding
metastable monotropic rectangular columnar phase. Quite
unexpected, the unsymmetrical compound (11) exhibits
a narrow,
0
1
Cr 183.7 (65.4) Iso
Iso 169.5 (-54.8) Colrec 157.8 (-
4.0) Cr
a
Cr 88 (-38.9) Cr’ 117 (70.4) Iso
Iso 106 (-6.7) Colhex 74 (-17.3) Cr
monotropic phase (identified as Colhex by POM, Figure 2), which
is very different to the behavior of its structurally related
symmetrical homologue compound (5): although both have
similar melting temperatures (114 vs. 117°C), they possessed
very different clearing temperatures (134 vs. 74°C). Differential
scanning calorimetry (DSC, Figure S24) results confirmed POM
observations. Recall that intermediates 3a-d, 4a and 4b did not
show mesophase, directly melting when heated into the isotropic
liquid, and crystallizing when cooled with some supercooling.
[
a] Cr-Cr”’: crystalline solids; Colhex: columnar hexagonal mesophase; Colrec
columnar rectangular mesophase; N: nematic phase; Iso: isotropic liquid.
Cumulated enthalpy. [b] Cumulated enthalpies.
:
*
Characterization of the mesophases by small angle X-ray
scattering (SAXS). The SAXS patterns were recorded for all
compounds but 11, at various temperatures (Figures 3 and S25,
Tables 2 and S3). They give patterns exhibiting the characteristic
signals of columnar mesophases, namely the scattering signals,

hch and h , emerging from lateral distances between molten
chains and stacking distances of mesogens, and the sharp
reflections (hk) from the two-dimensional arrangement of the
mesogenic columns separated in space by molten aliphatic
continuum. The presence of additional broad signals at small and
intermediate angular range, D1 and D2, was also detected, which
were associated to correlation lengths between 4 and 10 nm, and
evidenced the development of a local-range three-dimensional
superstructure between individual mesogens. The mesophase of
the series with fused rings bridges (5, 7, 9 and by extension to 11)
was logically found to be columnar hexagonal, Colhex, since the
mesogens come down to a unique pseudo discoid platform with
moreover an aspect ratio qch not far from unity (Table 2).[49,50]
These features allow easy orientational changes of stacked
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mesogens within and between columns, which equally distribute
the aliphatic chains in the periphery of the columns. Corollary, the
cross-section of the columns is averaged to a cylinder and the
symmetry of the lattice is augmented to hexagonal. In addition,
various mechanisms, such as the tilting of the mesogens inside
columns, compensate for the discrepancy between the column
envelope area and the space requirement of peripheral chains.
Along this line, the tilt angles found for the three compounds range
from 23 to 37°, for interface areas per alkyl chain overcoming
slightly the cross sectional area of a fully stretched chain (the
ratios qch range from 1.019 to 1.065, Table 2). The molecular
organization is driven by the optimal nanosegregation between
mesogenic cores and aliphatic periphery and is thus essentially
the same for the three compounds. As a matter of fact,
compounds mostly differ by the extensions of the Colhex phase, as
it exists in broad range, up to high temperatures, for the thieno-
thiophene or the phenyl bridges, but restricts to a narrow range
located at relatively low temperature for the thiophene bridge. The
reason is obviously that the mesogen is not really dumbbell-
shaped in this latter case and that the alkyl substituents
connected to the closely spaced phenanthrene segments
interfere in a detrimental manner with the regular face-to-face
stacking into columns.
At last, 8 exhibits a broad Colrec range at even higher temperature
than 6, but the change of geometry is nevertheless reflected in
the appearance of a 30-40° tilting inside columns and the related
lattice shrinking along b-axis, whereas 6 self-organizes in untilted
columns.
For the series with the bridges including a sigma bond, the
mesophase was found to be Colrec for 6 and 8, and the same very
likely applies to 10, although its mesomorphic range is limited to
a narrow monotropic one, which prevented the acquisition of a
conclusive SAXS pattern. Unlike the precedent rigid bridges,
these ones authorize rotation around the bond axis and hence
preserve the individuality of both mesogen halves, besides of
being longer and thus combining with higher aspect ratios. These
features hamper the orientation changes along the piles of -
stacked mesogens and thus naturally lead to columns with an
elongated cross-section that arrange in a columnar phase of lower
symmetry. Specifically, the cross-sections of columns were found
to align in the same direction, defining the a-axis of a rectangular
c2mm lattice. Again, the main difference between compounds lies
in the extension of the mesomorphic domains, with in particular
broad ranges persisting at high temperatures for 6 and 8, and only
a narrow monotropic phase in combination with a low clearing
temperature for 10. Focusing first on 10 and 6, whose connecting
bridges (i.e. biphenyl and bisthiophene) have comparable lengths,
the huge variations of the mesomorphic properties observed
could not be explained by the influence of the sole chemical
nature on the lateral interactions. Both bridges have however
different orientations of the terminal fused ring edge, so that the
phenanthrene segments pend aside for biphenyl or are in line with
the bridge for bisthiophene. This leads to a true dumbbell-shaped
geometry for the bisthiophene that promotes a regular face-to-
face stacking with an equal surrounding of aliphatic tails. To reach
the same configuration with the phenantrene segments and thus
the alkyl substituents pending aside, neighboring mesogens have
to shift and/or to change orientation along piles. This might be the
main origin of the early clearing transition of 10. Accordingly, the
mesogen geometry would also have a detrimental effect for 8,
despite that the contribution of the extended bridge to the
cohesion of the self-assembling would however counterbalance.
Figure 3. Supramolecular model. Fused core terms 7, 5 and 9 (and 11) self-
organize in a Colhex mesophase, with the mesogens stacked into tilted columns,
whose cross-section is averaged to a cylinder. Fused core members 8 and 6
self-organize in a Colrec mesophase, for which the dumbbell-shaped columns of
stacked mesogens are arranged in a rectangular c2mm lattice (Z = 2). The
electronic density distribution resulting from this particular column shape
explains the high intensity difference of fundamental reflections (20) and (11).
Along columns, the stacking is either tilted (=30-40°) for 8 or untilted for 6. The
mesophase type and the arrangement are likely the same for 10.
Table 2. Geometrical mesophases parameters.[a]
Phase
T
V

mol
a
b
h
mol

A
D
core
cyl
S
ch,cyl
h

q
ch,cyl
v
ch
A[Z]
7
5
Colhex
2021
0.93
23.48
-
477[1]
4.23
3.74
28
23
181
15.2
25.2
1.019
240
0.622
Colhex
1825
22.48
4.17
160
23.4
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1
20
0.98
.88
-
3.83
14.3
1.023
semiconductor materials. Furthermore, 5 and 6 show no charge
carrier mobility rate electric-field dependence, an important
feature for utilization of mesophase semiconductors.
0
438[1]
9
8
6
1
Colhex
2008
0.88
21.94
-
417[1]
4.82
3.82
37
36
0
154
14.0
26.5
1.065
250
0.63
Colrec
2169
0.97
50.40
19.25
971[2]
4.47
3.62
-
-
-
-
240
0.579
Colrec
2043
0.94
47.30
23.96
3.60
3.65
-
-
-
-
210
0
.604
1133[2]
0*
Colrec
2011
0.94
51.28
22.86
3.43
3.68
0
-
-
-
-
165
0.595
1172[2]
[
a] Mesophase, T, temperature of the measurement (°C); Vmol, molecular
3
-3
volume (Å ); , density (g cm ) calculated from partial volumes of reference
substances (accuracy ca. 4%); V,ch, aliphatic volume fraction (V,ch = Vch/Vmol);
2
2
a, b, lattice parameters (Å); A, area (Colhex: A = 2a /√3; Colrec: A = a×b; Å ); Z,
number of columns par lattice; hmol, columnar slice thickness (Å), hmol
mol/(Z×A); h , stacking distance from SAXS pattern; , out-of- plane tilt angle
=
V

of mesogens inside columns,  = arcos(h
of columnar cores (Å ), Acore = VchA/Z; Dcyl (Å), diameter of equivalent cylinder
of cross-sectional area Acore; Sch,cyl, cylinder area per chain (Å ), Sch,cyl

/hmol) (°); Acore, cross-sectional area
2
2
=
1
1
1
1
1
.0E-01
.0E-02
.0E-03
.0E-04
.0E-05
Dcyl×hmol/nch, nch being the number of chains per molecule (nch = 8); qch,cyl,
C
Colhex
Iso
chain packing ratio, qch,cyl = Sch,cyl/ch, ch being the cross-sectional area of a
molten chain. (*) The mesophase being monotropic, SAXS acquisition time
was limited, leading to some measurement uncertainties.
Charge carrier mobility by time-of-flight (TOF) technique.
Columnar discotic liquid crystals possessing polycyclic aromatic
core are well known as mesophase semiconductors,[51-55] the
discotic column formed by the stacked aromatic cores functioning
as electron transport pathway with one-dimensional feature of
molecular wire, while the peripheral alkyl chains serve as
insulators. DLC semiconductors are presently investigated as
active materials in printed organic thin-film devices, such as
organic photovoltaic solar cells (OPV),[56] organic field-effect
transistors (OFET),[26] and organic light-emitting diodes
0
50
100
150
Temperature / ºC
Figure 4. Model charge carrier mobility of 5 measured by time-of-flight (TOF).
Electric field dependency of photocurrent curves for 5 at 120°C in the Colhex
phase, cell thickness = 18.5 μm. Temperature dependence of charge carrier
mobility for hole (circle), measured on cooling from isotropic liquid.
(
OLED).[27] Intrinsic charge carrier mobility is an important
parameter for mesophase semiconductors. The electronic
transport data can be obtained by different techniques, such as
thin-film field-effect transistors, pulse radiolysis time-resolved
microwave conductivity (PR-TRMC), photocurrent time-of-flight
technique (TOF). TOF technique gives directly reliable hole and
electron mobility, and is suitable for the investigation of the
semiconducting property of columnar liquid crystals, with
homeotropic orientation of the samples between the ITO cells,
and sample thickness of 10~20 μm, similar to the thickness of
standard electronic devices.
Both discogens 5 and 6 were selected for the measurement of the
charge drift mobility rates. Actually, they exhibited the lowest
isotropization temperatures within the series, making them
suitable for filling the samples cells by capillary force in their
isotropic liquid state. Both 5 and 6 display non-dispersive
photocurrent decay curves (Figures 4 and 5), demonstrating the
high purity of the DLC samples and their stability as molecular
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x 10-3 cm V s . The hole mobility rate jumps to 0.03 cm V s-1
when it is cooled below 170°C (crystalline Colrec phase). On
further cooling, highly dispersive photocurrent decay curves
appear due to the crystalline grain boundaries playing the role of
deep traps for charge carriers, and no accurate mobility value can
be measured.
2
-1 -1
2
-1
From the above TOF charge carrier mobility investigation, it can
be concluded that these novel electron-rich thiophene-fused
discotic columnar mesogens are stable, applicable p-type organic
semiconductors. Both the ordered Colhex (discogen 5) and Colrec
(
discotic dimer 6) mesophases exhibit moderate hole mobility rate
-3
2
-1 -1
in range of 10 cm V s . More interestingly, the meta-stable
columnar crystalline phases show higher hole mobility with value
in the 10-2 cm V s-1 range. Furthermore, compound 5, with a
twisted aromatic core, forms crystalline thin films without grain
boundaries, which are suitable for charge hopping at ambient
temperature. The planar molecule 6 exhibits narrow mesophase
range and prefers to crystallize into small domains with grain
boundaries that act as deep electronic traps.
2
-1
1.0E-01
1.0E-02
1.0E-03
1.0E-04
1.0E-05
DFT calculations revealed that the most-stable structures of these
thiophene-fused molecules are in nearly co-planar conformation,
benefiting optimized - face-to-face stacking and columnar
arrangement. The calculated HOMO and LUMO locate
continuously along the linear fused-thiophene-containing
polycyclic aromatic cores, implying favorable hole and electron
hopping along the mesogenic columns. This study further reveal
that it is possible to control electron mobility, as whilst 5 and 6 only
show hole mobility, compound 7 shows both hole and electron
mobilities.[38] These results of relationship between molecular
geometry, mesomorphism, and semiconductivity might be a
useful hint for further molecular design of discotic mesophase
semiconductor.
C
Colrec
Iso
100
150
200
250
Temperature / ºC
Figure 5. Model charge carrier mobility of 6 measured by time-of-flight (TOF).
Electric field dependency of photocurrent curves for 6 at 200°C in the Colrec
phase, cell thickness = 18.4 μm. Temperature dependence of charge carrier
mobility for hole (circle), measured on cooling from isotropic liquid.
UV-vis absorption and Photoluminescence. Discotic liquid
crystalline compounds have great potential application in field of
OLED and OPVs, their optical absorption and emission properties
naturally arise our interests. The UV-Vis absorption spectra and
photoluminescence in solution and as thin-films of 5-8 have been
measured (Figure 6). The UV/Vis. absorption spectroscopy
Compound 5, which shows a moderate temperature range on
heating, from 110 to ca 134°C but that extends to ca. 70°C on
(
Figure 6a) of fused thiophene aromatics 5-8 show series of peaks
cooling, shows a low hole mobility rate of 2.59 x 10-5 cm V s-1 at
2
-1
for each compound, the peaks with the longer wavelength come
from the HOMO-LUMO excitation. The optical properties are
coincident with the theoretical calculation results. As the -
conjugated aromatic systems gradually increased from 5 to 8,
their absorption peaks are red-shifting to longer wavelengths, in
agreement with the gradual narrowing of the HOMO-LUMO
energy gaps calculated for homologous methoxy derivatives 5’ to
1
50°C in the isotropic liquid phase. This value jumps up to 1.15 x
2
-1
1
0-3 cm V s-1 at 120°C in the Colhex mesophase, and rises up
further to 0.01 cm V-1 s-1 on cooling down to the meta-stable
Colhex crystalline phase. The behavior of the electronic charge
carrier mobility matches well the temperature dependency of the
molecules dynamics and the order degree of molecular
semiconductors (as supported by DSC). It is stressed that until
2
8’ (Tables 3 and S1).
the ambient temperature,
5
still shows non-dispersive
The photoluminescence spectra of 5-8 in solution (Figure 6b)
display well resolved spectra with two intense peaks, and a
shoulder for each compound, almost mirroring images of their
respective absorption. However, their thin-film photoluminescent
spectra (Figure 6c) are red-shifted to longer wavelength with only
one peak. Thus, 5 and 7 are blue emitters, while 6 and 8 are
greenish to reddish emitters. For thin-film emissions, the
intermolecular - stacking interactions result in strong - orbital
photocurrent decay curves and the hole drift mobility can be
measured, though the POM textures (Figure S26) display
different domain boundaries begin to form.
Compound 6, which displays a Colrec mesophase also with a
moderate temperature range (40-50°C) and at much higher
temperature than 5, shows a hole mobility rate of 3.78 x 10-3 cm2
V-1 s-1 at 200°C on heating, while on cooling from the isotropic
liquid to 200°C, the hole mobility rate is slightly increased to 4.39
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Figure 6. (a) Normalized absorption (in micromolar THF solution), (b)
normalized emission in THF solution, and (c) normalized emission in thin film of
overlap and thus band gaps are narrowed. The emission
efficiency was measured in diluted solution. The absolute emitting
quantum yield of 5 is quite low, only 2.04%, compared to the other
compounds: QY of 6 increases to 10.68%, but more interestingly,
QY of 7 and 8 display almost equal values, around 18%, a quite
high value for a novel photoluminescent discogens. For these
thiophene-fused aromatics, the QY increases with the -
conjugating system extending, while the reason for this result is
not fully understood yet.
5-8 respectively.
Table 3. Photo-physical properties of fused thiophene aromatics.
[a]
[b]
em (film)[d]
Entry

abs

em (sol.)

Quantum
yield
[
c]
[e]

1.49105
2
57
5
2.00105
395
15
425
2.04
300
363
382
4
4
6.6810
6
.52104
5
258
290
403
425
2.0010
6
7
8
1.63105
440
68
500
446
579
10.68
18.03
18.06
4
4
5
4
9.8810
.5210
1.8810
7
252
283
370
393
2.00105
400
20
.13105
.28105
5
4
1
1
262
303
423
2.0010
8.98104
466
96
.33105
4
1
[
a] Absorption (abs) and emission (em) wavelengths in nm; [b] Absorption
-
1
-1
coefficient, , in L mol cm . [c] In micromolar THF solutions with solution
-
6
-1
concentration of 510 mol L . Excitation wavelength: 300 nm for 5; 360 nm
for 6; 285 nm for 7; 375 nm for 8. [d] Prepared solution in THF. Excitation
wavelength: 350 nm for 5; 360 nm for 6; 365 nm for 7; 430 nm for 8. [e]
Quantum yields in % were measured with solution concentration of 110
mol L in THF excited at 310 nm (5-8).
-
4
-
1
Conclusions
Several fused-thiophene discogens and two of their benzene
analogues have been synthesized with high efficiency by Suzuki
cross-coupling and tandem FeCl
3
oxidized intra- and
intermolecular Scholl reactions. The planar-cored compounds
aggregate in organic solvents due to strong - interactions, in
contrast to the core-twisted compounds which do not show such
a trend. All compounds nevertheless display thermotropic liquid
crystalline properties, consisting essentially in the formation of
Colhex and Colrec phases, for the fused and sigma-bridged dimers,
respectively, whose supramolecular arrangements were
comprehensively analyzed by POM, DSC, and SAXS. These new
thiophene-containing discogens exhibit much lower phase
transition temperatures than their benzene analogues, which is
an important advantage for devices fabrication by solution or
melting processing. Moreover, they behave as either blue, or
greenish to reddish emitters, depending on the conjugation
extension, with increasing QY, and two representatives of such
thienoacene-based discogenic structures demonstrated fast hole
mobility values, in the range 10-3 and 10-2 cm V s .
2
-1 -1
Finally, the demonstration that the versatile synthetic strategy
could be successfully extended to the synthesis of unsymmetrical
discogens is of both fundamental and applied interests. For
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instance, the preparation of Janus-type discogenic compounds,
with two edges of different chemical natures can modify and
adjust some properties, such as solubility, wettability, self-
organization, phase transition temperatures, without altering the
intrinsic electronic properties of the conjugated cores, and thus
may represent a very practical tool to circumvent potential
technological problems during their integration into electronic
devices.
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Entry for the Table of Contents (Please choose one layout)
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Tandem FeCl
3
oxidized intra- and
Kai-Chun Zhao, Jun-Qi Du, Hai-Feng
Wang, Ke-Qing Zhao,* Ping Hu, Bi-Qin
Wang, Hirosato Monobe,* Benoît
Heinrich and Bertrand Donnio*
intermolecular Scholl reactions
applied to the fabrication of discotic
mesogens, with tunable color-
emission and fast charge carriers
Page No. – Page No.
Board-like Fused-Thiophene Liquid
Crystals and Their Benzene
Analogues: Facile Synthesis, Self-
assembly, p-Type Semiconductivity,
and Photoluminescence
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