Polyaddition of 2,7-diethynyl-9,9-dioctylfluorene using regio- and stereoselective alkyne dimerization catalysts

Article abstract of DOI:10.1021/ma035181e

Three geometrical isomers of poly(9,9-dioctyl-2,7-fluorene ethynylene vinylene) [poly(1)] having (E)-, (Z)-, and gem-vinylene units have been prepared in high regio- and stereoselectivities by polyaddition of 2,7-diethynyl-9,9-dioctylfluorene (1) catalyze

Full text of DOI:10.1021/ma035181e

Macromolecules 2004, 37, 13-17
13
Articles
Polyaddition of 2,7-Diethynyl-9,9-dioctylfluorene Using Regio- and
Stereoselective Alkyne Dimerization Catalysts
Hir oyu k i Ka ta ya m a ,*,†,§ Ma r i Na k a ya m a ,† Ta d a sh i Na k a n o,† Ch ik a ya Wa d a ,†
Ken su k e Ak a m a tsu ,‡ a n d F u m iyu k i Oza w a *,†,§
Department of Applied Chemistry, Graduate School of Engineering, Osaka City University,
Sumiyoshi-ku, Osaka 558-8585, J apan, and Faculty of Science and Engineering, Konan University,
Okamoto, Higashinada-ku, Kobe 658-8501, J apan
Received August 11, 2003; Revised Manuscript Received November 4, 2003
ABSTRACT: Three geometrical isomers of poly(9,9-dioctyl-2,7-fluorene ethynylene vinylene) [poly(1)]
having (E)-, (Z)-, and gem-vinylene units have been prepared in high regio- and stereoselectivities by
polyaddition of 2,7-diethynyl-9,9-dioctylfluorene (1) catalyzed by three kinds of transition metal catalysts.
Thus, a palladium catalyst (2), in situ generated from Pd(OAc)2, 1,3-dimesitylimidazolinium chloride
(SIMes‚HCl), and Cs2CO3, efficiently catalyzes the (E)-selective reaction, giving (E)-rich poly(1) in over
99% selectivity, whereas the reaction using a catalytic amount of RuCl2(dCdCHPh)(PPri )2 (3) in the
3
presence of N-methylpyrrolidine forms (Z)-rich poly(1) in over 92% selectivity. On the other hand, a
rhodium catalyst [RhCl(PMe3)2]2 (4) forms poly(1) bearing gem-vinylene linkages in 94% selectivity. The
regio- and stereochemical courses well preserve the catalyst nature of 2-4 observed in dimerization
reactions of arylacetylenes as prototypes of the present polyaddition processes. All polymers exhibit
emission property and high thermal stability.
In tr od u ction
1).7,8 Thus, it has been found that polyaddition of 2,7-
diethynyl-9,9-dioctylfluorene (1) proceeds in highly re-
gio- and stereocontrolled ways on the choice of catalysts,
affording the polymers with (E)-, (Z)-, and gem-vinylene
linkages in over 92% selectivities. Although π-conjugat-
ed polymers of this type have been previously prepared
by palladium-catalyzed polycondensation,9 geometrical
control around vinylene linkage has remained almost
unexplored.
Poly(phenylenevinylene) (PPV) and related π-conju-
gated polymers have attracted a great deal of recent
interest owing to their remarkable electrooptical prop-
erties such as photo- and electroluminescence.1 These
properties are known to be significantly affected by
stereoregularity of the polymer backbone. For example,
it has been documented that the (E)/(Z) ratio of vinylene
linkages governs luminescence efficiency of PPV, which
is an essential factor in applying the polymers to light-
emitting devices.2,3 Consequently, stereochemical con-
trol of polymer frameworks is among the principal
subjects in the synthesis of π-conjugated polymers.
Transition metal-catalyzed organic transformations
have proven to be powerful tools of constructing well-
defined architecture of macromolecules.4 In this context,
regio- and stereoselective addition to alkyne substrates
must be utilized as a particularly simple and efficient
means of synthesizing π-conjugated polymers bearing
vinylene linkages, while synthetic studies in this ap-
proach have been extremely limited.5-8 Recently, Mori
et al. reported stereoselective synthesis of (E)- and (Z)-
poly(p-phenylene dimethylsilylene vinylene)s via rhod-
ium-catalyzed polyaddition of p-bis(dimethylsilyl)ben-
zene to p-diethynylbenzene.6
Resu lts a n d Discu ssion
The present polymerization is based on transition-
metal-catalyzed dimerization of arylacetylenes,10,11 which
may form three geometrical isomers of diarylbutenynes
(see the products in eq 1). To accomplish the regio-
and stereoselective synthesis of poly(1), we have needed
the catalysts leading to (E)-, (Z)-, and gem-isomers
of butenyne. Nolan et al. have developed a highly
(E)-selective catalyst (2), which is prepared in situ
from Pd(OAc)2, 1,3-dimesitylimidazolinium chloride
(SIMes‚HCl), and Cs2CO3 and converts phenylacetylene
into (E)-1,4-diphenyl-1-buten-3-yne in 97% selectivity.11b
Goldman et al. have reported that [RhCl(PMe3)2]2 (4)
causes perfectly gem-selective dimerization of pheny-
lacetylene.12 On the other hand, as for the dimerization
of arylacetylenes, (Z)-selective catalysts with high cata-
lytic activity have been limited.11a,13 We therefore
examined several transition-metal catalysts and found
a vinylideneruthenium complex RuCl2(dCdCHPh)-
In this paper, we describe new polyaddition systems
based on catalytic dimerization of arylacetylenes (Scheme
† Osaka City University.
(PPri ) (3)14 in combination with N-methylpyrrolidine
3 2
‡ Konan University.
to serve as a particularly effective catalyst (eq 1).15 Thus,
the dimerization of phenylacetylene in CH2Cl2 in the
presence of 3 (1 mol %) and N-methylpyrrolidine (20 mol
§ Present address: Institute for Chemical Research, Kyoto
University, Uji, Kyoto 611-0011, J apan.
* Corresponding author. E-mail: hiroyuki@scl.kyoto-u.ac.jp.
10.1021/ma035181e CCC: $27.50 © 2004 American Chemical Society
Published on Web 12/06/2003

14 Katayama et al.
Macromolecules, Vol. 37, No. 1, 2004
Sch em e 1
Ta ble 1. P olya d d ition of 1 Ca ta lyzed by 2-4
b
b
c
c
entry
catalyst
condition
yielda (%)
Mn,NMR
nav
Mn,GPC
Mw/Mn
(E):(Z):gemb
1d
2d
3e
4e
5f
6f
2
2
3
3
4
4
50 °C, 10 min
50 °C, 3 min
r.t., 24 h
70 °C, 24 h
r.t., 2 h
99
62
87
87
>99
>99
6200
2400
1900
2600
3900
5600
14.1
5.5
4.3
5.9
8.9
14000
3400
2500
3400
5400
11900
2.35
1.52
1.81
2.10
2.58
2.22
99:<1:<1
99:<1:<1
2:94:4
5:92:3
<6:<1:94
5:2:93
50 °C, 2 h
12.8
a
b
d
Isolated yield. Determined by 1H NMR spectroscopy. c Determined by GPC based on polystyrene standards. Solvent: N,N-
dimethylacetamide. Initial concentration: [1] ) 0.10 M, [Pd(OAc)2] ) 1.0 mM, [SIMes‚HCl] ) 2.0 mM, [Cs2CO3] ) 0.40 M. e Solvent:
1,2-dichloroethane. Initial concentration: [1] ) 0.10 M, [3] ) 5.0 mM, [N-methylpyrrolidine] ) 20 mM. f Solvent: benzene. Initial
concentration: [1] ) 0.10 M, [4] ) 5.0 mM.
%) was accomplished in 3 h at room temperature to give
(Z)-1,4-diphenyl-1-buten-3-yne in 96% selectivity. 2-Ethy-
nylfluorene was also dimerized smoothly at room tem-
perature, giving the corresponding (Z)-enyne in 90%
selectivity. The addition of N-methylpyrrolidine to the
system is of particular importance to develop the high
catalytic activity. This component very probably pro-
motes the elimination of â-hydrogen of the vinylidene
ligand and the chlorido ligand in 3 as HCl to generate
a catalytically active alkynylruthenium species.16 The
catalytic activity was rather sensitive to the sorts of
phosphine ligands, and 3 having bulky and basic tri-
isopropylphosphines exhibited the best performance of
the vinylideneruthenium complexes examined.17
nyl-9,9-dioctylfluorene (1) (Scheme 1). π-Conjugated
polymers bearing fluorene units are highly expected as
blue-light-emitting materials.1a,18 The results are listed
in Table 1. The polymerization using 2 [i.e., Pd(OAc)2
(1 mol %), SIMes‚HCl (2 mol %), Cs2CO3 (4 equiv)]
proceeded in N,N-dimethylacetamide at 50 °C for 10
min. The reaction mixture was poured into a large
quantity of MeOH to give a 99% yield of (E)-rich poly-
(1) as a yellowish-brown powder (entry 1), whose mo-
lecular weight (Mn) and average degree of polymeriza-
tion (nav)were estimated tobe 6200 and 14.1, respectively,
by end-group analysis using 1H NMR spectroscopy. The
GPC analysis indicated Mn,GPC of 14 000, the value of
which is significantly larger than the Mn,NMR value,
probably due to overestimation resulting from the rigid-
rod structure of poly(1).19 The molecular weight was
reduced to 2400 by shortening the reaction time to 3
min (entry 2).
Next, the polymerization was carried out in the
presence of 3 (5 mol %) and N-methylpyrrolidine (20 mol
%) in 1,2-dichloroethane at room temperature. After 24
h, the dark orange solution with fluorescence was
subjected to silica gel column chromatography eluted
with CH2Cl2 to remove the ruthenium catalyst. Con-
centration of the eluate to dryness afforded (Z)-rich poly-
(1) as an orange oily material in 87% yield (entry 3).
This reaction also proceeded in high (Z)-selectivity at
70 °C (entry 4). The polymerization catalyzed by rhod-
ium complex 4 proceeded in benzene at room temper-
ature for 2 h to give gem-rich poly(1) with Mn,NMR of
3900, which was isolated as a reddish-black solid in
almost quantitative yield by precipitation with MeOH
(entry 5). The molecular weight increased at 50 °C
(entry 6).
Having the (E)-, (Z)-, and gem-selective catalysts 2-4
in hand, we next examined polyaddition of 2,7-diethy-
All the polymers thus obtained were soluble in com-
mon organic solvents such as THF, CHCl3, and toluene

Macromolecules, Vol. 37, No. 1, 2004
Polyaddition of 2,7-Diethynyl-9,9-dioctylfluorene 15
F igu r e 2. UV-vis absorption and fluorescence (FL) spectra
(CHCl3) of (E)-, (Z)-, and gem-rich poly(1)s isolated from the
reaction system of entries 2, 4, and 5 in Table 1, respectively.
The spectra are normalized for comparison.
F igu r e 1. 1H NMR spectra (300 MHz, CDCl3) of (a) (E)-, (b)
(Z)-, and (c) gem-rich poly(1)s isolated from the reaction system
of entries 2, 4, and 5 in Table 1, respectively. The arrows mark
vinylic proton signals.
(Z)-, and gem-vinylene groups appeared separately at
δ 7.17 and 6.49 (3J HH ) 16.4 Hz), δ 6.78 and 5.99 (3J HH
) 12.0 Hz), and δ 6.06 and 5.83 (3J HH ) 0.0 Hz),
respectively. The peak integration provided the (E):(Z):
gem ratio of vinylene linkages in each polymer, as listed
in Table 1. Thus, the (E)-, (Z)-, and gem-selective nature
of catalysts 2-4 was well preserved in the polymeriza-
tion of 1, respectively. The signal at around δ 3.16
observed in all spectra is assigned as CtCH protons of
polymer termini. All polymers exhibited a CtC stretch-
ing band at around 2360 cm-1 in the IR spectra. The
(E)-rich poly(1) also showed an absorption peak at 944
cm-1 in medium intensity, which is assignable to C-H
bending vibration of the (E)-CHdCH group.
The dependence of optical properties of poly(1)s on
the structures of the polymer backbone was investigated
by UV-vis absorption and fluorescence (FL) spectros-
copy. Table 2 summarizes the results. Figure 2 com-
pares the spectra of the polymers with similar molecular
weights (Mn,NMR ) 2400-3900, entries 2, 4, and 5 in
Table 1) under equivalent conditions. In the absorption
spectra, the π-π* transition of the (E)-rich poly(1) was
observed at 410 nm (λmax), the value of which was red-
shifted as compared with that of (Z)-rich poly(1) (λmax
) 373 nm). This tendency is consistent with the general
observation that the (E)-vinylene unit forms a longer
π-conjugated system than the (Z)-vinylene unit.3 On the
other hand, both polymers exhibited almost identical
FL spectra with the emission maximum at 452 nm and
a shoulder peak at 480 nm. Interestingly, the FL
quantum yield of the (Z)-rich polymer (ΦF ) 0.42) was
slightly higher than that of the (E)-rich poly(1) (ΦF )
0.37). A similar phenomenon has been reported for (E)-
and (Z)-rich poly(phenylenevinylene)s.3 The absorption
and emission maxima of gem-rich poly(1) were both
observed at much shorter wavelengths than those of the
(E)- and (Z)-rich ones.20
Ta ble 2. Op tica l Da ta of (E)-, (Z)-, a n d gem -Rich P oly(1)s
a
a
UV λmax
(nm)
FL λmax
(nm)
b
polymer [Mn,NMR, (E):(Z):gem]
ΦF
(E)-rich poly(1) [6200, 99:<1:<1]
(E)-rich poly(1) [2400, 99:<1:<1]
(Z)-rich poly(1) [2600, 5:92:3]
gem-rich poly(1) [3900, <6:<1:94]
gem-rich poly(1) [5600, 5:2:93]
419
410
373
342
345
455c
452c
452d
375e
377e
0.31
0.37
0.42
0.32
0.27
a
UV-vis absorption and fluorescence (FL) spectra were re-
b
corded in a dilute CHCl3 solution at room temperature. The FL
quantum yield (ΦF) was estimated by using quinine sulfate in 1
d
N H2SO4 as a standard. c Excited at 410 nm. Excited at 380 nm.
e Excited at 340 nm.
and were stable in air. The structural analysis was
made by NMR and IR spectroscopy. There are two
points to be clarified about the microstructure of the
polymer backbone. One is the sequential arrangement
of the π-conjugated units. Thus, we must consider at
least two types of arrangements of fluorene, ethynylene,
and vinylene units, as illustrated in the following
diagram. Despite several attempts using the model
compounds, however, we could not obtain any crucial
information on this point.
Besides the emission property, poly(1)s exhibited
excellent thermal stability. Thermogravimetric analysis
(TGA) under a nitrogen atmosphere revealed that the
temperatures for 5% weight loss of poly(1)s were in
excess of 500 °C irrespective of their main-chain struc-
On the other hand, the other point, which is related
to the regio- and stereoregularity of the vinylene link-
ages, was clearly investigated by 1H NMR spectroscopy.
As seen from Figure 1, the vinylic proton signals of (E)-,

16 Katayama et al.
Macromolecules, Vol. 37, No. 1, 2004
125.1, 120.2, 120.1, 120.0 (each s, Ar), 106.7 (s, CHdCH), 96.9,
88.9 (each s, CtC), 36.9, 36.8 (each s, CH2). Anal. Calcd for
tures. This value is significantly higher than those of
typical fluorene-based π-conjugated polymers.21
C
30H20: C, 94.70; H, 5.30. Found: C, 94.47; H, 5.31.
In conclusion, we have succeeded in regio- and ste-
reocontrolled synthesis of poly(fluorene ethynylene
vinylene)s using catalytic polyaddition process. The
structure of vinylene units clearly reflects the nature
of catalysts observed in the prototype dimerization
reactions of arylacetylenes. This finding should be useful
for further designing of more efficient catalysts for the
polyaddition approach to π-conjugated polymers.
P olym er iza tion of 2,7-Dieth yn yl-9,9-d ioctylflu or en e
(1) Ca ta lyzed by P d (OAc)2/SIMes‚HCl/Cs2CO3 (2). A typi-
cal procedure is as follows (entry 1 in Table 1). To a solution
of 1 (70 mg, 0.16 mmol) in N,N-dimethylacetamide (1.6 mL)
were successively added Pd(OAc)2 (0.36 mg, 1.6 µmol), SIMes‚
HCl (1.1 mg, 3.2 µmol), and Cs2CO3 (209 mg, 0.640 mmol).
The mixture was stirred at 50 °C for 10 min, during which
the initially deep green solution gradually darkened. The
resulting fluorescent solution was immediately poured into
vigorously stirred MeOH (150 mL). The yellowish-brown solid
of (E)-rich poly(1) thus precipitated was collected by filtration
and washed with MeOH (69 mg, 99%). IR (KBr): 3310, 2925,
Exp er im en ta l Section
Gen er a l Exp er im en ta l P r oced u r e a n d Ma ter ia ls. All
manipulations were performed under a nitrogen atmosphere
using conventional Schlenk techniques. Nitrogen gas was
purified by passing successively through the columns of an
activated copper catalyst (BASF, R3-11) and P2O5 (Merck,
SICAPENT). IR spectra were recorded on a J ASCO FT/IR-
410 instrument. NMR spectra were recorded on a Varian
Mercury 300 (1H NMR, 300.11 MHz; 13C NMR, 75.46 MHz)
spectrometer. Chemical shifts are reported in δ (ppm), referred
2853, 2362, 1463, 944, 811 cm-1 1H NMR (CDCl3): δ 7.67-
.
7.62, 7.50-7.39 (each m, Ar), 7.17, 6.49 (each d, J ) 16.4 Hz,
CHdCH), 3.16 (s, terminal CtCH), 2.05-1.88, 1.25-0.55 (each
m, CH2 and CH3). 13C{1H} NMR (CDCl3): δ 107.6 (s, CHd
CH), 93.2, 89.7 (each s, CtC); only characteristic peaks were
reported due to complexity of the spectrum.
P olym er iza tion of 1 Ca ta lyzed by 3/N-Meth ylp yr r oli-
d in e. A typical procedure is as follows (entry 3 in Table 1). To
a solution of 1 (70 mg, 0.16 mmol) in 1,2-dichloroethane (1.6
mL) were successively added 3 (4.8 mg, 8.0 µmol) and N-
methylpyrrolidine (2.7 mg, 32 µmol). The mixture was stirred
at room temperature. The reaction progress was followed by
TLC. After 24 h, the resulting dark orange fluorescent solution
was directly subjected to flash column chromatography eluted
with CH2Cl2. The eluate was evaporated and dried under
vacuum overnight to afford (Z)-rich poly(1) as an orange oil
(61 mg, 87%). IR (KBr): 3310, 2926, 2854, 2360, 1466, 890,
1
to the H (of residual protons) and 13C signals of deuteration
solvents. GLC analysis was performed on a Shimadzu GC-14B
instrument equipped with a FID detector and a capillary
column CBP-1 (25 m × 0.25 mm). Gel permeation chromatog-
raphy (GPC) was carried out on a J ASCO GPC assembly
consisting of a model PU-980 pump, a model RI-1530 refractive
index detector, and three GPC gel columns (Shodex KF-801,
KF-803L, KF-805L). Polystyrene standards were used for
calibration, and THF was used as the mobile phase with a flow
rate of 1.0 mL/min. The UV-vis absorption and fluorescence
spectra were recorded on a J ASCO V-560 spectrophotometer
and a FP-750 spectrofluorometer, respectively. Thermogravi-
metric analysis (TGA) was conducted under a nitrogen atmo-
sphere on a Rigaku TAS-300 thermal analyzer at a heating
rate of 10 °C/min.
822 cm-1 1H NMR (CDCl3): δ 7.85-7.46 (m, Ar), 6.78, 5.99
.
(each d, J ) 12.0 Hz, CHdCH), 3.15 (s, terminal CtCH), 2.20-
1.85, 1.35-0.50 (each m, CH2 and CH3). 13C{1H} NMR
(CDCl3): δ 106.6 (s, CHdCH), 97.8, 89.3 (each s, CtC); only
characteristic peaks were reported due to complexity of the
spectrum.
Dichloromethane and 1,2-dichloroethane were dried over
CaH2 and distilled prior to use. Benzene was dried and distilled
P olym er iza tion of 1 Ca ta lyzed by [Rh Cl(P Me3)2]2 (4).
A typical procedure is as follows (entry 5 in Table 1). A solution
of 1 (266 mg, 0.606 mmol) and 4 (18 mg, 31 µmol) in benzene
(1.2 mL) was stirred at room temperature for 2 h. The reaction
progress was followed by TLC. The resulting dark red solution
was poured into vigorously stirred MeOH (150 mL). The
reddish-black solid of gem-rich poly(1) thus precipitated was
collected by filtration and dried under vacuum (265 mg, >99%).
from Na/benzophenone ketyl. RuCl2(dCdCHPh)(PPri )2 (3)
3
was prepared from [RuCl2(p-cymene]2, triisopropylphosphine,
and phenylacetylene according to the literature.14 2-Ethy-
nylfluorene and 2,7-diethynyl-9,9-dioctylfluorene were syn-
thesized by Sonogashira coupling reactions of the correspond-
ing iodoarenes with ethynyltrimethylsilane followed by desilyl-
ation with potassium carbonate in methanol.22 1,3-Dimesityl-
imidazolinium chloride (SIMes‚HCl) was synthesized according
to the literature.23 All other chemicals were obtained from
commercial suppliers and used without further purification.
Dim er iza tion of Ar yla cetylen es Ca ta lyzed by Ru Cl2-
(dCdCHP h )(P P r i3)2 (3) in th e P r esen ce of N-Meth ylp yr -
r olid in e. To a solution of phenylacetylene (204 mg, 2.00 mmol)
and anisole (40 mg, internal standard for GLC analysis) in
CH2Cl2 (2.0 mL) were added 3 (12 mg, 20 µmol) and N-
methylpyrrolidine (34 mg, 0.40 mmol) successively. The mix-
ture was stirred at room temperature for 3 h. GLC analysis
revealed the formation of (Z)-PhCHdCHCtCPh in 96% yield,
along with small amounts of (E)- (1%) and gem-isomers (3%).
Volatile materials were removed by pumping to give dark
orange oil, which was subjected to flash column chromatog-
raphy over silica gel eluted with hexane. Evaporation of the
eluate afforded a colorless oil of PhCHdCHCtCPh ((E):(Z):
gem ) 1:96:3), which was pure for elemental analysis (203 mg,
>99%). The NMR data were consistent with those reported.24
The dimerization of 2-ethynylfluorene was similarly carried
out.
IR (KBr): 3309, 2925, 2852, 2360, 1465, 1211, 947, 822 cm-1
.
1H NMR (CDCl3): δ 7.81-7.48 (m, Ar), 6.06, 5.83 (each s,
CHdCH), 3.16 (s, terminal CtCH), 2.13-1.61, 1.35-0.50 (each
m, CH2 and CH3). 13C{1H} NMR analysis was infeasible due
to low solubility.
F lu or escen ce (F L) a n d Qu a n tu m Yield Mea su r em en ts.
All emission studies were performed at room temperature in
optically dilute solutions with absorption maxima less than
0.1 to avoid the inner filter effect. The solutions for the
measurement were freshly prepared by dissolving the polymer
into spectroscopic grade CHCl3. The quantum yields were
measured relative to quinine sulfate in 1 N H2SO4 assuming
a quantum yield of 0.546 when excited at 350 nm. Corrections
for refractive indices and differences between the excitation
light intensities of different wavelengths were applied.
Ack n ow led gm en t. This work was supported by a
Grand-in-Aid for Scientific Research from the Ministry
of Education, Culture, Sports, Science and Technology,
J apan.
Id en tifica tion Da ta for (Z)-1,4-Bis(2-flu or en yl)bu t-1-
en -3-yn e. H NMR (CDCl3): δ 8.25 (br s, 1H, Ar), 7.98-7.95
1
Refer en ces a n d Notes
(m, 1H, Ar), 7.83-7.78 (m, 4H, Ar), 7.70 (br s, 1H, Ar), 7.56-
7.54 (m, 3H, Ar), 7.44-7.30 (m, 4H, Ar), 6.79 (d, J ) 11.9 Hz,
1H, CHdCH), 5.96 (d, J ) 11.9 Hz, 1H, CHdCH), 3.96, 3.94
(each s, 4H, CH2). 13C{1H} NMR (CDCl3): δ 143.8, 143.6, 143.3,
143.2, 142.1, 142.0, 141.4 (each s, Ar), 138.7 (s, CHdCH),
135.4, 130.6, 130.3, 128.0, 127.9, 127.2, 127.0, 126.9, 125.2,
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