Synthesis and properties of ion-conducting poly(anthrylacetylene) derivatives

Article abstract of DOI:10.1021/ma030019x

Poly(anthryacetylenes) bearing oligooxyethylene units were synthesized from 10-ethynyl-9-[3,6-dioxaheptyl]oxycarbonylanthracene (1) and 10-ethynyl-9-[3,6,9,12-tetraoxatridecyl]oxycarbonyl-anthracene (2) by using a transition metal catalyst, WCl₆, in 30% and 34% yields, respectively. Both of the polymers were black solids and soluble in chloroform, tetrahydrofuran, acetone, etc., but insoluble in alcohols, aliphatic hydrocarbons, etc. The UV-vis spectra of the polymers showed absorption maxima and band edges at around 570 and 750 nm, respectively, indicating that the polymer chains possess highly extended conjugation. These polymers exhibited blue emission (emission maxima ≈470 nm) upon photoexcitation at 380 nm. Poly(2) showed a fairly large ionic conductivity (4.1 × 10^-5 S/cm) at 80 °C upon doping with Li(CF₃SO₂)₂N.

Full text of DOI:10.1021/ma030019x

4786
Macromolecules 2003, 36, 4786-4789
Synthesis and Properties of Ion-Conducting Poly(anthrylacetylene)
Derivatives
S. M. Abd u l Ka r im ,† Ryoji Nom u r a ,† F u m io Sa n d a ,† Sh ir o Sek i,‡
Ma sa yosh i Wa ta n a be,‡ a n d Tosh io Ma su d a *,†
Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University,
Kyoto 606-8501, J apan, and Department of Chemistry and Biotechnology, Graduate School of
Engineering, Yokohama National University, Yokohama 240-8501, J apan
Received J anuary 10, 2003; Revised Manuscript Received April 28, 2003
ABSTRACT: Poly(anthryacetylenes) bearing oligooxyethylene units were synthesized from 10-ethynyl-
9-[3,6-dioxaheptyl]oxycarbonylanthracene (1) and 10-ethynyl-9-[3,6,9,12-tetraoxatridecyl]oxycarbonyl-
anthracene (2) by using a transition metal catalyst, WCl6, in 30% and 34% yields, respectively. Both of
the polymers were black solids and soluble in chloroform, tetrahydrofuran, acetone, etc., but insoluble in
alcohols, aliphatic hydrocarbons, etc. The UV-vis spectra of the polymers showed absorption maxima
and band edges at around 570 and 750 nm, respectively, indicating that the polymer chains possess
highly extended conjugation. These polymers exhibited blue emission (emission maxima ≈470 nm) upon
photoexcitation at 380 nm. Poly(2) showed a fairly large ionic conductivity (4.1 × 10-5 S/cm) at 80 °C
upon doping with Li(CF3SO2)2N.
In tr od u ction
by exerting properties stemming from their ion-conduct-
ing and conjugative properties. To our knowledge, there
is no report on substituted polyacetylenes containing
oxyethylene units. Thus, it is interesting to study the
synthesis and properties of substituted polyacetylenes,
especially ring-substituted poly(arylacetylenes) having
oligooxyethylenes.
In this paper, we report the synthesis of novel poly-
(anthrylacetylenes) with oligooxyethylene side chains.
Properties of the resulting polymers are further dis-
cussed.
Ion-conducting polymers are interesting materials for
its potential application in microelectronic devices. Their
applications include solid-state batteries, smart win-
dows, components in solid-state sensors, and solid-state
transistors.1,2 Poly(ethylene oxide) is one of the most
well-known ion-conducting polymers, but its high crys-
tallinity, which impairs the ionic conductivity unless
used at temperature above its melting point, and poor
mechanical properties preclude room temperature ap-
plication.3 However, several strategies have been de-
veloped to overcome these deficiencies, and amorphous
polymers containing oxyethylene units have been syn-
thesized. These include formation of block or random
copolymers,4 cross-linked network structures,5 and the
use of comb-branch polymers with oligomeric ethylene
oxide side chains,6 The major role of oxyethylene units
in these polymers is to take part in ion transport which
is the crucial part in ion-conducting polymers.
Substituted polyacetylenes have attracted much at-
tention as promising functional materials because of
their unique properties such as gas permeability, semi-
conductivity, photoconductivity, photo- and electro-
luminescence, nonlinear optical properties, etc.7,8 These
properties are based on their molecular architechture
featuring stiff and conjugated main-chain structure and
various side groups and can be tuned through both the
control of main-chain geometric structure and the
judicious choice of side groups. Among substituted
polyacetylenes, those obtained from monosubstituted
acetylenes with condensed aromatic rings are especially
interesting from the viewpoint that they provide ex-
tended conjugation to show large third-order suscepti-
bility in nonlinear optics along with other properties.9-11
Incorporation of oligooxyethylene units onto the con-
densed aromatic rings of substituted acetylenes may
lead to the development of novel functional polymers
Exp er im en ta l Section
Gen er a l. All the reagents used in monomer synthesis were
commercially obtained and used as received. The solvents used
in the experiments were purified by the usual methods.
Syn th esis of Mon om er s. 10-Bromo-9-anthracenecarbonyl
Chloride (a ).12 Into a suspension of 9,10-dibromoanthracene
(50.7 g, 151 mmol) in dry ether (400 mL) was added dropwise
a 1.6 M n-butyllithium solution in hexane (151 mmol) at -78
°C. After the reaction mixture was stirred for 30 min at -78
°C and then at 0 °C for another 30 min, the suspension was
transferred into an excess amount of dry ice (ca. 500 g) and
allowed to stand overnight. The resulting lithium salt of 10-
bromo-9-anthracenecarboxylic was collected as a solid after
removing ether by filtration. The salt was then dispersed in
water (500 mL) and acidified with 2 N HCl to precipitate 10-
bromo-9-anthracenecarboxylic acid. The resulting carboxylic
acid was isolated by filtration and dried under reduced
pressure. A chloroform suspension (400 mL) containing 20 g
(66.4 mmol) of 10-bromo-9-anthracenecarboxylic acid and
thionyl chloride (20 mL) was heated under reflux until the
mixture became homogeneous. The solution was concentrated
in vacuo to give 21.2 g (yield 100%) of 10-bromo-9-anthracene-
carbonyl chloride as a yellow solid. The crude product was used
for the following reaction without further purification. 1H NMR
(400 MHz, CDCl3) δ: 7.60-7.77 (m, 4H), 8.02-8.09 (m, 2H),
7.60-7.77 ppm (m, 2H).
10-Bromo-9-[3,6-dioxaheptyl]oxycarbonylanthracene (b). To
a solution of diethylene glycol monomethyl ether (3.6 g, 30
mmol) and pyridine (4.0 mL, 50 mmol) in dry chloroform (120
mL) was slowly added solid 10-bromo-9-anthracenecarbonyl
chloride (8.0 g, 25 mmol) with a spatula at room temperature,
and the solution was stirred overnight at ambient temperature
† Kyoto University.
‡ Yokohama National University.
* Corresponding author: Tel +81-75-5613; Fax +81-75-753-
5908; e-mail masuda@adv.polym.kyoto-u.ac.jp.
10.1021/ma030019x CCC: $25.00 © 2003 American Chemical Society
Published on Web 06/07/2003

Macromolecules, Vol. 36, No. 13, 2003
Poly(anthrylacetylene) Derivatives 4787
Sch em e 1a
a
(i) BuLi (1 equiv)/Et2O/-78 °C; (ii) CO2/H+; (iii) SOCl2/CHCl3; (iv) HO-(CH2CH2O)n-CH3/pyridine/CHCl3; (v) (trimethyl-
silyl)acetylene/Pd/Cu/Et3N/THF; (vi) n-Bu4NF/THF; (viii) WCl6/toluene/80 °C.
in a nitrogen atmosphere. After removing chloroform by
evaporation, the residue was extracted with benzene, washed
with 2 N HCl followed by water and then with brine, dried
over MgSO4, and concentrated to give a crude product.
Purification was carried out by SiO2 column chromatography
(hexane/ethyl acetate ) 1/1). Yellowish liquid. Yield 65% (6.6
126.82, 126.87, 127.05, 127.68, 129.30, 132.39, 169.08 ppm.
IR (KBr): 3283, 3065, 2876, 1724, 1282, 1207, 1107, 1030, 663
cm-1. Mass spectrum (FAB): Calcd for C26H28O6: m/e 436.4969.
Found: m/e 436.4951.
P olym er iza tion . Polymerizations were performed in a
Schlenk tube equipped with a three-way stopcock under a
nitrogen atmosphere. Unless otherwise specified, the poly-
merizations were carried out in toluene at 80 °C for 24 h; the
initial monomer concentration was 400 mM, and the catalyst
concentration was 20 mM. Polymers were collected by repeated
precipitation either in methanol or in hexane, and the yields
of the polymers were determined by gravimetry.
1
g). H NMR (400 MHz, CDCl3) δ: 3.37 (s, 3H), 3.57 (t, 2H, J
) 4.4 Hz), 3.69 (t, 2H, J ) 4.4 Hz), 3.92 (t, 2H, J ) 4.8 Hz),
4.77 (t, 2H, J ) 4.8 Hz), 7.53-7.58 (m, 4H), 8.07 (d, 2H, J )
8.0 Hz), 8.58 ppm (d, 2H, J ) 8.0 Hz).
10-Bromo-9-[3,6,9,12-tetraoxatridecyl]oxycarbonylanthra-
cene (c). This compound was prepared in the same manner
as 10-bromo-9-[3,6-dioxaheptyl]oxycarbonylanthracene. Yel-
P olym er Ch a r a cter iza tion . The molecular weights of
polymers were estimated by gel permeation chromatography
(GPC) with CHCl3 as an eluent and with polystyrene (PSt)
standards. IR spectra, ultraviolet-visible (UV-vis) spectra,
1
lowish liquid. Yield 57%. H NMR (400 MHz, CDCl3) δ: 3.30
(s, 3H), 3.33-3.71 (m, 12H), 3.92 (t, 2H, J ) 4.8 Hz), 4.78 (t,
2H, J ) 4.8 Hz), 7.52-7.62 (m, 4H), 8.09 (d, 2H, J ) 8.0 Hz),
8.58 ppm (d, 2H, J ) 8.0 Hz).
emission spectra, and NMR spectra were recorded on
a
Shimadzu FTIR-8100 spectrophotometer, a Shimadzu UV-
2200 spectrophotometer, a J ASCO FP-750 spectrophotometer,
and a J EOL EX-400 spectrometer, respectively. Thermogravi-
metric analyses (TGA) were conducted in air on a Perkin-
Elmer TGA7 thermal analyzer.
10-Ethynyl-9-[3,6-dioxaheptyl]oxycarbonylanthracene (1). A
dry THF (120 mL) solution containing 10-bromo-9-[3,6-dioxa-
heptyl]oxycarbonylanthracene (5.8 g, 14.4 mmol), triethyl-
amine (3 mL, 21.5 mmol), (trimethylsilyl)acetylene (4 mL, 28.3
mmol), PdCl2(PPh3)2 (330 mg, 0.5 mmol), and CuI (95 mg, 0.5
mmol) was kept stirring at room temperature for 10 days. The
Pd catalyst (ca. 200 mg) was added several times during the
reaction, and the reaction was monitored using 1H NMR. After
removing the solvent, ether was added to the residue. The
resulting mixture was filtered, and the filtrate was washed
with water and then with brine, dried over MgSO4, and
concentrated to give 10-(2-trimethylsilylethynyl)-9-[3,6-dioxa-
heptyl]oxycarbonylanthracene. This crude product was dis-
solved in dry THF (80 mL) and treated with a 1.0 M THF
solution of tetrabutylammonium fluoride (17 mL) at 0 °C for
15 min. Ethereal working up of the solution gave 1 as viscous
yellow liquid. Purification was carried out by SiO2 column
chromatography (hexane/ethyl acetate ) 1/1). The yield of 1
P r ep a r a tion of Solid P olym er Electr olytes. Lithium bis-
(trifluoromethanesulfonyl)imide (Li(CF3SO2)2N) was used as
an electrolyte salt for solid polymer electrolytes. Poly(1) and
poly(2), which had been dried under high vacuum at room
temperature for 24 h and stored in a glovebox (VAC, [O2] < 1
ppm, [H2O] <1 ppm), were used as a matrix of the solid
polymer electrolytes. A given amount ([lithium]/[ether unit]
) 0.08) of Li(CF3SO2)2N and either poly(1) or poly(2) were
dissolved in anhydrous THF to form a homogeneous solution.
The mixed solution was cast on a poly(tetrafluoroethylene)
(PTFE) plate. The solvent was allowed to slowly evaporate at
room temperature in the glovebox for 12 h and then completely
removed under high vacuum for 24 h to obtain the polymer
electrolyte film.
1
based on b was 80%. H NMR (400 MHz, CDCl3) δ: 3.37 (s,
3H), 3.57 (t, 2H, J ) 4.4 Hz), 3.69 (t, 2H, J ) 4.4 Hz), 3.92 (t,
2H, J ) 4.8 Hz), 4.05 (s, 1H), 4.77 (t, 2H, J ) 4.8 Hz), 7.53-
7.58 (m, 4H), 8.07 (d, 2H, J ) 8.0 Hz), 8.58 (d, 2H, J ) 8.0 Hz)
ppm. 13C NMR (100 MHz, CDCl3) δ: 58.73, 68.97, 70.22, 71.90,
79.90, 89.60, 125.4, 126.70, 126.80, 126.89, 127.05, 127.68,
129.20, 132.50, 169.10 ppm. IR (KBr): 3285, 3063, 2878, 1724,
1282, 1207, 1140, 1028, 663 cm-1. Mass spectrum (FAB): Calcd
for C22H20O4: m/e 348.1360. Found: m/e 348.1362.
Ion ic Con d u ctivity Mea su r em en t. Ionic conductivity was
determined by means of the complex impedance measure-
ments, using a computer-controlled Hewlett-Packard 4192A
LF impedance analyzer over the frequency range from 5 Hz
to 1 MHz The polymer electrolytes film was cut into disks of
13 mm in diameter. The polymer electrolyte films, sandwiched
between mirror-finished stainless steel electrodes, were sealed
in PTFE containers in the glovebox and were subjected to the
complex impedance measurements. The measurements were
carried out with heating from 40 to 130 °C, and the samples
were thermally equilibrated at each temperature for at least
1.5 h before the measurements.
10-Ethynyl-9-[3,6,9,12-tetraoxatridecyl]oxycarbonylanthra-
cene (2). This compound was prepared using the same proce-
dure as for 10-ethynyl-9-[3,6-dioxaheptyl]oxycarbonylanthra-
1
cene. Viscous yellow liquid. Yield based on c: 48%. H NMR
(400 MHz, CDCl3) δ: 3.30 (s, 3H), 3.33-3.71 (m, 12H), 3.92
(t, 2H, J ) 4.8 Hz), 4.05 (s, 1H), 4.78 (t, 2H, J ) 4.8 Hz), 7.52-
7.62 (m, 4H), 8.09 (d, 2H, J ) 8.0 Hz), 8.58 ppm (d, 2H, J )
8.0 Hz). 13C NMR (100 MHz, CDCl3) δ: 58.65, 64.67, 68.99,
70.40, 70.49, 70.60, 71.80, 79.80, 89.66, 125.56, 125.89, 126.71,
Resu lts a n d Discu ssion
Syn th esis of Mon om er . Scheme 1 illustrates the
synthetic route for the substituted PEO-containing

4788 Abdul Karim et al.
Macromolecules, Vol. 36, No. 13, 2003
Ta ble 1. P olym er iza tion of 1 a n d 2 w ith WCl6 (in Tolu en e,
80 °C, 24 h (48 h for 2); [M]0 ) 400 m M, [Ca t] ) 20 m M)
b
monomer yield, %a Mn × 10-3 b Mw/Mn
color solubilityc
1
2
30
34
33.2
4.1
3.2
2.1
black
black
soluble
soluble
a
By the gravimetric method. b Measured by GPC (eluent CHCl3,
PSt standards). c In THF, toluene, CHCl3, DMF, acetone, etc.
anthrylacetylene monomers. The monomers were pre-
pared starting from commercially available 9,10-di-
bromoanthracene via several steps. 9,10-Dibromo-
anthracene was transformed into the corresponding
monoacid chloride, which was then converted into the
bromoester. The Sonogashira coupling of the bromoester
with (trimethylsilyl)acetylene followed by desilylation
with tetrabutylammonium fluoride gave the monomers
1 and 2 in 52% and 27% total yields, respectively.
P olym er iza tion . Proper selection of catalysts for the
polymerization of substituted acetylenes is crucial.8a,13
For example, W, Mo, and Rh catalysts are suitable for
monosubstituted acetylenes, but they are hardly effec-
tive in the polymerization of sterically crowded disub-
stituted acetylenes. On the other hand, Nb and Ta
catalysts are effective for the polymerization of disub-
stituted acetylenes while they induce only cyclotrimer-
ization for monosubstituted acetylenes. Further, among
Mo, Rh, and W catalysts, W catalysts are particularly
efficient in the polymerization of aromatic monosubsti-
tuted acetylenes bearing substituents with large steric
hindrance. It has been found in our previous study that
the WCl6 catalyst is the most suitable for the polymer-
ization of anthrylacetylenes.10b In this study, therefore,
we chose only WCl6 as a catalyst for the polymerization
reactions. The results of the polymerization are shown
in Table 1. When polymerized with WCl6, both of the
monomers underwent polymerization smoothly to pro-
vide black solids soluble in common organic solvents.
The yields of poly(1) and poly(2) were 30% and 34%,
respectively. According to GPC, the number-average
molecular weights (Mn) of poly(1) and poly(2) were 33.2
× 103 (Mw/Mn ) 3.2) and 4.1 × 103 (Mw/Mn ) 2.1),
respectively.
F igu r e 1. UV-vis spectra of poly(1) (1.0 × 10-4 M) and
poly(2) (5.7 × 10-5 M) in chloroform at room temperature.
These polymers, thus, do not possess a selective cis
structure. A general feature of W catalysts is that it
provides trans-rich polymers from acetylenes, suggest-
ing that the present polymers possess trans-rich geo-
metrical structure.
P olym er P r op er ties. The obtained polymers did not
show glass transition temperatures according to DSC
measurements in the range of -30 to 100 °C. These
polymers were soluble in common organic solvents such
as toluene, acetone, chloroform, tetrahydrofuran (THF),
dimethyl sulfoxide (DMSO), and N,N-dimethyform-
amide (DMF) but were insoluble in hexane, higher
alkanes, and alcohols.
The weight loss of poly(1) and poly(2) in air started
at 327 and 239 °C, respectively, in thermogravimetric
analyses (TGA) whereas the onset temperature of
weight loss of poly(phenylacetylene) is known to be
around 250 °C.10a These results suggest that poly(1) is
superior but poly(2) is inferior to poly(phenylacetylene)
in thermal stability. The TGA curves of poly(1) and
poly(2) showed inflection points at around 450 and 480
°C, respectively, which are presumably due to the
cleavage of pendant ester groups, because the values of
percent weight loss agree with those of the pendant
molecular weights (ca. 49% and 58%). The reason for
lower onset temperature of poly(2) than that of poly(1)
is not clear at this stage; however, since the patterns of
the TGA curves are the same, it is reasonable to think
that the longer flexible ethylene oxide chain is respon-
sible for it.
The UV-vis spectra of poly(1) and poly(2) are shown
in Figure 1. The absorption bands tailing from 450 to
750 nm can be attributed to the π-π* electronic transi-
tion associated with the π-conjugated polymer back-
bones. The peaks below 450 nm are due to the absorp-
tion resulting from the electronic transition by the
anthryl groups. The absorption maximum of poly(1) was
found to be at 570 nm (ꢀ ) 5.4 × 103 M-1 cm-1), while
poly(2) showed an absorption maximum at around 530
nm (ꢀ ) 2.5 × 103 M-1 cm-1). The absorption band edges
were observed at around 750 nm for poly(1) and 720
nm for poly(2), which are quite red-shifted compared
with that of poly(phenylacetylene) (band edge ∼ 600 nm)
prepared by the same catalyst.10c These results suggest
that the conjugation lengths of the main chain of the
present polymers are extremely extended.14
Ch a r a ct er iza t ion . The characterization of poly(1)
and poly(2) was performed by using IR and NMR
spectroscopies. In the IR spectra of monomers 1 and 2,
an absorption peak due to the stretching vibration of
CtC bond was observed at around 2100 cm-1. The
stretching and bending vibrations of the tC-H group
were clearly observed at 3280 and 660 cm-1, respec-
tively, in the IR spectra of both monomers. On the other
hand, these signals completely disappeared in the
1
spectra of the polymers. In the H NMR spectra of the
polymers, the signals at around 4.1 ppm assigned to the
acetylenic proton (tCH) of the monomers were un-
detectable. Similarly, the signals at around 80 and 89
ppm due to the acetylenic carbons of the monomers
disappeared in the 13C NMR spectra of the polymers.
All of these results indicate that opening of the triple
bonds of the monomers occurred during the polymeri-
zation, and the polymer backbones are composed of
alternating double bonds.
Highly stereoregular cis polymers formed from phen-
ylacetylenes in the presence of Rh catalysts are known
to show a sharp signal based on the olefinic protons in
the main chain around 6-7 ppm in 1H NMR.8a,13 On
the other hand, the present polymers gave olefinic and
aromatic protons as very broad signals in this region.

Macromolecules, Vol. 36, No. 13, 2003
Poly(anthrylacetylene) Derivatives 4789
side chain of poly(2) are preferable, compared to two
oxyethylene units of poly(1), in terms of lithium ion
solvation as well as their faster molecular motion. The
ion-conducting property together with the conjugated
structure allowing to exhibit strong fluorescence may
open up new applied fields of these polymers.
Con clu sion
In the present study, we have demonstrated the first
example of the synthesis of polylacetylenes with oligo-
oxyethylene in the side chain. WCl6 catalyst provided
black solid polymers soluble in common organic sol-
vents. The resulting polymers were widely conjugated
and exhibited fluorescence that could be recognized with
the naked eye. Poly(2) showed relatively high ionic
conductivity upon doping with Li(CF3SO2)2N, reaching
4.1 × 10-5 S/cm at 80 °C.
F igu r e 2. Emission spectra of poly(1) (1.0 × 10-4 M) and
poly(2) (5.7 × 10-5 M) (excited at 380 nm) in chloroform at
room temperature.
Ack n ow led gm en t. The authors are grateful to Dr.
H. Ushitora for the measurement of mass spectra. We
acknowledge the financial support by KAWASAKI
STEEL 21st Century Foundation for the present study.
This work was partly supported by a Grant-in-Aid for
Scientific Research on Priority Areas from the J apanese
Ministry of Education, Culture, Sports, Science, and
Technology.
Refer en ces a n d Notes
(1) Armand, M. B. Annu. Rev. Mater. Sci. 1986, 16, 245.
(2) Ratner, M. A.; Shriver, D. F. Chem. Rev. 1988, 88, 109.
(3) Gorecki, W.; Andreani, R.; Berthier, C.; Armand, M.; Mali,
M.; Ross, J .; Brinkman, D. Solid State Ionics 1986, 18 & 19,
295.
(4) (a) LeNest, J . F.; Gandini, A.; Cheradame, H. Macromolecules
1984, 17, 63. (b) Luo, Y.-Z.; Teo, H. H.; Booth, C. Macromol.
Chem. Rapid Commun. 1983, 4, 773.
(5) (a) LeNest, J . F.; Gandini. A.; Cheradame, H.; Cohen-Addad,
J . P. Polym. Commun. 1987, 28, 302. (b) Watanabe, M.;
Kanba, M.; Sanui, K.; Ogata, N. Solid State Ionics 1988, 28-
30, 911.
(6) (a) Allcock, H. R.; Napierala, M. E.; Olmeijer, D. L.; Cameron,
C. G.; Kuharcik, S. E.; Reed, C. S.; O’Connor, S. J . M.
Electrochim. Acta 1998, 43, 1145. (b) Allcock, H. R.; Austin,
P. E.; Neenan, T. X.; Sisko, J . T.; Blonsky, P. M.; Shriver, F.
Macromolecules 1986, 19, 1508. (c) Spindler, R.; Shriever, D.
F. J . Am. Chem. Soc. 1988, 110, 3036. (d) Cowie, J . M. G.;
Martin, A. C. S. Polymer 1987, 28, 627.
F igu r e 3. Relationships between reciprocal of temperature
and ionic conductivity of poly(1) and poly(2) ([LiN(SO2CF3)2]/
[O] ) 0.08).
(7) Nagai, K.; Masuda, T.; Nakagawa, T.; Freeman, B. D.;
When poly(1) was excited at the absorption based on
the main-chain chromophore, no emission peak was
observed. However, a clear emission peak centering at
around 470 nm was detected by photoexciting at 380
nm in chloroform. This emission peak corresponds to a
blue color emission which can be recognized with the
naked eye (Figure 2). A similar phenomenon but even
stronger luminescence was observed with polymer 2
when excited at 380 nm (Figure 2).14 These emissions
are attributable to the excimer between pendants, which
indicates that the stacking of pendant anthryl ring is
possible.
An interesting feature of the polymers is that they
exhibit relatively high ionic conductivity upon doping
with Li(CF3SO2)2N. Figure 3 shows the relationships
between reciprocal of temperature and ionic conductivity
of poly(1) and poly(2) containing Li(CF3SO2)2N. Both of
the plots of the ionic conductivity exhibited positively
convex profiles, as seen in conventional polyether-based
polymer electrolytes.1-6 Poly(2) showed much higher
ionic conductivity than poly(1), reaching 4.1 × 10-5 S/cm
at 80 °C. It is clear that four oxyethylene units in the
Pinnau, I. Prog. Polym. Sci. 2001, 26, 721.
(8) (a) Masuda, T. In Polymeric Material Encyclopedia; Salam-
one, J . C., Ed.; CRC: New York, 1996; Vol. 1, p 32. (b)
Shirakawa, H.; Masuda, T.; Takada, K. In Chemistry of
Triple-Bonded Functional Groups; Patai, S., Ed.; J ohn Wiley
& Sons: New York, 1994; Vol. 2, Chapter 23. (c) Long, N. J .
Angew. Chem., Int. Ed. Engl. 1995, 34, 21.
(9) Musikabhumma, K.; Masuda, T. J . Polym. Sci., Part A:
Polym. Chem. 1998, 36, 3131.
(10) (a) Nanjo, K.; Karim, S. M. A.; Nomura, R.; Masuda, T. J .
Polym. Sci., Part A: Polym. Chem. 1999, 37, 277. (b) Nomura,
R.; Karim, S. M. A.; Kajii, H.; Hidayat, R.; Yoshino, K.;
Masuda, T. Macromolecules 2000, 33, 4313. (c) Karim, S. M.
A.; Nomura, R.; Kajii, H.; Hidayat, R.; Yoshino, K.; Masuda,
T. J . Polym. Sci., Part A: Polym. Chem. 2000, 38, 4717.
(11) Masuda, T.; Karim, S. M. A.; Nomura, R. J . Mol. Catal. 2000,
165, 125.
(12) Bayliss, M. A.; Homer, R. B.; Shepherd, M. J . J . Chromatogr.
1998, 445, 393.
(13) Masuda, T. In Catalysis in Precision Polymerization; Koba-
yashi, S., Ed.; Wiley: Chichester, England, 1997; p 67.
(14) UV-vis and emission spectra of the polymers were also taken
in THF, but no solvent effect was observed.
MA030019X