Synthesis and properties of polymers from monosubstituted acetylene derivatives bearing ferroelectric liquid crystalline groups

Article abstract of DOI:10.1021/ma035765g

Novel liquid crystalline polyacetylene derivatives were developed as advanced LC conjugated polymers with quick response to an electric field used as external force. In practice, we synthesized ferroelectric LC conjugated polymers by introducing fluorine-

Full text of DOI:10.1021/ma035765g

Macromolecules 2004, 37, 4783-4793
4783
Synthesis and Properties of Polymers from Monosubstituted Acetylene
Derivatives Bearing Ferroelectric Liquid Crystalline Groups
Hir om a sa Goto,†,‡ Xia om a n Da i,‡ Ta k en or i Ueok a ,‡ a n d Ka zu o Ak a gi*,†,‡,§
Tsukuba Research Center for Interdisciplinary Materials Science (TIMS), Institute of Materials
Science, Center for Tsukuba Advanced Research Alliance (TARA), University of Tsukuba, Tsukuba,
Ibaraki 305-8573, J apan
Received November 25, 2003; Revised Manuscript Received February 10, 2004
ABSTRACT: Novel liquid crystalline polyacetylene derivatives were developed as advanced LC conjugated
polymers with quick response to an electric field used as external force. In practice, we synthesized
ferroelectric LC conjugated polymers by introducing fluorine-containing chiral LC groups into side chains
of polyacetylenes. Phase-transition behaviors of these polymers were examined by differential scanning
calorimetry and polarizing optical microscopy. Mesophases as well as higher order structures were
evaluated with X-ray diffraction measurements. The polymers synthesized showed chiral nematic (N*),
twist grain boundary smectic A (TGBA*), and chiral smectic (SmC*) phases in the heating and cooling
processes. Observation of the SmC* phase allows us to expect that the polymer should exhibit
ferroelectricity.
Ta ble 1. P olym er Str u ctu r es
In tr od u ction
mesogen
type
fluorine
atomc
spacer
Conjugated polymers with liquid crystalline (LC)
groups in their side chains are currently drawing
interest from the viewpoint of multifunctional electrical
and optical materials.1-16 Polyacetylene is the simplest
among all of the conjugate organic polymers, and after
doping by iodine or AsF5, it shows as high an electrical
conductivity as metal. However, it is difficult to be
characterized with standard experimental techniques
due to its insolubility and infusibility. Various substit-
uents have been introduced into the main chain, result-
ing in soluble and fusible polyacetylene derivatives.
With introduction of LC groups into polyacetylene, it is
expected that the orientation of the LC side chains may
enhance the alignment of the main chain via the
spontaneous orientation of the LC groups. The sponta-
neous orientation and externally forced alignment of the
LC side chains enable us to control electrical and optical
properties as well as their anisotropies.17-23 When an
electric field is employed as an external force, ferroelec-
tric LC (FLC) are more desirable than ordinary LC ones
because the former are expected to respond more quickly
to the electric field owing to their spontaneous polariza-
tion than the latter. The ferroelectric liquid crystallinity
is due to spontaneous polarization generated in the
chiral smectic C phase (SmC*) when it is surface
stabilized. Recently, we synthesized polyacetylene de-
rivatives substituted with chiroptical LC groups and
confirmed the formation of the SmC* phase,21,23 al-
though the liquid crystalline phase was unstable. Here,
we synthesized advanced FLC polyacetylene derivatives
with more thermally stable SmC* phase (Scheme 1).
Polymer structures we synthesized in this report are
summarized in Table 1
polymer
ringa
esterb
lengthd
type 1
poly-1
poly-2
poly-3
poly-4
poly-5
poly-6
poly-7
poly-8
poly-9
2
2
2
2
2
3
3
3
3
1
1
3
10
10
10
3
3
10
6
1
1
1
1
1
1
1
1
1
1
1
type 2
10
a
b
Number of phenylene rings in mesogenic core. Number of
ester groups in mesogen. c Number of fluorine atoms on chiral
d
carbon. Number of carbon atoms in alkyl chain.
Exp er im en ta l Section
Tech n iqu es. All 1H NMR and 13C NMR spectra were
measured with a BRUKER AM500 FT-NMR spectrometer.
CDCl3 was used as a deuterated solvent, and TMS was used
as an internal standard. 19F NMR spectra were recorded on a
BRUKER AVANCE 500 spectrometer. To determine the chem-
ical shifts of the 19F resonance, CF3C6H5 was used as a stand-
ard (δ ) -63.72 ppm, referenced against CFCl3 at 0.00 ppm).
The 2D NMR analysis (1H-13C and H-19F NMR obtained by
1
HMQC, heteronuclear multiquantum correlation spectroscopy,
and HOESY, heteronuclear Overhauser effect spectroscopy,
respectively) was carried out on selected samples for further
confirmation of their structure. Infrared spectroscopic mea-
surement was carried out with a J asco FT-IR 550 spectrometer
using KBr method. Phase-transition temperatures were de-
termined using a Perkin-Elmer differential scanning calorim-
eter (DSC 7) apparatus at a constant heating/cooling rate of
10 °C/min, where first cooling and then heating processes were
recorded. Optical texture observation was performed using a
Nikon polarizing optical microscope equipped with a Linkam
THMS 600 heating and cooling stage. Purities of intermediates
and final compounds were checked by HPLC analysis. Molec-
ular weights of the polymers were determined by gel perme-
ation chromatography (GPC) with a Shodex A-80M column and
a J asco HPLC 870-UV detector with tetrahydrofuran (THF)
used as the solvent. XRD measurements were performed with
a Rigaku D-3F diffractometer in which X-ray power and
scanning rate were set at 1200 mW and 5 deg/min, respec-
* To whom correspondence should be addressed.
† Tsukuba Research Center for Interdisciplinary Materials
Science.
‡ Institute of Materials Science.
§ Center for Tsukuba Advanced Research Alliance.
10.1021/ma035765g CCC: $27.50 © 2004 American Chemical Society
Published on Web 05/22/2004

4784 Goto et al.
Macromolecules, Vol. 37, No. 13, 2004
Sch em e 1
tively. Molecular mechanics (MM) calculations for the poly-
mers were carried out by a Silicon Graphics Cerius2 system.
Ma ter ia ls. N,N-Dimethylformamide (DMF), tetrahydrofu-
ran (THF), and CHCl3 were distilled prior to use. The chiral
alcohol (S)-(-)-2-fluorooctanol (1) was prepared according to
the method reported by Nohira et al.24 in which (R)-(+)-1,2-
epoxyoctane was reacted with pyridinium poly(hydrogen fluo-
ride) in ether. Diethylazodicarboxylate (40 wt% in toluene)
(DEAD), triphenylphosphine (TPP), 1,3-dicyclohexylcarbodi-
imide (DCC), and 4-dimethylaminopyridine (DMAP) were used
as received from Tokyo Kasei (TCI).
ppm): 15.17, 29.00, 66.29, 69.00, 83.32, 115.13, 119.10, 127.21,
128.31, 131.85, 132.58, 145.32, 159.64, 167.7.
8-Br om o-1-octyn e (3). A solution of sodium acetylide (44
g, 18 wt % in xylene, 0.16 mol) was very slowly added to a
solution of 1,6-dibromohexane (120 g, 0.49 mol) in 60 mL of
DMF by pressure-equalized dropping funnel. The reaction
mixture was refluxed for 24 h at 50 °C. The precipitate was
removed by filtration, and the solvent was evaporated. Vacuum
distillation afforded 20.2 g of colorless oily product (70-73 °C/4
mmHg). Yield ) 67%. IR (KBr, cm-1): 3305 (νCH ), 2117 (w,
≡
1
C≡C), 636 (m, γHC≡). H NMR (500 MHz, CDCl3, δ from TMS,
ppm): 1.26-1.62 (m, 6H, CH2), 1.86 (t, J ) 2.6 Hz, 1H, HC≡),
2.14 (m, 2H, HCtCCH2), 2.81 (m, 2H, CH2CH2Br), 3.46 (t,
J ) 6.9 Hz, 2H, CH2Br). 13C NMR (125 M Hz, CDCl3, δ from
TMS, ppm): 18.43, 27.44, 28.05, 28.43, 32.80, 33.98, 66.51,
84.72.
Syn th esis. 5-(4-Cya n o-4′-bip h en oxy)-1-p en tyn e (1). A
mixture of 4-cyano-4′-hydroxybiphenyl (21.3 g, 0.11 mol),
5-chloro-1-pentyne (11.7 g, 0.11 mol), K2CO3 (15.2 g, 0.11 mol),
and KI (1.82 g, 11 mmol) in 100 mL of DMF was refluxed for
72 h under an argon atmosphere. Then the solution was
poured into a large amount of acetone, the solution was filtered
off, and the filtrate was evaporated. The crude product was
washed thoroughly with water and extracted with ether. The
ether layer was dried over CaCl2 overnight. After the organic
solution was evaporated, the yellow solid was further purified
by recrystallization from ethanol to afford 11.2 g of white
powder (yield ) 39%). IR (KBr, cm-1): 3258 (s, νHC≡), 2220 (s,
12-Br om o-1-d od ecyn e (4). This compound was prepared
using a method similar to that described for 2. Quantity
used: sodium acetylide (40.0 g, 18 wt % in xylene, 0.15 mol),
1,10-dibromodecane (40.0 g, 0.13 mol), DMF (20 mL). Vacuum
distillation afforded a colorless oily product (130-134 °C/4
mmHg; yield, 64.2%, 18.9 g). IR (KBr, cm-1): 3300 (s, νCH ),
≡
2110 (w, C≡C), 643 (m, γHC≡). 1H NMR (500 MHz, CDCl3, δ from
TMS, ppm): 1.29-1.88 (m, 16H), 1.93 (t, J ) 2.6 Hz, 1H,
HC≡), 2.17 (m, 2H, HCtCCH2), 3.40 (t, J ) 6.9 Hz, 2H, CH2-
Br). 13C NMR (125 MHz, CDCl3, δ from TMS, ppm): 16.39,
28.14, 28.71, 29.05, 29.07, 29.31, 29.37, 29.42, 32.83, 33.96,
66.08, 84.73.
νCN), 2100 (w, νC≡C), 1248 (s, νCOC), 691 (m, γ
). 1H NMR
HC≡
(500 MHz, CDCl3, δ from TMS, ppm): 1.97 (t, J ) 2.6 Hz, 1H,
HC≡), 2.03 (quint, J ) 6.4 Hz, 2H, CH2CH2≡CH), 2.42 (dt,
J ) 2.7 Hz, 2H, HCtCCH2), 4.12 (t, J ) 6.2 Hz, 2H, OCH2),
7.01 (d, J ) 8.1 Hz, 2H, ph), 7.51 (d, J ) 8.1 Hz, 2H, ph), 7.61
(d, J ) 8.4 Hz, 2H, ph), 7.68 (d, J ) 8.3 Hz, 2H, ph). 13C NMR
(125 MHz, CDCl3, δ from TMS, ppm): 15.13, 28.10, 66.29,
68.97, 83.01, 110.15, 115.12, 119.07, 127.11, 128.36, 131.57,
132.57, 145.24, 159.55. Anal. Calcd for C18H15NO: C, 82.73;
H, 5.79; N, 5.36. Found: C, 82.66; H, 5.75; N, 5.33.
12-(4′-Bip h en oxy-4-ca r boxylic a cid )-1-d od ecyn e (5). A
solution of 4′-hydroxybipheny-4-carboxylic acid (25 g, 0.12 mol),
KI (2 g, 0.012 mol) and KOH (50 g, 0.9 mol) in water (100 mL)
and ethanol (160 mL) was stirred for 15 h at room tempera-
ture. Then compound 4 (7.15 g, 0.03 mol) was added, and the
solution was refluxed for 1 week at 55 °C. The solution was
allowed to cool to room temperature, and ether was added to
the solution. The organic layer was washed with water
thoroughly and dried over CaCl2. After evaporation of the
solvent, the crude product was recrystallized from acetone to
afford 28 g of white powder (yield ) 61%). IR (KBr, cm-1): 3295
(s, νHC≡), 2868, 2666, 2546 (m, νCOOH), 2113 (w, νC≡C), 1681
5-(4′-Bip h en oxy-4-ca r boxylic a cid )-1-p en tyn e (2). Com-
pound 1 (8 g, 0.03 mol) was dissolved in a mixed solution of
ethanol (150 mL) and water (100 mL). Then KOH (42 g, 0.75
mol) was added to the stirred mixture. The solution was
refluxed for 72 h at 60 °C. After the organic solvent was
evaporated, the residue solution was neutralized with 1 N HCl
and stirred overnight. The solution was filtered to give 5.2 g
1
of white solid (yield ) 62%). IR (KBr, cm-1): 3305 (s, ν
),
HC≡
(νCdO), 1294 (νC)C), 655 (m, γHC≡). H NMR (500 MHz, CDCl3,
2860, 2672, 2551 (m, br, νCOOH), 1683 (s, νCdO), 1274 (s, νCOC),
633 (m, γ HC≡). 1H NMR (500 MHz, CDCl3, δ from TMS, ppm):
1.97 (t, J ) 2.6 Hz, 1H, HC≡), 2.03 (quint, J ) 6.4 Hz, 2H,
CH2CH2≡CH), 2.60 (dt, J ) 2.8 Hz, 2H, HCtCCH2), 4.15 (t,
J ) 6.2 Hz, 2H, OCH2), 7.28 (d, J ) 8.1 Hz, 2H, ph), 7.63 (d,
J ) 8.4 Hz, 2H, ph), 7.72 (d, J ) 8.3 Hz, 2H, ph), 7.95 (d, J )
8.3 Hz, 2H, ph). 13C NMR (125 MHz, CDCl3, δ from TMS,
δ from TMS, ppm): 1.22-1.77 (m, 16H), 1.94 (t, J ) 2.8 Hz,
1H, HC≡), 2.17 (m, 2H, HCtCCH2), 3.98 (t, J ) 6.6 Hz, 2H,
CH2Br), 6.67 (d, J ) 8.1 Hz, 2H, ph), 6.69 (d, J ) 8.4 Hz, 2H,
ph), 7.41 (d, J ) 8.4 Hz, 2H, ph), 7.45 (d, J ) 8.1 Hz, 2H, ph).
13C NMR (125 MHz, CDCl3, δ from TMS, ppm): 16.31, 26.02,
28.50, 28.74, 29.06, 29.32, 29.37, 29.42, 29.50, 29.74, 66.10,
84.79, 114.75, 115.45, 127.66, 127.95, 133.21, 133.84, 144.57,

Macromolecules, Vol. 37, No. 13, 2004
Polymers Bearing Liquid Crystalline Groups 4785
154.59, 167.71.
ph). 13C NMR (125 MHz, CDCl3, δ from TMS, ppm): 14.04,
(S)-2-F lu or oocta n ol (6). To a stirred solution of pyri-
dinium poly(hydrogen fluoride) (25 mL) in a Teflon flask was
added dropwise via a syringe (R)-1,2-epoxyoctane (9.66 g, 75.5
mmol) in ether (37 mL) at 0 °C. The solution was stirred for 5
h under an argon atmosphere. Then the reaction mixture was
poured into ∼100 mL of crushed ice water. The crude product
was extracted by ether and washed with water several times
22.56, 24.64, 29.01, 31.52, 31.67, 70.51, 70.71, 92.07 (d, J CF )
171.5 Hz), 115.71, 115.71, 127.47, 127.60, 128.55, 137.27,
153.00, 153.37.
4-((S)-2-F lu or o-octyloxy)p h en ol (10). Compound 9 (3 g,
12 mmol) was treated with palladium carbon in methanol (50
mL) under hydrogen gas flow for 2 days. After completion of
the reaction, the crude product was purified by column
chromatography (silica gel, n-hexane/ethyl acetate ) 2) to
afford 1.8 g (yield ) 61%) of white crystal. IR (KBr, cm-1):
with
a Teflon separating funnel. The organic layer was
neutralized by saturated NaHCO3 solution and dried over
anhydrous sodium sulfate. The solvent was removed by
evaporation. Final purification by vacuum distillation yielded
5.90 g (yield ) 53.1%) of 1 as colorless liquid (68-72 °C at 6
mmHg). IR (cm-1): 3398 (m, νOH), 2929, 2859 (s, νCH2). 1H NMR
(500 MHz, CDCl3, δ from TMS, ppm): 0.89 (t, 3H, J ) 6.9 Hz,
CH3), 1.29-1.72 (m, 10H, CH2C*HF(CH2)5CH3), 2.56 (s, 1H,
OH), 3.60-3.73 (m, 2H, C*HFCH2OH), 4.49-4.63 (dm, 1H,
J HF ) 49.81 Hz, OCH2C*HF). 13C NMR (125 MHz, CDCl3, δ
from TMS, ppm): 14.05, 22.58, 24.97, 29.13, 30.93, 31.69,
64.97, 94.8 (d, J CF ) 167.7 Hz).
1
3290 (m, νOH), 1261 (νCOC). H NMR (500 MHz, CDCl3, δ from
TMS, ppm): 0.69 (t, J ) 7.3 Hz, 3H, CH3), 1.28-1.72 (m, 10H,
CH2), 3.96-4.03 (m, 2H, CH2), 4.78 (dm, 1h, J HF ) 49.1 Hz,
OCH2C*HF), 6.02 (s, 1H, OH), 6.74 (d, 2H, 7.2 Hz, ph), 6.61
(d, 2H, 7.3 Hz, ph). 13C NMR (125 MHz, CDCl3, δ from TMS,
ppm): 13.99, 16.77, 22.56, 29.09, 31.51, 31.66, 70.66, 92.15 (d,
J CF ) 171.4 Hz), 115.9, 116.2, 150.46, 152.55.
Eth yl 4-[(S)-2-F lu or ooctyloxy]ben zoa te (11). To a mix-
ture of ethyl p-hydroxybenzoate (6.00 g, 36 mmol) and 9.44 g
(36 mmol) of triphenylphosphine (TPP) in 80 mL of THF was
added dropwise a solution of 16.0 g (in toluene solution, 36
mmol) of diethyl azodicarboxylate (DEAD), 4.44 g (30 mmol)
of 6, and 90 mL of THF. The reaction mixture was stirred at
room temperature overnight. The precipitate was removed by
filtration, the filtrate was evaporated to remove the solvent,
and the residue was purified by column chromatography (silica
gel, hexane/ethyl acetate ) 2/1). The crude product was
recrystallized from an ethyl acetate:hexane mixture and dried
under vacuum to afford 8.01 g of 7 as white solid in 90.2%
4-(8-Octyn yloxy)-4′-bip h en ol (7). Compound 3 (12.0 g,
63.5 mmol) in acetone (30 mL) was added dropwise to a stirred
refluxing suspension consisting of 4,4′-biphenyldiol (35.4 g, 190
mmol) and anhydrous potassium carbonate (26.2 g, 190 mmol)
in 2-butanone (400 mL). After the addition was completed, the
solution was heated under reflux for 24 h. The precipitated
potassium bromide and the excess of potassium carbonate were
removed by filtration, and the filtrate was evaporated. Puri-
fication by column chromatography (silica gel, hexane/ethyl
acetate ) 2) and recrystallization from ethanol afforded 18 g
(yield ) 96%) of white solid. IR (KBr, cm-1): 3290 (m, νOH),
2110 (w, νC≡C), 1255 (s, νCOC). 1H NMR (500 MHz, CDCl3, δ
from TMS, ppm): 1.25-1.82 (m, 8H, CH2), 1.95 (t, J ) 2.7
Hz, 1H, HC≡), 2.19 (m, 2H, HCtCCH2), 3.96 (t, 2H, J ) 6.5
Hz, OCH2), 4.73 (s, 1H, OH), 6.78 (d, J ) 8.7 Hz, ph), 6.92 (d,
2H, J ) 8.7 Hz, ph), 7.50 (d, 2h, J ) 8.6 Hz, ph), 7.34 (d, 2H,
J ) 8.7 Hz, ph). 13C NMR (125 MHz, CDCl3, δ from TMS,
ppm): 18.41, 26.05, 28.73, 29.31, 29.51, 68.05, 68.73, 84.80,
114.72, 115.31, 127.45, 127.74, 133.23, 133.65, 144.59, 154.58.
4-(12-Dod ecyn yloxy)-4′-bip h en ol (8). Compound 4 (9.24
g, 38 mmol) in 2-butanone (30 mL) was added dropwise to a
stirred refluxing suspension consisting of 4,4′-biphenyldiol
(50.0 g, 269 mmol), anhydrous potassium carbonate (53.8 g,
389 mmol), and 2-butanone (500 mL). Once the addition was
complete, the reaction solution was heated under reflux for
24 h. The precipitated potassium bromide and the excess of
potassium carbonate were filtered off, and the filtrate was
evaporated to give a solid. Purification by column chromatog-
raphy (silica gel, hexane/ethyl acetate ) 2) and recrystalliza-
tion from ethanol afforded 7.17 g (53.9%) of white solid. Mp )
137-140 °C. IR (KBr, cm-1): 3289 (m, νOH), 2112 (w, νC≡C),
1252 (νCOC). 1H NMR (500 MHz, CDCl3, δ from TMS, ppm):
1.25-1.82 (m, 16H, CH2), 1.94 (t, J ) 2.7 Hz, 1H, HC≡), 2.18
(m, 2H, HCtCCH2), 3.98 (t, 2H, J ) 6.5 Hz, OCH2), 4.76 (s,
1H, OH), 6.88 (d, 2H, J ) 8.7 Hz, ph), 6.94 (d, 2H, J ) 8.7 Hz,
ph), 7.42 (d, 2h, J ) 8.6 Hz, ph), 7.45 (d, 2H, J ) 8.7 Hz, ph).
13C NMR (125 MHz, CDCl3, δ from TMS, ppm): 18.41, 26.06,
28.49, 28.75, 29.09, 29.31, 29.37, 29.51, 29.12, 68.05, 68.71,
84.80, 114.78, 115.58, 127.66, 127.94, 133.22, 133.63, 144.57,
154.57.
1
yield. Mp ) 47-48 °C. IR (KBr, cm-1): 1680 (νCdO). H NMR
(500 MHz, CDCl3, δ from TMS, ppm): 0.89 (t, 3H, J ) 6.8,
CH3), 1.23-1.78 (m, 10H, CH2), 4.04-4.13 (m, 2H, OCH2), 4.33
(q, 2H, J ) 7.1 Hz, CH2), 4.82 (dm, 1H, J HF ) 51.7 Hz,
OCH2C*HF), 6.93 (d, 2H, J ) 6.9 Hz, ph), 7.99 (d, 2H, J ) 8.9
Hz). 13C NMR (125 MHz, CDCl3, δ from TMS, ppm): 14.00,
14.39, 22.56, 24.89, 29.10, 31.74, 60.57, 69.79, 91.71 (d, J CF
172.5 Hz), 114.18, 115.29, 131.60, 162.26, 166.24.
)
4-[(S)-2-F lu or ooctoxy]ben zoic a cid (12). Compound 11
(4.00 g, 13.5 mmol) was hydrolyzed by heating it in a solution
of NaOH (2.69 g, 67 mmol) in a mixed solution of 15 mL of
water (15 mL) and methanol (24 mL) for 4 h at 50 °C. The
methanol was evaporated, and the residue solution was diluted
with water and acidified to pH ) 2 with 2 N hydrochloric acid.
The solution was extracted with ether, washed with water
thoroughly, and dried over anhydrous sodium sulfate. The
ether layer was removed by evaporation and dried under
reduced pressure. Product 5 was obtained as white solid in
98.1% yield (3.55 g). IR (KBr, cm-1): 2863, 2673, 2564 (br, s,
1
ν
COOH), 1685 (νCdO). H NMR (500 MHz, CDCl3, δ from TMS,
ppm): 0.90 (t, J ) 6.9 Hz, 3H, CH3), 1.25-1.86 (m, 10H, CH2),
4.08-4.17 (m, 2H, OCH2), 4.84 (dm, 1H, J HF ) 51.7 Hz,
OCH2C*HF), 6.97 (d, 2H, J ) 8.9 Hz, ph), 8.07 (d, 2H, J ) 8.9
Hz, ph). 13C NMR (125 MHz, CDCl3, δ from TMS, ppm): 14.04,
22.55, 24.84, 29.17, 31.43, 31.65, 69.99, 91.64 (d, J CF ) 172.5
Hz), 114.21, 115.36, 132.45, 162.98, 171.40.
(R)-(-)-1-Met h ylh ep t yl-4′-p en t yn oxyb ip h en yl-4-ca r -
boxyla te (m on o-1). Into a 100 mL three-necked round-bottom
flask was placed 2 (2.5 g, 8.9 mmol) and DEAD (3.87 g, 8.9
mmol) in 30 mL of THF under argon. Then (S)-octanol (1.45
mL) and TPP (2.33 g, 8.9 mmol) in 20 mL of THF was added
to the solution by a pressure-equalized dropping funnel. After
the reaction mixture was stirred for 12 h, the solution was
extracted by CHCl3 and washed with water thoroughly. The
solution was dried by CaCl2 overnight. Recrystallization from
ethanol afforded 2.8 g of white crystals of m on o-1 (yield )
81%). [R]D26: -34.5°. IR (KBr, cm-1): 3310 (s, νHC≡), 2120 (w,
1-P h en yl m eth oxy-4-((S)-2-flu or o-octyloxy)ben zen e (9).
A solution of 4-benzyloxyphenol (4 g, 20 mmol) and DEAD (8.7
g, 20 mmol) in 20 mL of THF was added to a solution of TPP
(5.3 g, 20 mmol) and 6 (2.2 g, 15 mmol) in THF (25 mL) by a
pressure-equalized dropping funnel. After completion of the
addition, the solution was stirred for 72 h. Then the solvent
was evaporated, and the crude product was purified by column
chromatography (silica gel, n-hexane/ethyl acetate ) 2) and
recrystallized from acetone to afford 3.8 g (yield ) 78%) of
white crystal. IR (KBr, cm-1): 1260 (s, νCOC). 1H NMR (500
MHz, CDCl3, δ from TMS, ppm): 0.89 (t, J ) 7.0 Hz, 3H, CH3),
1.29-1.72 (m, 10H, CH2), 4.64 (br, ph-CH2O-ph), 3.94-4.06
(m, 2H, OCH2), 4.77 (J HF ) 49.1 Hz, OCH2C*HF), 6.63 (d, J )
7.2 Hz, 2H, ph), 6.90 (d, J ) 7.2 Hz, 2H, ph), 7.23 (t, J ) 6.58,
1H, ph), 7.29 (d, J ) 7.1 Hz, 2H, ph), 7.40 (d, J ) 7.3 Hz, 2H,
ν
C≡C), 1700 (s, νCdO), 640 (m, γHC≡). 1H NMR (500 MHz, CDCl3,
δ from TMS, ppm): 0.87 (t, 3H, J ) 7 Hz, CH3), 1.28-1.80
(m, 13 H, CH2, CH3), 1.98 (t, 1H, J ) 2.5 Hz, HC≡), 2.01 (m,
2H, HCtCCH2), 2.43 (m, 2H, CH2), 4.12 (t, 2H, J ) 6.09 Hz,
OCH2), 5.16 (sextet, 1H, J ) 6.1 Hz, COOC* H CH3), 6.99 (d,
2H, J ) 8.7 Hz, ph), 7.55 (d, 2H, J ) 7.3 Hz, ph), 7.61 (d, 2H,
J ) 7.2 Hz, ph), 8.07 (d, 2H, J ) 9.4 Hz, ph). 13C NMR (125
MHz, CDCl3, δ from TMS, ppm): 14.01, 15.19, 20.12, 22.60,
25.44, 28.18, 29.19, 31.77, 36.13, 66.28, 68.98, 71.67, 83.37,

4786 Goto et al.
Macromolecules, Vol. 37, No. 13, 2004
114.98, 126.42, 128.36, 129.09, 130.05, 132.62, 145.03, 159.15,
166.17. 19F NMR (470 MHz, CDCl3, δ, ppm): -186.45.
(R)-(-)-1-Meth ylh ep tyl-4′-d ecyloxybip h en yl-4-ca r box-
yla te (m on o-2). This compound was prepared using a method
similar to that described for m on o-1. Quantity used: 5 (1 g,
2.64 mmol) and DEAD (1.15 g, in toluene, 2.64 mmol) in THF
(3 mL); (S)-octanol (0.43 mL) and TPP (0.7 g, 2.64 mmol) in
THF (2 mL). Yield: 75%, 0.97 g (pale orange solid). IR (KBr,
cm-1): 3320 (s, νHC≡), 2130 (w, νC≡C), 1700 (s, νCdO), 640 (m,
1 week at room temperature. Then the insoluble fraction of
the solution was filtered off, and the filtrate was purified by
column chromatography (silica gel, benzene) to afford 1.5 g of
white crystal (yield ) 61%). [R]D27: +3.0°. IR (KBr, cm-1): 3300
(m, νHC≡), 2130 (w, νC≡C), 1730(s, νCdO), 1252 (s, νCOC), 640 (w,
1
γHC≡). H NMR (500 MHz, CDCl3, δ from TMS, ppm): 0.90 (t,
3H, J ) 7.1 Hz, CH3), 1.30-1.71 (m, 10H, CH2), 1.82 (t, 1H,
J ) 2.6 Hz, HC≡), 1.85 (m, 2H, CH2), 2.23 (m, 2H, HCtCCH2),
4.13 (m, 4H, OCH2, OCH2C*HF), 4.80 (dm, 1H, J HF ) 49.5
Hz, CH2C*HF), 6.95 (d, J ) 2H, 6.9 Hz, ph), 7.02 (d, 2H, J )
7.5 Hz, ph), 7.58 (d, 2H, J ) 7.3 Hz, ph), 7.67 (d, 2H, J ) 7.4
Hz, ph), 8.22 (d, 2H, 8.5 Hz, J ) 8.5 Hz, ph). 13C NMR (125
MHz, CDCl3, δ from TMS, ppm): 14.06, 15.19, 22.57, 24.88,
28.17, 29.02, 31.50, 31.60, 67.98, 70.22, 70.41, 83.37, 91.93 (d,
J CF ) 171.9 Hz), 115.04, 115.39, 122.59, 126.62, 127.65, 128.44,
130.70, 132.32, 144.91, 145.88, 156.33, 159.34, 171.49. 19F
NMR (470 MHz, CDCl3, δ, ppm): -187.55.
4-((S)-2-F lu or ooctyloxy)-p h en yl-4′-d od ecyn yloxy-4-bi-
p h en yl-ca r boxyla te (m on o-7). This compound was prepared
using a method similar to that described for m on o-6. Quantity
used: 5 (0.52 g, 1.3 mmol), 10 (1.3 g, 1.4 mmol), DCC (0.46 g,
2.2 mmol), and DMAP (0.27 g, 2.2 mmol) in CH2Cl2 (40 mL).
Yield: 63%, 0.5 g (white crystal). IR (KBr, cm-1): 3300 (m,
νHC≡), 2130 (w, νC≡C), 1730(s, νCdO), 1252 (s, νCOC), 640 (w, γHC≡).
1H NMR (500 MHz, CDCl3, δ from TMS, ppm): 0.90 (t, 3H,
J ) 7.0 Hz, CH3), 1.25-1.70 (m, 26H, CH2), 1.93 (t, 1H, J )
2.6 Hz, HC≡), 2.16 (m, 2H, HCtCCH2), 4.02 (m, 4H, OCH2,
OCH2C*HF), 4.83 (dm, 1H, J HF ) 49.8 Hz, OCH2C*HF), 6.98
(m, 4H, ph), 7.13 (d, 2H, J ) 7.1 Hz, ph), 7.58 (d, 2h, J ) 7.5
Hz, ph), 7.88 (d, 2H, J ) 8.3 Hz, ph), 8.22 (d, 2H, J ) 8.4 Hz,
ph). 13C NMR (125 MHz, CDCl3, δ from TMS, ppm): 14.05,
18.42, 18.78, 21.91, 21.57, 24.65, 25.63, 28.78, 29.10, 29.27,
29.38, 29.44, 29.52, 31.51, 31.65, 68.16, 70.23, 70.42, 83.34,
91.93 (d, J CF ) 171.5 Hz), 115.03, 115.39, 122.80, 126.59,
127.59, 128.40, 130.69, 132.04, 144.92, 145.97, 156.33, 159.62,
171.50. 19F NMR (470 MHz, CDCl3, δ, ppm): -187.54.
1
γHC≡). H NMR (500 MHz, CDCl3, δ from TMS, ppm): 0.87 (t,
3H, J ) 6.7, CH3), 1.18-1.81 (m, 29 H, CH2, CH3), 1.93 (t, 1H,
J ) 2.5 Hz, HC≡), 2.17 (m, 2H, HCtCCH2), 3.98 (t, 2H, J )
6.52, OCH2), 5.16 (sextet, 1H, J ) 6.6 Hz, COOC*H CH3), 6.98
(d, 2H, J ) 7.4 Hz, ph), 7.04 (d, 2H, J ) 6.8 Hz, ph), 7.01 (d,
2H, J ) 7.0 Hz, ph), 8.06 (d, 2H, J ) 8.3 Hz, ph). 13C NMR
(125 MHz, CDCl3, δ from TMS, ppm): 13.99, 15.16, 18.33,
20.04, 22.53, 25.55, 25.97, 26.15, 28.67, 29.11, 29.25, 29.35,
29.46, 31.69, 32.75, 36.05, 65.98, 70.71, 71.57, 84.67, 114.86,
126.30, 128.23, 128.93, 129.95, 132.22, 145.03, 159.34, 166.11.
4-Octoxy-4′-(12-d od ecyn yloxy)bip h en yl (m on o-3). This
compound was prepared using a method similar to that
described for m on o-1. Quantity used: DEAD (5.66 g, in
toluene 13.0 mmol) and 1-octanol (1.26 g, 9.7 mmol) in THF
(30 mL); 8 (3.00 g, 8.5 mmol) and TPP (3.34 g, 13.7 mmol) in
THF (15 mL). Yield: 46%, 1.82 g (white solid). Mp ) 114-
117 °C. IR (KBr, cm-1): 3287 (m, νHC≡), 2110 (w, νC≡C), 1251
(s, νCOC), 637 (w, γHC≡). 1H NMR (500 MHz, CDCl3, δ from TMS,
ppm): 0.90 (t, 3H, J ) 6.9 Hz, CH3), 1.25-1.89 (m, 28H, CH2),
1.94 (t, 1H, J ) 2.7 Hz, HC≡), 2.19 (m, 2H, HCtCCH2), 3.99
(t, 4H, J ) 6.6 Hz, OCH2), 6.94 (d, 4H, J ) 8.7 Hz, ph), 7.46
(d, 4H, J ) 8.7 Hz, ph). 13C NMR (125 MHz, CDCl3, δ from
TMS, ppm): 14.10, 14.69, 16.41, 22.67, 26.06, 26.08, 28.17,
28.75, 29.09, 29.38, 29.43, 29.45, 29.51, 31.63, 32.64, 33.99,
66.05, 66.12, 84.79, 114.77, 127.65, 133.35, 158.26.
4-[(S)-2-F lu or ooct oxy]-4′-(12-d od ecyn yloxy)b ip h en yl
(m on o-4). This compound was prepared using a method
similar to that described for m on o-1. Quantity used: 8 (2 g,
5.7 mmol) and DEAD (3.70 g, in toluene, 8.5 mmol) in THF
(10 mL); TPP (2.33 g, 8.5 mmol) and 6 (0.84 g, 5.7 mmol) in
THF (20 mL). Yield: 59.5%, 1.62 g (white solid). Mp ) 112-
113 °C. IR (KBr, cm-1): 3286 (m, νHC≡), 2112 (w, νC≡C), 1251
(s, νCOC), 634 (w, γHC≡). 1H NMR (500 MHz, CDCl3, δ from TMS,
ppm): 0.90 (t, 3H, J ) 6.9, CH3), 1.24-1.94 (m, 26H), 1.94 (t,
1H, J ) 2.7 Hz, HC≡), 2.19 (m, 2H, HCtCCH2), 3.98 (t, 2H,
J ) 6.6 Hz, OCH2), 4.10 (m, 2H, OCH2C*HF), 4.83 (dm, 1H,
J HF ) 49.6 Hz, OCH2C*HF), 6.94 (d, 2H, J ) 8.7 Hz, ph), 6.96
(d, 2H, J ) 8.7 Hz, ph), 7.46 (d, 2H, J ) 8.6 Hz, ph), 7.47 (d,
2H, J ) 8.7 Hz, ph). 13C NMR (125 MHz, CDCl3, δ from TMS,
ppm): 14.05, 18.41, 22.56, 24.54, 24.88, 26.07, 28.50, 28.76,
29.09, 29.32, 29.51, 31.64, 31.67, 31.70, 46.51, 66.11, 69.58,
70.05, 84.60, 92.00 (d, J CF ) 171.6 Hz), 114.78, 127.72, 133.17,
134.10, 144.57, 148.48, 157.67, 158.32. 19F NMR (470 MHz,
CDCl3, δ, ppm): -187.74.
4-[4-((S)-2-F lu or ooct yloxy)b en zoyloxy]-4′-(7-oct yn yl-
oxy)bip h en yl (m on o-8). This compound was prepared using
a method similar to that described for m on o-6. Quantity
used: 7 (0.81 g, 2.7 mmol), 12 (0.7 g, 2.6 mmol), DCC (0.82 g,
3.9 mmol), and DMAP (0.48 g, 3.9 mmol) in CH2Cl2 (50 mL).
Yield: 90%, 0.85 g (white crystal). IR (KBr, cm-1): 3285 (m,
νHC≡), 2112 (w, νC≡C), 1737(s, νCdO), 1255 (s, νCOC), 640 (w, γHC≡).
1H NMR (500 MHz, CDCl3, δ from TMS, ppm): 0.90 (t, 3H,
J ) 7.0, CH3), 1.25-1.91 (m, 18H, CH2), 1.95 (t, 1H, J ) 2.6
Hz, HC≡), 2.22 (dt, 2H, J ) 7.0, HCtCCH2), 4.01 (t, 2H, J )
6.5 Hz, OCH2), 4.10-4.22 (m, 2H, CH2), 4.87 (dm, 1H, J HF
)
49.1 Hz, OCH2C*HF), 6.97 (d, 2H, J ) 8.7 Hz, ph), 7.01 (d,
2H, J ) 8.9 Hz, ph), 7.24 (d, 2H, J ) 8.6 Hz, ph), 7.51 (d, 2H,
J ) 8.7 Hz, ph), 7.58 (d, 2H, J ) 8.7 Hz, ph), 8.18 (d, 2H, J )
8.8 Hz, ph). 13C NMR (125 MHz, CDCl3, δ from TMS, ppm):
14.02, 15.56, 16.41, 22.54, 24.52, 26.09, 29.07, 29.46, 29.50,
31.63, 31.64, 67.93, 69.65, 70.01, 94.77, 91.93 (d, J CF ) 171.8
Hz), 114.45, 114.87, 121.94, 122.39, 122.53, 127.74, 128.15,
132.37, 133.43, 138.64, 150.01, 159.01, 163.14.19F NMR (470
MHz, CDCl3, δ, ppm): -187.40.
(S)-2-F lu or ooct yl-4′-p en t yn oxyb ip h en yl-4-ca r b oxyl-
a te (m on o-5). This compound was prepared using a method
similar to that described for m on o-1. Quantity used: 2 (1.4 g
5 mmol) and DEAD (2.17 g, in toluene, 5 mmol) in THF (3
mL); 6 (0.74 g, 5 mmol) and TPP (1.3 g, 5 mmol) in THF (3
mL). Yield: 51%, 1.08 g (white solid). IR (KBr, cm-1): 3300
(m, νHC≡), 2130 (w, νC≡C), 1730(s, νCdO), 1250 (s, νCOC), 640 (w,
4-[4-((S)-2-F lu or ooctyloxy)ben zoyloxy]-4′-(12-d od ecyn -
yloxy)bip h en yl (m on o-9). This compound was prepared
using a method similar to that described for m on o-6. Quantity
used: 8 (0.65 g, 1.9 mmol), 12 (0.50 g, 1.9 mmol), DCC (0.77
g, 3.7 mmol), and DMAP (0.46 g, 3.7 mmol) in 5 mL of CH2-
Cl2. The residue was purified by column chromatography (silica
gel, benzene/hexane ) 2) followed by recrystallization from
ethanol. Yield: 0.87 g, 76% (white solid). IR (KBr, cm-1): 3300
(m, νHC≡), 2130 (w, νC≡C), 1730(s, νCdO), 1254 (s, νCOC), 642 (w,
1
γHC≡). H NMR (500 MHz, CDCl3, δ from TMS, ppm): 0.90 (t,
3H, 7.0 Hz, CH3), 1.35-1.58 (m, 10 H, CH2), 1.86 (t, 1H, J )
2.6 Hz, HC≡), 2.03 (m, 2H, HCtCCH2), 2.44 (m, 2H, CH2),
4.13 (t, 2H, J ) 6.1 Hz, OCH2), 4.44 (m, 2H, OCH2C*HF), 4.82
(dm, 1H, J ) 48.7 Hz, OCH2C*HF), 7.01 (d, 2H, J ) 7.1 Hz,
ph), 7.5 Hz (d, 2H, J ) 6.9 Hz, ph), 7.63 (d, 2H, J ) 7.2 Hz,
ph), 8.12 (d, 2H, J ) 8.4 Hz, ph). 13C NMR (125 MHz, CDCl3,
from TMS, ppm): 14.04, 15.19, 22.55, 24.79, 28.17, 29.05,
31.43, 31.63, 66.16, 66.28, 68.96, 83.37, 91.53 (d, J CF ) 172.0
Hz), 115.00, 126.52, 127.69, 128.40, 130.29, 132.43, 145.52,
159.24, 166.30. 19F NMR (470 MHz, CDCl3, δ, ppm): -187.74.
4-((S)-2-Flu or ooctyloxy)-p h en yl-4′-p en tyloxy-4-biph en -
yl-ca r boxyla te (m on o-6). A solution of 2 (1.4 g, 5 mmol), 10
(0.8 g, 5 mmol), DCC (1.1 g, 5 mmol), and DMAP (0.64 g, 5
mmol) in 80 mL of CH2Cl2 and 30 mL of THF was stirred for
1
γHC≡). H NMR (500 MHz, CDCl3, δ from TMS, ppm): 0.90 (t,
3H, J ) 6.9, CH3), 1.25-1.91 (m, 26H), 1.94 (t, 1H, J ) 2.6,
HC≡), 2.17-2.22 (m, 2H), 4.00 (t, 2H, J ) 6.5 Hz, OCH2),
4.11-4.22 (m, 2H), 4.86 (dm, 1H, J HF ) 50.5 Hz, OCH2C*HF),
6.96 (d, 2H, J ) 8.7 Hz, ph), 7.01 (d, 2H, J ) 8.9 Hz, ph), 7.24
(d, 2H, J ) 8.7 Hz, ph), 7.51 (d, 2H, J ) 8.7 Hz, ph), 7.58 (d,
2H, J ) 8.5 Hz, ph), 8.17 (d, 2H, J ) 8.9 Hz, ph). 13C NMR
(125 MHz, CDCl3, δ from TMS, ppm): 14.05, 15.58, 16.42,
22.56, 24.56, 26.07, 24.51, 26.76, 29.07, 29.39, 29.44, 29.52,
30.91, 31.60, 31.67, 67.98, 69.66, 70.04, 94.75, 91.91 (d, J CF
)

Macromolecules, Vol. 37, No. 13, 2004
Polymers Bearing Liquid Crystalline Groups 4787
Sch em e 2
Sch em e 3
10). Compound 8 is then reacted with the fluorine-
containing compound 6 or 1-octanol according to the
Mitsunobu reaction to yield m on o-3 and m on o-4 as
monomers.
Compound 2 was esterified with a fluorine-atom-
containing compound 6 by combination of DEAD and
TPP to yield m on o-5 with (S)-configuration.
171.6 Hz), 114.44, 114.85, 121.97, 122.41, 122.50, 127.71,
128.12, 132.36, 133.40, 138.63, 149.99, 158.61, 162.95. 19F
NMR (470 MHz, CDCl3, δ, ppm): -187.47.
Syn th esis of th e Typ e 2 Mon om er s. Type 2 mono-
mers having three aromatic rings in the mesogenic core
are outlined in Scheme 4. Mon o-6 and m on o-7 struc-
turally resemble m on o-8 and m on o-9, but the esters
of the joint group in the mesogen face different direc-
tions, so the LC director along the ester group faces in
the opposite direction to those of m on o-8 and m on o-9.
The first step of m on o-6 and m on o-7 syntheses
consists of etherification of 4-benzyloxyphenol with 6
by DEAD and TPP to yield 9 with (S)-configuration.
Compound 9 was then deprotected using H2 and PdC
in methanol to obtain 10 with a hydroxyl group. Then
compound 10 was coupled with 2 or 5 using DCC and
DMAP to synthesize m on o-6 (n ) 3) or m on o-7(n ) 10),
respectively.
p-Hydroxybenzoate was esterified with 6 by the
Mitsunobu reaction to yield 11 with (S)-configuration.
Ethyl moiety in 11 was removed by NaOH in mixed
solution of methanol/water to give 12. Compound 12 was
then esterified with compound 7 or 8 by DCC and
DMAP in CH2Cl2 to afford m on o-8 (n ) 6) or m on o-9
(n ) 10), respectively.
P olym er iza tion . Fe(acac)3-AlEt3, a Ziegler-Natta
catalyst, and MoCl5-Ph4Sn, a metathesis catalyst, can
polymerize monosubstituted acetylene derivatives. In
particular, very high molecular weights can be obtained
by the Fe catalyst in the polymerization of phenylacety-
lene or 4-pheny-l-butyne.27 However, these systems are
not valid for polymerizations of monomers with ester
groups due to the fact that metal ions react with the
ester group in the monomer, which results in deactiva-
tion of the catalyst. Thus, we adopted a rhodium
P olym er iza tion . A typical procedure for the polymerization
is as follows: under argon atmosphere, 4.8 mL of triethylamine
(NEt3) was added to 15 mg (0.03 mmol) of (bicyclo[2,2,1]hepta-
2,5-diene)chlororhodium (I) dimer, [Rh(NBD)Cl]2, in a Schlenk
flask with stirring. After aging the solution for 30 min at room
temperature, 200 mg (0.33 mmol) of m on o-9 and 5 mL of THF
were added. Polymerization was carried out for 24 h at 60 °C.
The solution was poured into a large amount of methanol and
stirred for 24 h. After filtration, the polymer was further
washed with 25 mL of a mixed solution of THF/EtOH ) 1/24
and dried under vacuum to afford brown powder.
Resu lts a n d Discu ssion
Syn th esis of th e Typ e 1 Mon om er s. The synthetic
routes of the type 1 monomers having two aromatic
rings in mesogen core are shown in Schemes 2 and 3.
Compound 1 was prepared by etherification of 4-cy-
ano-4′-hydroxybiphenyl in the presence of K2CO3 and
KI in DMF. Then the cyano group in 1 was converted
into a carboxylic group by KOH in mixed solution of
ethanol/water to give 2. 8-Bromo-1-octyne (3) or 12-
bromo-1-dodecyne (4) was prepared by reacting dibro-
mohexane or dibromodecane with sodium acetylide in
DMF, respectively. Compounds 2 and 5 were coupled
with (S)-octanol according to the Mitsunobu reaction
using DEAD and TPP followed by silica gel column
chromatography and recrystallization to afford m on o-1
(n ) 3) and m on o-2 (n ) 10). This reaction is character-
ized by SN2-type Walden inversion at the chiral center
but with no racemization, resulting in the formation of
ester with (R)-configuration.25
4,4′-Biphenyldiol is etherified with 3 and 4 in the
presence of K2CO3 and KI to afford 7 (n ) 6) and 8 (n )

4788 Goto et al.
Macromolecules, Vol. 37, No. 13, 2004
Sch em e 4
F igu r e 1. FT-IR spectra of m on o-9 and poly-9.
Ta ble 3. Resu lts of Op tica l Absor p tion a n d CD
Sp ectr oscop y Mea su r em en ts
optical absorptiona
CDa
polymer
λ (nm)
ꢀ (×104)
λ (nm)
284
∆ꢀ
poly-1
poly-2
poly-3
poly-4
poly-5
poly-6
poly-7
poly-8
poly-9
292
295
296
273
294
296
301
292
268
2.32
1.66
2.01
3.76
2.84
2.76
2.60
3.10
9.10
-1.09
-2.40, -3.57
330, 246
292
299
296, 270
293, 260
282
-1.41
0.75
-1.25, 3.90
-1.21, 0.54
-2.1
280
-5.1
a
Maximum values; measured in CHCl3.
molecular weight distributions (MWD, calculated by Mw/
Mn, Mw ) weight average molecular weights) are 1.5-
3.7.
Living polymerization of phenyl acetylene using an
Rh complex catalyst was reported by Masuda et al.29
Percec and Oda performed living polymerization of vinyl
monomers bearing FLC substituents with controlled
degree of polymerization (DP).30 In our study, we were
not able to obtain polymer by living polymerization. This
may be due to the fact that the steric repulsion between
bulky substituents of the FLC during the polymerization
in the solvent resulted in a decrease of polymerization
activity.
In the IR spectra, the polymer shows no absorptions
characteristic of the acetylene moiety in the monomer,
HC≡ stretching at 3300 cm-1, CtC symmetry stretch-
ing vibration at 2100 cm-1, and HC≡ out-of-plane
vibration about 630 cm-1 for the monomers. IR spectra
of m on o-9 and poly-9 are shown in Figure 1. All the
acetylene absorptions disappear in the IR spectra of the
polymers, indicating that the polymerizations were
performed successfully by reaction of the opening of the
triple bond.
Ta ble 2. Molecu la r Weigh ts of P olym er s
polymer
Mn
Mw
MWDa
yield (%)
DPb
poly-1
poly-2
poly-3
poly-4
poly-5
poly-6
poly-7
poly-8
poly-9
21 600
8 300
9 100
15 000
14 000
8 300
4 500
11 100
11 200
80 200
14 000
13 600
44 000
28 000
14 700
10 000
21 700
17 900
3.7
1.7
1.5
2.9
2.0
1.8
2.2
2.0
1.6
64
68
61
41
63
67
62
54
59
55
17
20
32
33
16
7
20
19
a
b
MWD ) Mw/Mn. DP ) degree of polymerization calculated
by Mn/mru (mru ) molecular weight of molecular repeat unit).
complex catalyst, [Rh(NBD)Cl]2, where NBD stands for
2,5-norbornadiene, for polymerization of the acetylene
monomers with FLC substituent because the Rh com-
plex catalyst has no poisoning interaction with the polar
ester group. Polymerizations of the acetylene monomers
(m on o-1-9) were carried out in triethylamine/THF at
60 °C for 24 h. After the polymerization reaction, lower
molecular weight fractions were removed by washing
with methanol followed by filtration to yield brown solid.
All the polymers synthesized were fusible and soluble
in common organic solvents such as THF and chloro-
form. The polymerization results are summarized in
Table 2.
Results of absorption and CD (circular dichroism)
spectroscopy measurements are summarized in Table
3. All of the polymers show a Cotton effect in CD spectra
except poly-3 (poly-3 having no chiral moiety). Those
results can be attributed to the presence of the optically
active moiety in the LC substituents, and the asym-
metry in the chiral center of the compounds is main-
tained after the polymerization. Only poly-5 shows a
positive Cotton effect in the CD; however, the reason
for this is unclear.
1
In the H NMR (500 MHz) spectra, no signals char-
acteristic of the acetylenic moiety in the monomer, e.g.,
the triplet signal at 1.93 ppm originating from acetylene
hydrogen (HC≡) as well as the CtC at 68 and 84 ppm
Number-average molecular weights (Mn) of the dif-
ferent polymers vary between 4500 and 21 600. The

Macromolecules, Vol. 37, No. 13, 2004
Polymers Bearing Liquid Crystalline Groups 4789
Ta ble 4. NMR Resu lts for P olym er s
1H NMRa
13C NMRa
19F NMRb
polymer
-C*HF- (J HF in Hz)c
-C*HCH3-
olefinc,d
-C*HF- (J CF in Hz)c
-C*HF-
poly-1
poly-2
poly-3
poly-4
poly-5
poly-6
poly-7
poly-8
poly-9
5.10 (sextet)
5.15 (sextet)
6.07 (s, 0.96He)
f
f
f
4.83 (d, 51.6)
4.76 (d, 49.4)
4.76 (d, 52.1)
4.82 (d, 49.0)
4.85 (d, 47.1)
4.70 (d, 49.3)
91.52 (d, 172.1)
91.55 (d, 172.5)
91.53 (d, 172.2)
91.92 (d, 171.9)
91.48 (d, 171.8)
91.56 (d, 172.6)
-187.74
-187.76
-187.47
-187.46
-187.36
-187.45
6.05 (s, 0.79 He)
6.14 (s, 0.10 He)
6.10 (s, 0.10 He)
f
f
a
b
Chemical shift value (δ, in CDCl3, ppm form TMS), asterisk (*) ) chiral center. Trifluorotoluene was used as an internal standard
(δ in CDCl3). c d ) doublet, s ) singlet. Olefin proton of cis form. e Integral value of proton signal in 1H NMR. f Did not clearly appear.
d
in 13C NMR (125 Hz) appeared. These results indicate
that an opening of the acetylenic carbon in the monomer
catalyzed by the Rh complex catalyst gives a linear
polymer with conjugated double bond. From the results
1
of H NMR spectra, poly-1 and poly-5-7 have peaks
at 6.05-6.14 ppm characteristic of a proton attached
to a cis double bond.28 On the other hand, poly-2-4,
poly-8, and poly-9 show no peak corresponding to the
cis form. This result suggests that poly-1 and poly-5-7
are predominantly cis configuration, and poly-2-4,
poly-8, and poly-9 were isomerized from the cis into
trans configuration during the polymerization. In gen-
eral, polymerization of acetylene monomer by Rh com-
plex catalyst yields cis-rich polymer. The cis-trans
isomerization during the acetylene polymerization is
dependent on temperature. In this experiment, we
attempted polymerizations of the monomers with rela-
tively bulky substituents at reflux temperature so as
to increase reactivity. The polymer main chains of
poly-1 and poly-5-7 may be partly isomerized (cis
content <100%) and showed an olefin proton signal
around 6 ppm in the 1H NMR due to residual cis
content, while other polymer main chains were isomer-
ized to trans configuration ≈100% during the reaction.
It is probable that polymerization at low temperature
produces cis-rich polymers; however, in this case, higher
molecular weight FLC polymers cannot be obtained.
1
In H NMR measurement, a signal due to the hydro-
gen atom attached onto the chiral carbon appeared at
5.1 ppm as a sextet for m on o-1 and m on o-2. The
corresponding polymers, poly-1 and poly-2, showed the
same δ value signal at 5.1 ppm. Also, a doublet signal
due to a hydrogen atom attached to the chiral carbon
with a fluorine atom for m on o-4-9 appeared around
4.9 ppm, the signal was unchanged after polymerization.
A signal due to the fluorine atom appeared around -187
ppm in 19F NMR (470 MHz) of all the monomers and
polymers. A doublet signal appeared in the 13C NMR of
m on o-4-9 and poly-4-9 at 91.5 ppm due to C-F
F igu r e 2. Polarizing optical micrographsof m on o-9. Oily
streak texture of chiral nematic (N*) phase at 159 °C (top).
Line texture of chiral smectic C (SmC*) phase at 134 °C
(bottom).
smectic A (SmA*) in the heating process, and it showed
SmA* and the striated fan-shaped texture of chiral
smectic B (SmB*) in the cooling process. In the SmA*
phase, m on o-6 and m on o-7 showed a broad halo in the
wide-angle region in XRD which can be ascribed to the
distance between the molecules in the LC phase. The
wide-angle halo became sharp in the SmB* phase due
to the fact that the distances between the LC molecules
were constant. This result supports the fact that mon o-6
and m on o-7 show no SmC* but show SmB* in the
cooling process. Mon o-8 showed the fingerprint texture
of the N* and the striated fan-shaped texture of the
SmC* phases. On cooling from the isotropic phase,
m on o-9 showed the N* and SmC* phases and two
unidentified higher order smectic phases. The SmC*
phase is observed in a wide temperature range for
m on o-8 and m on o-9. Figure 2 shows the typical N* and
the SmC* textures of m on o-9. Temperature-dependent
1
coupling (J CF ) 172 Hz). H-19F heteronuclear Over-
hauser effect spectroscopy (HOESY) results indicate
1
that the doublet at 4.9 ppm in the H NMR (500 MHz)
due to the proton on the chiral carbon and the signal at
-187 ppm in 19F NMR (470 MHz) due to the fluorine
atom attached onto the chiral center are correlated.
NMR results of the polymers are summarized in Table
4.
The acetylene monomers m on o-1-5 showed no me-
sophase. The precursor 12 exhibited enantiotropic chiral
nematic (N*) with fingerprint texture and unidentified
smectic X (SmX) phases. This is probably due to the
formation of a hydrogen-bonding dimer of 12. Mon o-7
showed the focal conic fan-shaped texture of chiral

4790 Goto et al.
Macromolecules, Vol. 37, No. 13, 2004
F igu r e 5. XRD patterns of poly-9.
F igu r e 3. XRD patterns of m on o-9.
F igu r e 6. DSC curves of poly-8.
shown in Figure 5. When poly-9 was allowed to cool
from the isotropic state, the polymer showed the fin-
gerprint texture typical of the N* phase and a filament
texture at 193 °C under POM observation, as shown in
Figure 8 (top). At the same time, the XRD pattern of
poly-9 measured in the LC phase at 190 °C gave two
reflection peaks. The sharp peak at the small-angle
region and broad halo at the wide-angle region cor-
respond to a distance of 38.3 (layer spacing) and 4.62 Å
(distance between side chains). This is a typical pattern
of the smectic phase. In other words, a SmA-type layer
structure exists in this phase for poly-9. The optical
texture and the results of XRD measurement is due to
poly-9 forming twist grain boundary smectic A (TGBA*)
phase, since the TGBA* phase possesses both charac-
teristics of the N* and smectic A phases. The TGBA*
helical axis is parallel to the smectic layer planes, and
the director in the layer rotates discontinuously around
the twist axis.26 When temperature was allowed to cool
to 160 °C, the d-spacing of the small-angle reflection
decreased from 38.3 to 33.0 Å. This result suggests the
formation of a tilted smectic phase. A parabolic texture
of the SmC* phase for poly-9 was observed in this
temperature range under POM, as shown in Figure 8
(bottom). When the temperature was further cooled to
120 °C, the d-spacing of the small-angle reflection
increased from 33.0 to 35.4 Å and the wide-angle
reflection became sharp. This structure was unchanged
in the glassy state.
F igu r e 4. Polarizing optical micrographs of poly-4. Baˆtonnets
texture of SmA* at 140 °C (top). Striated baˆtonnets texture of
SmX at 120 °C (bottom).
XRD patterns were obtained from the powder sample
of m on o-9 at 160, 130, and 90 °C (Figure 3).
P oly-1 (spacer length: n ) 3) showed no liquid
crystallinity. P oly-2 (spacer length: n ) 10) showed the
sanded texture. P oly-3 showed the SmA and SmX and
poly-4 showed the baˆtonnets texture of the SmA* and
the SmX phases during the cooling process, as shown
in Figure 4. Mon o-6 showed no SmC*; on the other
hand, poly-6 of the corresponding polymer exhibited the
SmC*. This is probably due to the LC side chains
aligning themselves with the polyacetylene main chain,
and this order allows the side chains to form an SmC*
array. This phenomenon could be referred to the so-
called polymer effects. XRD patterns of poly-9 were
Similarly, poly-8 shows TGBA* in both cooling and
heating processes. P oly-8 also showed filament texture
of the TGBA* and striated fan-shaped texture of the
SmC* phases with enantiotropic nature; however, poly-8
and poly-9 showed no square grid pattern of the TGBC*
phase. This is the first time the TGBA* phase has been
observed in LC conjugated polymers. DSC thermograms
of poly-8 and m on o-9, poly-9 are shown in Figures 6

Macromolecules, Vol. 37, No. 13, 2004
Polymers Bearing Liquid Crystalline Groups 4791
Ta ble 5. Th er m a l Tr a n sition of Mon om er s a n d P olym er s
phase-transition temperature (°C)
compd
heating
cooling
12
K‚105‚SmX 121‚N*‚138‚Iso*
K‚102‚SmB*‚110‚SmA*‚181‚Iso*
K‚105‚SmA*‚165‚Iso*
K‚107‚SmC*‚130‚N*‚167‚Iso*
K‚114‚SmC*‚149‚N*‚168‚Iso*
a
K‚96‚SmX‚118‚N*‚135‚Iso*
K‚58‚SmB*‚101‚SmA*‚162‚Iso*
K‚47‚SmB*‚93‚SmA*‚162‚Iso*
K‚87‚SmC*‚127‚N*‚164‚Iso*
K‚79‚SmX2‚84‚SmX1‚98‚SmC* 147‚N*‚166‚Iso*
a
mono-6
mono-7
mono-8
mono-9
poly-1
poly-2
poly-3
poly-4
poly-5
poly-6
poly-7
poly-8
poly-9
g‚52‚SmX‚87‚Iso*
g -bSmX‚61‚Iso*
g‚144‚SmA‚164‚Iso
g‚142‚SmX-bSmA‚158‚Iso
g‚121‚SmA*‚149‚Iso*
g‚117‚SmX-bSmA*‚144‚Iso*
g‚78‚SmC*‚124‚SmA*‚140‚Iso*
g‚111‚SmC*‚160‚SmA*‚305‚Iso*
g‚110‚SmX‚118‚SmC*‚162‚SmA* 203‚Iso*
g‚113‚SmC*-bTGBA*-bN*‚214‚Iso*
g‚97‚SmX‚121‚SmC*-bTGBA*-bN*‚208‚Iso*
g‚80‚SmA*‚180‚Iso*
g‚135‚SmA*‚306‚Iso*
g‚120‚SmA*‚209‚Iso*
g‚121‚SmC*-bTGBA*-bN*‚217‚Iso*
g‚104‚SmX‚126‚SmC*-bTGBA*-bN*‚213‚Iso*
a
b
No LC phase. No distinct transition was observed in DSC. K, crystal; SmX, unidentified LC phase; SmA, smectic A phase; SmA*,
chiral smectic A phase; SmB*, chiral smectic B phase; SmC*, chiral smectic C phase; TGBA*, twist grain boundary smectic A* phase; N*,
chiral nematic phase; Iso*, isotropic.
F igu r e 7. DSC curves of m on o-9 and poly-9.
and 7, respectively. Thermal transitions of m on o-8 are
enantiotropic, and three peaks associated, respectively,
with the Iso*-N*, N*-SmC*, and SmC*-K (K: crystal)
transitions during the heating and cooling scans appear.
An exothermic peak due to cis-trans isomerization of
F igu r e 8. Polarizing optical micrographs of poly-9. Filament
texture of twist grain boundary (TGBA*) phase at 193 °C (top).
Parabolic texture of SmC* phase at 165 °C (bottom).
the polyacetylene main chain was observed around 180
°C during the first heating process of the DSC measure-
ments for poly-1, poly-5, poly-6, and poly-7. In the
second heating scan of DSC thermograms, poly-8
displays two peaks in both the heating and cooling cycle.
In the heating process, two peaks at 121 and 217 °C
were observed, which can be ascribed to the g-SmC* (g
) glassy state) and N*-Iso* transitions; however, no
clear peak of the SmC*-TGBA* transition was ob-
served. The phase transition is second order in nature;
on the other hand, poly-8 shows visible change of the
optical texture at 168 °C under the POM observations.
Also, a peak corresponding to the phase transition from
TGBA* to N* did not appear clearly in the DSC
measurements. This can be due to the fact that TGBA*
is a frustrated LC phase. Mon o-9 shows three peaks
due to K-SmC*, SmC*-N*, and N*-Iso* in the heating
process and five peaks due to Iso*-N*, N*-SmC*,
SmC*-SmX1, SmX1-SmX2, and SmX2-K during the
cooling process. P oly-9 showed two distinct peaks due
to the SmX-SmC* and N*-Iso* transitions at 126 and
213 °C on the second heating, respectively, but SmC*-
TGBA* and TGBA*-N* transitions did not clearly
appear in the DSC measurements. P oly-6 and poly-7,
with the ester group facing the opposite direction from
those of poly-8 and poly-9, show no TGBA* phase, and
they exhibit monotropic SmC* phase. Phase-transition
temperatures of 12, the monomers, and the polymers
are summarized in Table 5.

4792 Goto et al.
Macromolecules, Vol. 37, No. 13, 2004
F igu r e 9. Possible change of the LC structures.
Generally there are two possible structures for the
LC-substituted polyacetylene derivatives, where the side
chains are located on either one side or both sides of
the main chain in the LC layers. They are abbreviated
as “one-sided” and “both-sided” structures, respectively.
In the case of poly-3, molecular mechanics (MM)
calculations imply that the d-space (interlayer distance)
of the one-sided and both-sided structures is 34.7 and
67.5 Å, respectively. XRD measurements gave a d-space
of 55.2 Å, which is close to that predicted for the both-
sided structure. Mon o-9 shows peaks at 38.3 (160 °C,
N*), 33.5 (130 °C, SmC*), and 38.3 Å (90 °C, SmX1), and
poly-9 shows peaks at 38.3 (190 °C, N*), 33.0 (160 °C,
SmC*), and 35.4 Å (120 °C: SmX, and room tempera-
ture: glassy state) in XRD measurements. These results
suggest that poly-9 forms the one-sided structure
because the layer spacing of m on o-9 and poly-9 show
similar values in XRD measurement in each LC tem-
perature range. Taking into account the results of the
XRD measurements of the monomers and the polymers
and the MM calculations, it can be argued that poly-3
and poly-4 have the both-sided structure while poly-8
and poly-9 the one-sided structure.
In the cooling process, poly-8 and poly-9 show first
the N* phase after the Iso*. The nematic phase has low
order and high symmetry compared to the other liquid
crystal phases31 as well as the lowest viscosity. The N*
phase is the chiral form of the nematic phase. The phase
consists of local nematic layers which are continuously
twisted with respect to each other and show an overall
helical structure. The long molecular axis of the asym-
metric structure is oriented to a single direction in each
layer. The property strongly depends on the chirality
of the mesogen. In the case of the LC polymers, the
asymmetric side chains align to one direction along the
director of each layer in the N* phase, and it is possible
to form one-sided structure for poly-8 and poly-9 in the
N*. The polymers can transform into the TGBA*, SmC*,
and glassy state maintaining the one-sided structure
of the N*. On the other hand, poly-3 and poly-4 show
no N* phase in the cooling process. They first form the
SmA* with bilayer structure after Iso* in the cooling
process and can be transformed into the glassy state
via the SmX with both-sided structure. Possible LC
structures along with the phase transitions are shown
in Figure 9.
F igu r e 10. Schematic illustration of possible conduction of
one-sided and both-sided polymer structures.
tivity measurement were prepared by gradually cooling
to room temperature from the isotropic phase. Although
the color of the sample changed to dark purple after the
doping, the optical texture was unchanged.
Electrical conductivities of poly-3, poly-4, poly-8, and
poly-9 after iodine doping were 3.5 × 10-7, 7.3 × 10-7
,
5.3 × 10-5, and 1.8 × 10-4 S/cm, respectively. This result
indicated that the polymers of the one-sided structure
showed 100-500 times higher conductivities than the
polymers of the both-sided structure. The distance
between the main chains of the polymers with the one-
sided structure is shorter than that of the polymers with
the both-sided structure. This can cause better electrical
conduction between the polymer main chains by the
hopping mechanism than the polymer with both-sided
structure. This would cause poly-8 and poly-9 with the
one-sided structure to give higher electrical conductivi-
ties than poly-3 and poly-4 with the both-sided struc-
ture. A possible conduction of the one-sided structure
and the both-sided structure of the polymers is shown
in Figure 10.
In conclusion, novel LC polyacetylene derivatives
have been synthesized by introducing achiral LC
groups or chiral LC groups into the side chains. Three
polymers (poly-5-7) showed a monotropic SmC* phase,
and two polymers (poly-8, poly-9) showed an enantio-
tropic SmC* phase, whose temperature range was
quite wide (in the range of 50 °C). This is the first re-
port of polyacetylene derivatives showing SmC*. Poly-
mers with SmC* have the ability to respond more
quickly to an external electric field than non-FLC ones.
Therefore, the conjugated polymers bearing FLC sub-
stituents can be used in electrooptical applications such
as unique electronic devices with high-speed response.
Also, it may be possible to use them in an FLC memory
type display.
We performed iodine doping of the polymers in the
glassy state (solid state), which retains the former liquid
crystalline order. The polymer samples for the conduc-

Macromolecules, Vol. 37, No. 13, 2004
Polymers Bearing Liquid Crystalline Groups 4793
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(12) Iino, K.; Goto, H.; Akagi, K.; Shirakawa, H.; Kawaguchi, A.
Ack n ow led gm en t . We thank Professor Hideki
Shirakawa for valuable discussions and advice. We also
thank Messrs. Yutaka Bannai and J yunnya Murakami
(Institute of Materials Science, U. Tsukuba) for their
assistance. This work was supported by Grant-in-Aids
for Scientific Research from the Ministry of Education,
Culture, Sports, Science and Technology, J apan, and
“Promotion of Creative Interdisciplinary of Materials
Science for Novel Functions” of the 21st century Center
of Excellence (COE) program of the Ministry of Educa-
tion, Culture, Sports, Science and Technology, J apan,
and The Ogasawara Foundation for Promotion of Sci-
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