Synthesis and characterization of an efficiently fluorescent poly(phenylenevinylene) possessing pendant dendritic phenyl groups

Article abstract of DOI:10.1021/ma050252q

We have synthesized a thermally stable and high molecular weight fluorescent poly-(phenylenevinylene) (PPV) incorporating side-chain-tethered dendritic phenyl groups (DENPPV) through Gilch route; this DENPPV has a low abundance of tolane-bisbenzyl defects

Full text of DOI:10.1021/ma050252q

Macromolecules 2005, 38, 10429-10435
10429
Synthesis and Characterization of an Efficiently Fluorescent
Poly(phenylenevinylene) Possessing Pendant Dendritic Phenyl Groups
K. Dinakaran, Shu-Min Hsiao, Chia-Hung Chou, So-Lin Shu, and Kung-Hwa Wei*
Department of Materials Science and Engineering, National Chiao Tung University,
Hsinchu, Taiwan 30049, R.O.C.
Received February 4, 2005; Revised Manuscript Received August 10, 2005
ABSTRACT: We have synthesized a thermally stable and high molecular weight fluorescent poly-
(phenylenevinylene) (PPV) incorporating side-chain-tethered dendritic phenyl groups (DENPPV) through
Gilch route; this DENPPV has a low abundance of tolane-bisbenzyl defects. Intramolecular energy transfer
from the dendritic phenyl side group to the PPV backbone was evidenced from UV-vis and photolumi-
nescence spectra of the DENPPV polymer and its model compound. Copolymers of DENPPV with
2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene (MEHPPV) display excellent photoluminescence
both in solution and in the solid state; the highest quantum yield we observed was 82%. The
electroluminescence of the copolymer MEHPPV/DENPPV (molar ratio: 25/75) was 70% higher than
that of MEHPPV (0.12 lm/W vs 0.07).
Introduction
weak feature of PPV derivatives that have flexible side
chains is that they are sensitive to a combination of air
and light.11 In contrast, phenyl-substituted PPVs have
higher resistance to photooxidation than do other
substituted PPVs.12 LEDs having longer lifetimes can
be fabricated from a single phenyl group substituted
PPVs that contain few head-to-head (HH) and tail-to-
tail (TT) couplings,13,14 such couplings referred to as
tolane-bis(benzyl) (TBB) defects. It has also been
demonstrated that polymers presenting fourth-genera-
tion dendrimers have a diminished amount of intermo-
lecular π-stacking and, consequently aggregate forma-
tion is inhibited.15 The photonic effects observed by the
dendronization of polymers have been explored in recent
years.16 We have already demonstrated that higher
luminescence efficiencies exist for polyfluorenes pos-
sessing side-chain tethered polyhedral oligomeric sils-
esquioxane (POSS).17a Moreover, Frechet-type dendrim-
ers, a benzyl alcohol dendrimer, have been shown to
have high photoluminescence.17b In contrast to the
Frechet-type dendrimers, Mullen-type dendrimers,18,19
which are polyphenylene dendrimers, are both shape-
persistent and chemically stable. Therefore, their π-stack-
ing is precluded at lower dendritic generations than it
is for the Frechet type. Their three-dimensional shield-
ing ability has been demonstrated by using perylene
dyes as core units.18 The Mullen type dendrimers do not
interfere with the charge transport or emission proper-
ties of the polyfluorene. Dendrimer substitution has
been performed to hinder excimer formation and exciton
migration to oxidized ketonic sites, which thereby
increases the color stability of the devices.19 In the
present study, we have employed the dendritic phenyl
(Mullen-type) PPV, which offers the following advan-
tages: (i) It permits spatial control of the polymer chain
and shields it from interchain excimer formation; (ii) it
is a fully conjugated PPV; (iii) it provides a very low
abundance of TBB defects as a result of electronic (the
stronger acidity of the bromomethyl moiety at the ortho
position of the highly conjugated dendritic phenyl group)
and steric effect of the substituent; (iv) its rigid aromatic
structure provides higher stability to thermal oxidation;
(v) its excitation energy is transferred to the polymer
Electroluminescence devices based on organic thin
films are of great interest because of their potential
applications as large-area light-emitting displays that
require a low driving voltage and have good process-
ability and a fast response time.1 Although many poly-
(phenylenevinylene) (PPV) derivatives have been syn-
thesized and applied in light-emitting diode (LED)
applications, very few display high photoluminescence
efficiencies.2 There are a number of reasons for these
low photoluminescence efficiencies: (a) Conjugated
backbones tend to stack cofacially with one another as
a result of favorable interchain π-π interactions, which
leads to a self-quenching of excitons. (b) An imbalance
of hole/electron injection and transport occurs in the
emission layer in devices because most emissive poly-
mers conduct holes in preference to electrons.3 (c)
Trapping of excitons by defect sites in the polymer
backbone causes nonradiative decay. These structural
defects in the polymer not only reduce the photolumi-
nescence quantum yield but also are responsible for the
short operational lifetimes of LED devices.4
Various techniques have been proposed to improve the
efficiency of PPVs, either by modifying their chemical
structure with bulky side groups or by using a copo-
lymerization approach to incorporate conjugated phe-
nylenevinylene segments among nonconjugated spac-
ers.5 For example, soluble PPV derivative with bulky
alkoxy side groups, poly[2-methoxy-5-(2-ethylhexyloxy)-
1,4-phenylenevinylene] (MEHPPV) has been de-
veloped.6-9 More recently, various bulky substituents,
such as alkoxy, alkylsilyl, phenyl, and fluorenyl groups,
have been substituted at the 2- or 2,5-positions of the
PPV backbone to suppress the aggregation, caused by
intermolecular interactions, that quench the formation
of excimers.9,10 Three new soluble PPV derivatives have
been obtained through use of the Horner-Witting-
Emmons (HWE) reaction; these materials in the solid
state display a photoluminescence quantum yields of
61%,10d which is higher than that of MEHPPV. One
* Corresponding author. E-mail: khwei@cc.nctu.edu.tw. Tele-
phone: 886-35-731871. Fax: 886-35-724727.
10.1021/ma050252q CCC: $30.25 © 2005 American Chemical Society
Published on Web 11/12/2005

10430 Dinakaran et al.
Macromolecules, Vol. 38, No. 25, 2005
Synthesis of 2′-(2,3,4,5-Tetraphenyl-4′-phenyl)-1,4′′-
dimethylbenzene (D-CH3). Suzuki Coupling Reaction.
Carefully purified DENBr, (1.0 g 1.84 mmol), 5-(4,4,5,5-
tetramethyl-1,3,2-dioxaborolan-2-yl)xylene (0.43 g 1.84 mmol),
and (PPh3)4Pd0 (1 mol %) were dissolved in a mixture of toluene
and 2 M aqueous K2CO3 (1.5:1). The solution was placed under
a nitrogen atmosphere and heated under reflux with vigorous
stirring for 48 h. The mixture was poured into water and
extracted with ethyl acetate. The organic extracts were washed
with brine and then dried (MgSO4). The solvent was removed
by rotary evaporation and the residue was purified by column
chromatography (silica gel; 2% ethyl acetate in hexane, Rf 0.3)
to provide 650 mg (65%) of the title product. 1H NMR (300
MHz, CDCl3) δ: 7.64 (s, 1H), 7.25 (s, 1H), 7.10-7.18 (m, 10H),
7.02-7.09 (m, 2H), 6.81-6.90 (m, 14H), 2.33 (s, 3H), 2.16 (s,
3H). 13C NMR (300 Hz CDCl3) δ:142.08, 142.07, 142.06, 141.73,
141.12, 140.94, 140.70, 140.38, 140.33, 140.21, 140.12, 139.71,
139.61, 135.43, 132.53, 131.95, 131.89, 131.85, 131.67, 131.27,
130.75, 130.56, 130.33, 128.74, 128.16, 127.93, 127.43, 127.25,
126.97, 126.59, 125.93, 125.67, 21.38, 20.23. Anal. Calcd For
C44CH34: C, 93.91; H, 6.09. Found: C, 93.91; H, 6.01. HRMS:
calcd for C44H34, 562.2661; found, 562.2662.
Synthesis of 2-(2,3,4,5-Tetraphenyl-4′-phenyl)-1,4-di-
bromomethylbenzene (D-CH2Br). A mixture of D-CH3, (1.0
g, 1.77 mmol) NBS (0.63 g, 3.55 mmol), and AIBN (0.04 g) was
heated under reflux in carbon tetrachloride under nitrogen for
5 days. The reaction mixture was filtered to remove succin-
imide, the solvent was evaporated, and the residue was
purified by column chromatography. 1H NMR (500 MHz,
CDCl3), δ: 7.62 (s, 1H), 7.46 (d, J ) 7.92 Hz, 1H), 7.34 (d, J )
7.70 Hz, 1H) 7.24-7.15 (m, 10H), 6.94-6.88 (m, 15H), 4.46 (s,
2H), 4.35 (s, 2H).
backbone, which leads to enhanced device performance
and quantum efficiency. The preparation of this polymer
is also a part of our effort to a production of fully
conjugated PPVs possessing bulky pendants. To deter-
mine the minimal steric requirements necessary to
prevent of aggregation and to enhance the solubility in
organic solvents, we also prepared copolymers with
MEHPPV. In this paper, we report the synthesis of a
new PPV derivative containing dendritic phenyl groups
on its side chains (DENPPV) as an example of highly
thermally stable, and TBB defect-free phenyl-substi-
tuted PPV; in addition, we describe the performance of
these polymers as emissive layers in LEDs.
Experimental Section
Materials and Characterization. Bromoxylene, n-butyl-
lithium, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane,
tetraphenylcyclopentadienone, and 4-bromophenylacetylene
were purchased from Aldrich and were used as received. All
other solvents were distilled before use. 1H and 13C nuclear
magnetic resonance (NMR) spectra were obtained using a
Bruker DRX 300 MHz spectrometer. Mass spectra were
obtained on a JEOL JMS-SX 102A spectrometer. Fourier
transform infrared (FTIR) spectra were acquired using a
Nicolet 360 FT-IR spectrometer. Gel permeation chromato-
graphic analyses were performed on a Waters 410 differential
refractometer and a Waters 600 controller (Waters Styragel
Column). All GPC analyses of polymers were performed in
THF solutions at a flow rate of 1 mL/min at 40 °C; the samples
were calibrated using polystyrene standards. Thermogravi-
metric analyses (TGA) and differential scanning calorimetry
(DSC) measurements were performed under a nitrogen atmo-
sphere at heating rates of 20 and 10 °C/min, respectively, using
Du Pont TGA-2950 and TA-2000 instruments, respectively.
UV-vis absorption and photoluminescence (PL) spectra were
recorded on an HP 8453 spectrophotometer and a Hitachi
F-4500 luminescence spectrometer, respectively. Before inves-
tigating the thermal stability of the synthesized polymers,
their polymer films were annealed in air at 200 °C for 2 h.
Synthesis of 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-
2-yl)xylene. n-Butyllithium (1.6 M in hexane, 17.0 mL, 27.09
mmol) was added, by syringe, to a solution of bromoxylene (5.0
g, 28.7 mmol) in THF (100 mL) at -78 °C. The mixture was
stirred at -78 °C, warmed to -10 °C for 15 min, and cooled
again at -78 °C for 15 min 2-Isopropoxy-4,4,5,5-tetramethyl-
1,3,2-dioxaborolane (15.0 g, 80.9 mmol) was added rapidly to
the solution, and the resulting mixture was warmed to room
temperature and stirred for 24 h. The mixture was poured into
water and extracted with ethyl acetate. The organic extracts
were washed with brine and dried over magnesium sulfate.
The solvent was removed by rotary evaporation and the
residue was purified by column chromatography (silica gel,
hexane, Rf 0.12) to provide 4.63 g (74%) of the title product.
1H NMR (300 MHz, CDCl3): δ 7.54 (s, 1H), 7.06 (dd, 2H, J )
7.6 Hz), 2.41 (s, 3H), 2.22 (s, 3H), 1.19-1.37 (m, 12H). HRMS:
calcd for C14H21O2B, 232.1634; found, 232.1636.
Synthesis of 2,3,4,5-Tetraphenyl-4′-bromophenyl (DEN-
Br). A mixture of tetraphenylcyclopentadienone and 4-bro-
mophenylacetylene was refluxed in xylene at 135 °C under
nitrogen for 48 h. The reaction mixture was then slowly added
into water (150 mL) and extracted with ethyl acetate (3 × 50
mL). The combined extracts were dried (MgSO4), the solvent
was evaporated, and the residue was purified by column
chromatography (hexane/ethyl acetate, 4:1) to afford 2 (3.23
g, 72%). 1H NMR (300 MHz, CDCl3) δ: 7.62 (s, 1H), 7.35 (d, J
) 8.1 Hz, 2H), 7.09-7.14 (m, 4H), 7.02 (d, J ) 8.5 2H), 6.87-
7.00 (m, 16H). 13C NMR (300 MHz, CDCl3) δ: 142.22, 142.19,
142.00, 141.46, 141.26, 141.13, 140.82, 140.60, 140.45, 140.28,
140.18, 140.12, 139.95, 139.77, 139.67, 135.43, 132.53, 131.95,
131.89, 131.85, 131.67, 131.27, 130.75, 130.45, 130.38, 128.14,
128.09, 127.65, 127.43, 127.19, 127.14, 126.1 0, 121.12. Anal.
Calcd for C36H25Br: C, 80.59; H, 4.66. Found: C,80.81; H, 4.89.
HRMS: calcd for C36H25Br, 536.1139; found, 536.1140.
13C NMR (500 MHz, CDCl3), δ: 142.27, 141.79, 141.66,
141.24, 140.87, 140.25, 139.91, 139.86, 139.51, 139.40, 137.96,
137.36, 135.50, 131.57, 131.52, 131.47, 131.21, 130.83, 129.95,
128.48, 128.15, 127.60, 126.99, 126.93, 126.65, 126.29, 125.74,
125.63, 125.38, 32.72, 31.44. Anal. Calcd for C44H32Br2: C,
73.34; H, 4.48. Found: C, 73.05; H, 4.41. HRMS: calcd for
C44H32Br2, 720.0871; found, 720.0848.
General Procedure for the Synthesis of Copolymers.
A 1 M solution of potassium tert-butoxide in THF was added
to a solution of the monomer D-CH2Br in dry THF at room
temperature, and then the mixture was stirred for 4 h.
Addition of the THF solution to methanol precipitated the
polymer, which was collected, washed with methanol, and
stirred with a mixture of methanol and water (1/1) for 1 h.
The polymer was again collected, stirred with a mixture of
methanol and water (1/1) for 1 h, filtered, washed with
methanol, and dried at 60 °C for 24 h.
Device Fabrication and Testing. The electroluminescent
(EL) devices were fabricated on an ITO-coated glass substrate
that was precleaned and then treated with oxygen plasma
before use. A layer of poly(ethylene dioxythiophene):poly-
(styrenesulfonate) (PEDOT:PSS, Baytron P from Bayer Co.;
ca. 40 nm thick) was formed by spin-coating from its aqueous
solution (1.3 wt %). The EL layer was spin-coated at 1500 rpm
from the corresponding toluene solution (15 mg mL-1) on top
of the vacuum-dried PEDOT:PSS layer. The nominal thickness
of the EL layer was 65 nm. Using a base pressure below 1 ×
10-6 Torr. a layer of Ca (30 nm) was vacuum deposited as the
cathode and a thick layer of Al was deposited subsequently
as the protecting layer. The current-voltage characteristics
were measured using a Hewlett-Packard 4155B semiconductor
parameter analyzer. The power of the EL emission was
measured using a Newport 2835-C multifunction optical meter.
The brightness was calculated using the forward output power
and the EL spectra of the devices; a Lambertian distribution
of the EL emission was assumed.
Results and Discussion
The dendritic phenyl substitute, 2,3,4,5-tetraphenyl-
4′-bromophenyl, was synthesized according to Scheme
1. Suzuki coupling of xylene boronic acid with 2,3,4,5-
tetraphenyl-4′-bromophenyl in toluene, in the presence

Macromolecules, Vol. 38, No. 25, 2005
Fluorescent Poly(phenylenevinylene) 10431
Scheme 1. Synthesis of Dendritic Phenyl Bromide
copolymers DENPPV, 88DENPPV, 75DENPPV,
63DENPPV, 50DENPPV, 25DENPPV, and MEH-
PPV, respectively. Figure 1 displays the FTIR spectra
of DENPPV and MEHPPV. The absorption bands that
appear at 1581-1596 cm-1, are characteristic of CdC
bonds. The absorption bands at 3056 and 961 cm-1 are
due to stretching modes for the vinylene CdC bond and
C-H out-of-plane bending, respectively, of the trans
configuration. The 1H NMR and 13 C H NMR spectra of
DENPPV have been presented as Supporting Informa-
tion. The aromatic and vinyl protons appear within the
range of 7.60-6.84 ppm. PPVs containing TBB defect
(head-to-head (H-H) or tail to tail (T-T) couplings, that
are formed as the result of a side reactions4,20 are
responsible for the CH2-CH2 groups that present the
peaks at 2.5-2.9 ppm. We did not observe peaks for
H-H couplings in the 1H NMR spectrum of the obtained
polymer. It is clear that this side reaction is suppressed
because of (i) the electronic effect arising from the
stronger acidity of the bromomethyl moiety at the ortho
position of the dendritic phenyl group and (ii) the steric
effect of the substituting dendritic phenyl group. We
of tetrakis(triphenylphosphine)palladium(0) as catalyst,
gave the dendritic phenyl-substituted xylene derivative.
The dendritic phenyl-substituted dibromo monomer (D-
CH2Br) was synthesized by bromination of 2′-(2,3,4,5-
tetraphenyl-4′-phenyl)-1,4′′-dimethylbenzene with NBS,
using AIBN as the radical initiator. The polymers were
prepared according to Scheme 2.
The copolymers were prepared using comonomer feed
ratios of D-CH2Br and 2-methoxy-5-(2-ethyl)hexyloxy-
1,4-bis(bromomethyl)benzene of 100:00, 88:12, 75:25, 63:
37, 50:50, 25:75, and 0:100; we name the corresponding
Scheme 2. Synthesis of DEN PPV and Copolymers

10432 Dinakaran et al.
Macromolecules, Vol. 38, No. 25, 2005
Figure 1. IR spectra of DENPPV and MEHPPV.
Table 1. Molecular Weights and Thermal Properties of
DENPPV and Copolymers
TGA
mol wtc
5 wt % loss
polymer
Mn
Mw
PDIa Tg (°C)b temp (°C)
DENPPV
88DENPPV 120 000 173 000
75DENPPV 110 600 136 000
63DENPPV
50DENPPV
25DENPPV
100 000 280 000
2.1
1.5
1.1
1.9
1.5
2.0
243
226
208
198
186
145
502
468
448
427
398
389
98 000 188 000
78 000 110 000
95 000 238 000
Figure 2. (a) UV and PL spectra of the DENPPV and a
dendritic phenyl model compound and (b) energy level diagram
of DENPPV and MEHPPV.26
a PDI ) Polydispersity index. b Tg ) Glass transition temper-
ature. c Molecular weights were calculated with relative to poly-
styrene standard.
reduction (Ered) and oxidation (Eox) potentials for DEN-
PPV were 1.63 and 1.13, respectively. The highest
occupied and lowest unoccupied molecular orbital (HOMO
and LUMO) energies were estimated electrochemically
to be -5.43 and -2.77 eV, respectively, with a band gap
of 2.66 eV. Figure 2b presents the energy level diagram
of DENPPV and MEHPPV. The LUMO of DENPPV
is higher than that of MEHPPV, while the HOMO of
DENPPV is lower than that of MEHPPV. From Figure
2, parts a and b, we conclude that intramolecular energy
transfer can occur effectively from the phenylated
dendrimer units to the polymer backbone.
The UV and PL spectra of the polymers in THF
solution are presented in Figure 3. The absorption peak
maximum of each polymer appears between 423 and 485
nm. The polymer solutions display intense blue-green
emissions (peak maxima at 492-551 nm), which are
blue-shifted as the concentration of the dendritic phenyl
monomer in the copolymer increased. The DENPPV
polymer displays an emission maximum at 492 nm and
a shoulder peak in the range 520-550 nm. We attribute
the shoulder peak that appears in the PL spectrum of
DENPPV to the vibronic effect of the aromatic ring of
the substituent phenylated dendrimer, because these
two peaks differ by 1100-1200 cm-1, calculated using
peak maximum values of PL spectrum.23 Surprisingly,
this shoulder peak was not prominent in the PL spectra
of the copolymers. On the other hand, the emission at
598 nm, which is due to aggregation appeared in the
spectra of MEHPPV and 25DENPPV. In Figure 3, we
observe that excimer formation is suppressed signifi-
cantly upon increasing the content of dendritic phenyl
monomer in MEHPPV.
measured the molecular mass and polydispersity index
(PDI) of each copolymer by GPC using THF as the
eluent; the results are presented in Table 1. We deter-
mined the weight-average molecular weights of the
polymers to be in the range (1.6-3) × 105 with poly-
dispersities ranges from 1.1 to 2.1. The DENPPV
polymer exhibits limited solubility in THF and in DMF,
and it has very low solubility when its molecular weight
reaches above 3 × 105. The glass transition temperature
(Tg) of DENPPV occurs at 243 °C, which is much higher
than that of MEHPPV, that can extended device
longevity.21,22 TGA of the DENPPV copolymers dis-
played that their 5% weight losses occurred between 502
and 336 °C. These thermal stabilities and glass transi-
tion temperatures are higher than those of other phe-
nylated PPVs reported previously. The higher glass
transition and thermal stability are due to the restricted
polymer chain mobility and resistant to thermal oxida-
tion imparted by the rigid dendritic phenyl group.
The PL spectrum of the dendritic phenyl exhibits a
peak maximum at 370 nm (Figure 2a), while the
maximum absorption peak due to the π-π transition
of the backbone of DENPPV appeared at 423 nm. A
large overlapped area from the two respective peaks is
present indicating the possible intramolecular energy
transfer since it is known that energy transfer can occur
readily when the PL of a chromophore having a wide
band gap overlaps with the electronic absorption of the
other chromophore possessing a narrow one. We mea-
sured the energy band gap of the polymers using the
oxidation and reduction potentials obtained from cyclic
voltammetry and the UV-vis absorption spectra. The

Macromolecules, Vol. 38, No. 25, 2005
Fluorescent Poly(phenylenevinylene) 10433
Table 2. Absorption and Photoluminescence Data of
DENPPV and Copolymers
ꢀ (M-1
L
M
a
polymer
cm-1
)
ODb
(nm)c (mol/cm3)d ηs e ηtf f
DENPPV
72 900 0.241 47
65
45
52
65
60
45
85
5.04
3.09
2.75
2.07
5.33
1.33
1.48
0.67 0.65
0.66 0.68
0.55 0.82
0.47 0.41
0.50 0.42
0.33 0.30
0.30 0.27
88DENPPV 11 920 0.0855
75DENPPV 60 070 0.0862
63DENPPV 21 506 0.167 58
50DENPPV 52 185 0.169 08
25DENPPV 92 065 0.4284
MEHPPV
99 274 0.140 78
a ꢀ ) Decadic molar extinction coefficient (dm3 mol-1cm-1). b OD
) Absorbance or optical density in the solid state. c L ) Thickness
of the thin film. d M ) Fluorescent chromophore concentration in
the film of each composite. e ηtf ) Thin-film quantum yield
estimated by using coumarin 6 dispersed in PMMA film at a
concentration <10-3 M.25 f ηs ) Solution quantum yield estimated
by using coumarin 6 in THF as the reference.
Figure 3. UV and PL spectra of DENPPV and copolymers.
Figure 4. Excitation spectra of the copolymers in THF
solution.
Figure 5. UV and PL spectra of DENPPV and copolymer
thin films.
Figure 4 presents the excitation spectra of the poly-
mers in solution; they indicate that the well-resolved
small peak at 300 nm is due to the substituent dendritic
phenyl group, which also confirms that energy transfer
occurs from the side chain to the polymer backbone. We
observe from Figure 4 that the excitation spectra are
the same as the UV-vis spectra; this finding indicates
the high purity of the emitting chromophores.
where OD is the optical density, c is the concentration
of the polymer in solution, and l is the optical path
length of the sample. We determined the fluorescent
chromophore concentration (M) in the thin film using
eq 2:
M ) OD/ꢀL (mol/cm3)
(2)
The thin film PL spectra was observed to be similar
to those of the solutions, e.g., DENPPV undergoes no
significant red shift in the film. In contrast, the MEH-
PPV, lacking dendron substituents exhibits a marked
red shift in its solid state from its solution state
absorption and emission spectra (551 vs 582 nm), which
we believe can be attributed to interactions, such as π-π
stacking, between the chromophores. These spectra also
suggest that the aggregation and migration of the
chromophores are reduced in the dendrimers and indi-
cate that even the first-generation dendrimers can
effectively suppress π-π stacking among polymer chains.
Table 2 presents the quantum yields of polymers in the
solid state and in solution, and their photoluminescence
data. The decadic molar extinction coefficient (ꢀ) was
determined in THF using eq 1:
where L is the thickness of the film.
DENPPV displays a quantum yield of 0.67 in THF,
calculated with reference to coumarin 6; this quantum
yield is for about 2-fold higher than that of the well-
established MEHPPV, in the solid state it is 0.65. The
copolymer 75DENPPV displays a higher quantum yield
(0.82) in the solid state than that of DENPPV, which
can be explained by quantum confinement.24 The higher
quantum yields of copolymers 88DENPPV and 75
DENPPV in their solid state than that of solution can
be explained as being due to the steric effect of dendritic
phenyls where the PPV backbone forces the pendant
dendritic phenyl ring to point away (one up and one
down) from the conjugated plane. Such a three-dimen-
sional structure prevents PPV stacking in any dimen-
sion, providing higher quantum yields.10d
We fabricated double-layer LED devices having the
configuration ITO/poly(3,4-ethylenedioxythiophene) (PE-
ꢀ ) OD/cl (dm3 mol-1 cm-1
)
(1)

10434 Dinakaran et al.
Macromolecules, Vol. 38, No. 25, 2005
transfer that occurs from the dendritic phenyl groups
to the PPV backbone. The PL quantum yield of DEN-
PPV (67%) is among the highest values reported for
fully conjugated PPV. The copolymer DENPPV/ME-
HPPV molar ratio of 75/25 exhibited increased values
of ηEL and ηPL that may make them useful as active
layers in devices such as LEDs and photovoltaic diodes.
Supporting Information Available: 1H NMR and 13C
NMR spectra of DENPPV and the monomer. This material
is available free of charge via the Internet at http://pubs.ac-
s.org.
Acknowledgment. The authors thank the National
Science Council, Taiwan, for financial support through
NSC 92-2120-M-009-009.
References and Notes
(1) (a) Yang, Z.; Karasz, F. E.; Geise, H. J. Macromolecules 1993,
26, 6570. (b) Strukelj, M.; Papadimitrakopoulos, F.; Miller,
T. M. Science 1995, 267, 1969. (c) Grem, G.; Leditzky, G.;
Ullrich, B.; Leising, G. Adv. Mater. 1992, 4, 3621. (d)
Berggren, M.; Ingana¨s, O.; Gustafsson, G.; Carberg, J. C.;
Rasmusson, J.; Anderson, M. R.; Hjertberg, T.; Wennerstron,
O. Nature 1994, 372, 444.
Figure 6. EL spectra of DENPPV and copolymers.
(2) (a) Greenham, N. C.; Samuel, I. D. W.; Hayes, G. R.; Phillips,
R. T.; Kessener, Y. A. R. R.; Moratti, S. C.; Holmes, A. B.;
Friend, R. H. Chem. Phys. Lett. 1995, 241, 89. (b) Samuel, I.
D. W.; Rumbles, G.; Collison, C. J.; Crystall, B.; Moratti, S.
C.; Holmes, A. B. Synth. Met. 1996, 76, 15. (c) Gettinger, C.
L.; Heeger, A. J.; Drake, J. M.; Pine, D. J. J. Chem. Phys.
1994, 101, 1673. (d) Hwang, D.-H.; Kim, S. T.; Li, X. C.;
Chuah, B. S.; Demello, J. C.; Friend, R. H.; Moratti, S. C.;
Holmes, A. B. Polym. Prepr. 1997, 38, 319.
(3) (a) Bao, Z.; Peng, Z.; Galvin, M. E.; Chandross, E. A. Chem.
Mater. 1998, 10, 1201. (b) Chung, S. J.; Kwon, K. Y.; Lee, S.
W.; Jin, J. I.; Lee, C. H.; Lee, C. E.; Park, Y. Adv. Mater.
1998, 10, 1112. (c) Chen, Z. K.; Meng, H.; Lai, Y. H.; Huang,
W. Macromolecules 1999, 32, 4351. (d) Greenham, A. C.;
Morrati, S. C.; Bradley, D. D. C.; Friend, R. H.; Burn, P. L.;
Holmes, A. B. Nature (London) 1993, 365, 628.
Figure 7. Plots of current density vs voltage and lumines-
cence vs voltage of the devices prepared from 75DENPPV and
MEHPPV.
(4) Becker, H.; Spreitzer, H.; Kreuder, W.; Kluge, E.; Schenk,
H.; Parker, I.; Cao, Y. Adv. Mater. 2000, 12, 42.
(5) Sokolik, I.; Yang, Z.; Karasz, F. E.; Morton, D. C. J. Appl.
Phys. 1993, 74, 3584. (b) Yang, Z.; Karasz, F. E.; Geise, H. J.
Macromolecules 1993, 26, 6570. (c) Pasco, S. T.; Lahti, P. M.;
Karasz, F. E. Macromolecules 1999, 32, 6933. (d) Mikroyan-
nidis, J. A. Chem. Mater. 2003, 15, 1865.
DOT):poly(styrene sulfonic acid) (PSS)/DENPPV/Ca/Al.
The EL spectrum of the DENPPV device was similar
to its PL spectrum in that it displays an intense signal
having a peak maximum at 499 nm (Figure 6.). The
copolymer MEHPPV/DENPPV at a molar ratio of 25/
75 exhibits an even more intense signal at 547 nm.
Figure 7 presents the variations of the current density
and brightness of the EL devices prepared from MEH-
PPV and 75DENPPV. The electroluminescence of
copolymer 75DENPPV displays highest efficiency (0.12
lm/W), it is 70% higher than that of MEHPPV (0.07
lm/W) measured under similar conditions. All of these
polymers shows better electroluminescence efficiency
(ηEL) providing that a minimization of the self-quenching
has occurred by attaching the bulky dendrons on the
polymer backbone and by preventing aggregation of the
polymer chains without altering their electronic proper-
ties and better device structure.
(6) Gustafsson, G.; Cao, Y.; Treacy, G. M.; Klavetter, F.; Colaneri,
N.; Heeger, A. J. Nature 1992, 357, 477.
(7) Aratani, S.; Zhang, C.; Pakbaz, K.; Hoger, S.; Wudl, F.;
Heeger, A. J. J. Elec. Mater. 1993, 22, 745.
(8) Yang, Y.; Heeger, A. J. Appl. Phys. Lett. 1994, 64, 1245.
(9) Braun, D.; Heeger, A. J. Appl. Phys. Lett. 1991, 58, 1982.
(10) (a) Chu, H. Y.; Hwang, D.-H.; Do, L.-M.; Chang, J.-H.; Shim,
H.-K.; Holmes, A. B.; Zyung, T. Synth. Met. 1999, 101, 216.
(b) Hsieh, B. R.; Yu, Y.; Forsythe, E. W.; Schaaf, G. M.; Feld,
W. A. J. Am. Chem. Soc. 1998, 120, 231. (c) Lee, S. H.; Jang,
B.-B.; Tsutsui, T. Chem. Lett. 2000, 1184. (d) Peng, Z.; Zhang,
J.; Xu, B. Macromolecules 1999, 32, 5162.
(11) (a) Andersson, M. R.; Yu, G.; Heeger, A. J. Synth. Met. 1997,
885, 1275. (b) Wudl, F.; Srdanov, G.; US Patent No. 5 189
136, 1993.
(12) Johansson, D. M.; Xiangjun Wang; Tomas Johansson; Inga-
nas, O.; Yu, G.; Srdanov, G.; Andersson, M. R. Macromol-
ecules 2002, 35, 4997.
Conclusion
In this study, we synthesized a high molecular-weight
poly(phenylenevinylene) (PPV) containing bulky den-
dritic phenyl groups (DENPPV) as PPV side chains.
The dendritic phenyl-substituted monomer was synthe-
sized through Suzuki coupling reaction and then po-
lymerized using the Gilch route. The dendritic phenyl
group is found to involved in the intramolecular energy
(13) Becker, H.; Spreitzer, H.; Kreuder, W.; Kluge, E.; Vestweber,
H.; Schenk, H.; Treacher, K. Synth. Met. 2001, 122, 105.
(14) Johansson, D. M.; Theander, M.; Srdanov, G.; Yu, G.; Inganas,
O.; Andersson, M. R. Macromolecules 2001, 34, 3716.
(15) Klarner, G.; Miller, R. D.; Hawker, C. J. Polym. Prepr. 1998,
39, 1006.
(16) Frauenrath, H. Prog. Polym. Sci. 2005, 30 325.

Macromolecules, Vol. 38, No. 25, 2005
Fluorescent Poly(phenylenevinylene) 10435
(17) Chou, C.-H.; Hsu, S. L.; Dinakaran, K.; Chiu, M. Y.; Wei, K.
H. Macromolecules 2005, 35, 745. (b) Chou, C.-H.; Shu, C.-
F. Macromolecules 2002, 35, 9673.
(18) Qu, J.; Zhang, J.; Grimsdale, A. C.; Mu1len, K.; Jaiser, F.;
Yang, X.; Neher, D. Macromolecules 2004, 37, 8297.
(19) Pogantsch, A.; Wenzel, F. P.; List, E. J. W.; Leising, G.;
Grimsdale, A. C.; Mullen, K. Adv. Mater. 2002, 14, 1061.
(20) Becker, H.; Spreitzer, H.; Ibrom, K.; Kreuder, W. Macromol-
ecules 1999, 32, 4925.
(21) Dogariu, A.; Gupta, R.; Heeger, A. J.; Wang, H. Synth. Met.
1999, 100, 95.
(22) Shin, D. C.; Ahn, J. H.; Kim, Y. H.; Kwon, S. K. J. Polym.
Sci., Part A: Polym. Chem. 2000, 38, 3086.
(23) Chen, S. H.; Su, A. C.; Chou, H. L.; Peng, K. Y.; Chen, S. A.
Macromolecules 2004, 37, 167.
(24) Johansson, D. M.; Srdanov, G.; Yu, G.; Theander, M.; Inganas,
O.; Andersson, M. R. Macromolecules 2000, 33, 2525.
(25) Swanson, S. A.; Wallraff, G. M.; Chen, J. P.; Zhang, W.;
Bozano, L. D.; Carter, K. R.; Salem, J. R.; Villa, R.; Scott, J.
C. Chem. Mater. 2003, 15, 2305.
(26) Jin, S. H.; Jang, M. S.; Suh, H. S.; Cho, H. N.; Lee, J. H.;
Gal, Y. S. Chem. Mater. 2002, 14, 643.
MA050252Q