Synthesis and optoelectronic properties of alternating copolymers containing anthracene unit in the main chain by radical ring-opening polymerization

Article abstract of DOI:10.1021/ma100820z

Novel alternating copolymers composed of anthracene moiety and halostyrene unit were synthesized by ring-opening polymerization of cyclic monomers, 10-methylene-9,10-dihydroanthryl-9-spiro-p-chlorophenylcyclopropane and its bromo derivative. Reversible ad

Full text of DOI:10.1021/ma100820z

Macromolecules 2010, 43, 7011–7020 7011
DOI: 10.1021/ma100820z
Synthesis and Optoelectronic Properties of Alternating
Copolymers Containing Anthracene Unit in The Main
Chain by Radical Ring-Opening Polymerization
Hideharu Mori,* Izumi Tando, and Hiromi Tanaka
Department of Polymer Science and Engineering, Department of Organic Device Engineering,
Graduate School of Science and Engineering, Yamagata University, 4-3-16, Jonan, Yonezawa, 992-8510, Japan
Received April 14, 2010; Revised Manuscript Received July 15, 2010
ABSTRACT: Novel alternating copolymers composed of anthracene moiety and halostyrene unit were
synthesized by ring-opening polymerization of cyclic monomers, 10-methylene-9,10-dihydroanthryl-9-spiro-
p-chlorophenylcyclopropane and its bromo derivative. Reversible addition-fragmentation chain transfer
and conventional free radical polymerizations were employed for the purpose. In both cases, the ring-opening
polymerization proceeded predominantly to afford alternating copolymer containing anthracene unit in the
main chain. Incorporations of optoelectronic groups, involving diphenylamine, carbazole, and phenothia-
zine, on the halostyrene moieties of the alternating copolymers were conducted by palladium-catalyzed
reactions. Novel nonconjugated copolymers having perfect alternating structures were obtained, in which the
alternate arrangement of two distinct electronic functionalities is formed owing to the ring-opening
polymerization system. Resulting anthracene-based alternating copolymers having two distinct electronic
functionalities exhibited characteristic fluorescence resonance energy transfer, as confirmed by UV-vis and
fluorescence spectra.
Introduction
anthracene-based polymers and molecules having an additional
optoelectronic component, such as triphenylamine,16-19 car-
The design and synthesis of novel polymers having two distinct
electronic functionalities, such as donor and acceptor chromo-
phores, are attracting significant attention, because of interesting
photophysical and optoelectronic properties, and possible appli-
cations for organic light emitting devices, photovoltaics, and
organic field-effect transistors.1-7 For these optoelectronic ap-
plications, it is important to control various factors, such as
electron donating and accepting properties involving highest
occupied molecular orbital (HOMO)/lowest unoccupied molecular
orbital (LUMO) energy levels, polymer architectures (dendrimers
and block and alternating copolymers) with the location and
stacking of the chromophores, and interfaces of two distinct
functionalities. In particular, the manipulations of energy, electron,
and charge transfers between two distinct electronic components
play crucial roles to achieve excellent photophysical and opto-
electronic properties.
Anthracene-containing polymers have attracted significant
research interest, due to their attractive features as fluorescent
labels, photon harvesters, and electro- and photoluminescent
materials. In addition to anthracene-based conjugated polymers,
increasing attention has been recently paid to nonconjugated
polymers with anthracene units in the main chain, such as poly-
(trimethyleneanthrylene)s,8,9 poly(octamethyleneanthrylene)s,10
and poly(9,10-oxymethyleneanthrylene)s.11 Nonconjugated poly-
mer having anthracene units linked in the 9,10-position with
flexible alkyl chains was reported to afford paramagnetism by
doping with iodine and enhanced electrical conductivity.11 Various
polyamides,12,13 polyesters,14,15 polyethers,14 and polyurethanes13
containing anthracene units in the main chain have been synthe-
sized by several groups. Much attention has been also paid to
bazole,20-22 and phenothiazine,23,24 because the combination of
two distinct electronic functionalities in a single system provides a
great variety of photophysical and optoelectronic properties. In
order to manipulate characteristic energy, electron, and charge
transfers between the two distinct electronic functionalities, var-
ious architectures have been employed, such as conjugated and
nonconjugated polymers having anthracene moiety in the side
chain18,22 and main chain,19,21 Langmuir-Blodgett films,20 and
small molecules.17,23,24
In a previous communication,25 we reported the synthesis of
well-definedpolymers containing anthracenemoieties inthe main
chain by radical ring-opening polymerization, which belongs to
chain-growth polymerization, via reversible addition-fragmen-
tation chain transfer (RAFT) process. Radical ring-opening
polymerization is attractive because functional groups such as
ethers, esters, amides, and carbonates can be incorporated into
the backbone of polymer chain,26 which cannot be achieved by
conventional radical polymerization of vinyl monomers. Recently,
several attempts have been made to extend the controlled radical
polymerization to ring-opening polymerization of cyclic mono-
mers, such as cyclic ketene acetals27-30 and cyclic acrylates,31
which afford well-defined polyesters and poly(R-ketoester)s, re-
spectively. Another important advantage of the radical ring-open-
ing polymerization is the feasibility to obtain perfect alternating
structure, which is originated from the structure of cyclic mono-
mers having two different potential monomer units. In our
previous system,25,32 10-methylene-9,10-dihydroanthryl-9-spiro-
phenylcyclopropane (MDS)33,34 was employed as a cyclic mono-
mer, and the resulting polymer actually had a perfect alternating
structure composed of the anthracene moiety and styrene unit,
owing to the ring-opening polymerization system (Scheme 1).
There are two possible mechanisms for the homopolymerization
*To whom correspondence should be addressed. E-mail: h.mori@
yz.yamagata-u.ac.jp. Telephone:þ81-238-26-3765. Fax: þ81-238-26-3092.
r 2010 American Chemical Society
Published on Web 08/04/2010
pubs.acs.org/Macromolecules

7012 Macromolecules, Vol. 43, No. 17, 2010
Mori et al.
Scheme 1. Ring-Opening Polymerization of 10-Methylene-9,10-dihydroanthryl-9-spirohalophenylcyclopropane, Where AIBN = 2,20-Azobis-
(isobutyronitrile) and CTA = Benzyl Dithiobenzoate
Scheme 2. Postmodifications of Alternating Copolymers Comprised of Anthracene Moiety and Halostyrene Unit
of MDS; conventional 1,2-vinyl addition to afford vinyl polymer
having the cyclopropane ring in the side chain and ring-opening
reaction to furnish directly the anthracene moiety in the main
chain. In this system, ring-opening of the cyclic monomer was
found to proceed predominantly during radical polymerization in
the presence of a suitable chain transfer agent (CTA).25,32 In
addition to the strain release of the cyclopropane ring and aroma-
tization, the formation of a stable benzyl radical may be another
driving force to open the ring and to attain the anthracene-
containing polymers having low polydispersity via RAFT polym-
erization.
In this study, we focused on the controlled synthesis of the
alternating polymers composed of the anthracene unit with an
additional optoelectronic group, such as triphenylamine, phe-
nothiazine, and carbazole derivatives. Polymers with carbazole
pendant groups are of considerable scientific and industrial
interest due to their attractive features, such as hole-transporting,
high charge-carrier, and electroluminescent properties.35 Phe-
nothiazine is a heterocyclic compound with electron-rich sulfur
and nitrogen heteroatoms. Compared with carbazole derivatives,
phenothiazine ring acts as a stronger electron donor by virtue of
the extra sulfur heteroatom.36,37 Triphenyl amine is a well-known
electron donor due to electron rich nitrogen atom and a famous
hole transporting materials that have been widely employed as a
constitutional unit for organic light-emitting diodes and organic
photovoltaic functional materials.18,19,38 As cyclic monomers,
here we employed 10-methylene-9,10-dihydroanthryl-9-spiro-p-
chlorophenylcyclopropane (MDS-Cl) and its bromo derivative
(MDS-Br), which are vinylcyclopropane derivatives having
halophenyl groups. Similar to the nonsubstituted cyclic monomer
(MDS),33,34 both MDS-Cl and MDS-Br undergo ring-opening
polymerization with the release of the ring strain of the cyclo-
propane ring and the formation of a stable aromatic ring as the
driving force, as shown in Scheme 1. The radical ring-opening
polymerization of the cyclic monomers, MDS-Cl and MDS-Br,
afforded to novel alternating copolymers composed of the an-
thracene moiety and halostyrene unit. Among various controlled
radical polymerizations, we have chosen the RAFT process
because it is the most versatile with respect to the monomer and
the reaction medium, and leads to the development of novel
polymeric materials with a variety of functional groups and
unique properties.39-45 Incorporations of optoelectronic groups
on the halogen moiety of the halostyrene unit were conducted by
palladium-catalyzed postmodifications (Scheme 2). Resulting
polymers are composed of the anthracene moiety in the main
chain and additional optoelectronic moiety, triphenylamine,
N-phenylcarbazole, and N-phenylphenothiazine, in the side chain.
These copolymers can be regarded as nonconjugated copolymers

Article
Macromolecules, Vol. 43, No. 17, 2010 7013
Scheme 3. Synthesis of 10-Methylene-9,10-dihydroanthryl-9-spiroha-
lophenylcyclopropanes
crude product. The crude monomer was purified by reprecipita-
tion into hexane, and by column chromatography on silica with
hexane/ethyl acetate (v/v = 5/1) as the eluent to afford a pale
yellow solid (1.10 g, 28%). 1H NMR (CDCl3): δ (ppm)
2.28-2.37 (m, 3H, CH2CH-Ar), 5.64 (d, 2H, CH2dC), 6.79-
7.69 (m, 12H, Ar). Note that the monomer, MDS-Cl, was
highly reactive and the neat product could not be handled at
room temperature. In order to avoid unfavorable polymeriza-
tion reaction, the purified product was diluted with toluene
immediately after the column purification and the evaporation
of the eluent was conducted under mild conditions. Typically, a
stock solution (0.335M) containing the cyclic monomer
(MDS-Cl) and toluene was prepared in a silanized glass tube
capped with a two-way glass stopper under nitrogen, and stored
in the dark around 0 °C.
having perfect alternating structures, in which the alternate arrange-
ment of two distinct electronic functionalities is formed owing to the
ring-opening polymerization system.
Experimental Section
Similarly, 10-methylene-9,10-dihydroanthryl-9-spiro-p-bro-
mophenylcyclopropane (MDS-Br) was prepared by Wittig
reaction of anthrone-9-spiro-p-bromophenylcyclopropane, which
was prepared by the reaction of 10-diazoanthrone with p-bromos-
tyrene. Anthrone-9-spiro-p-bromophenylcyclopropane was ob-
tained as a yellow solid (yield =30%); mp =145 °C. 1H NMR
(CDCl3): δ (ppm) 2.55 (m, 2H, CH2CH-Ar), 3.04 (t, 1H,
CH2CH-Ar), 6.42-7.70 (m, 10H, Ar), 8.38-8.43 (dd, 2H,
CH-C-CdO in Ar). MDS-Br was obtained as a yellow solid
Materials. 2,20-Azobis(isobutyronitrile) (AIBN, Kanto Chemi-
cal, 97%) was purified by recrystallization from methanol. The
synthesis of benzyl dithiobenzoate (BDB) was conducted accord-
ing to procedures reported previously.46,47 BDB was purified by
vacuum distillation using a glass tube oven (Shibata GTO-250RS)
to give a red oil.
10-Diazoanthrone was prepared by the reaction of anthrone
with tosylazide according to a method reported previously.48
p-Chlorostyrene (Kanto Chemical, 98%), p-bromostyrene (ACROS,
96%), methyltriphenylphosphonium bromide (ACROS, 98%),
n-BuLi (Kanto Chemical, 2.6 M hexane solution), toluene (dehy-
drated, Kanto Chemical, 99.5%) carbazole (Kanto Chemical,
97%), phenothiazine (Kanto Chemical, >98.0%), diphenyl amine
(Tokyo Kasei Kogyo, >99.0%), sodium tert-butoxide (NaO-t-Bu,
Tokyo Kasei Kogyo, >98.0%), tri-tert-butylphosphine (P(t-Bu),
Wako Chemicals, 96%), and bis(dibenzylidene acetone)palladium
(Pd2(dba)3, ACROS) were used as received. Other materials were
used without further purification.
Monomer Synthesis. The cyclic monomer 10-methylene-9,10-
dihydroanthryl-9-spiro-p-chlorophenylcyclopropane (MDS-Cl)
was prepared by Wittig reaction of anthrone-9-spiro-p-chlorophe-
nylcyclopropane (Scheme 3), according to a method reported
previously.25,33 The cyclopropane compound was prepared by
the reaction of 10-diazoanthrone with vinyl monomer, p-chloros-
tyrene, according to the procedure reported in the literature49 with
slight modifications.
1
(yield =27%). H NMR (CDCl3): δ (ppm) 2.29-2.36 (m, 3H,
CH2CH-Ar), 5.64 (d, 2H, CH2dC), 6.79-7.69 (m, 12H, Ar).
The H NMR spectra of the cyclopropane compounds and
1
the cyclic monomers, MDS-Cl and MDS-Br, are shown in
Figures S1 and S2, respectively (see Supporting Information).
General Polymerization Procedure. For a typical polymeriza-
tion, the toluene solution of MDS-Cl (0.335 mol/L, 1.82 mL,
0.61 mmol), BDB (3.0 mg, 0.012 mmol), and AIBN (1.0 mg,
0.006 mmol) were placed in a silanized glass ampule equipped
with a magnetic stirring bar. Then, the orange color solution,
which may be originated from yellow color of the monomer
(MDS-Cl) mixed with red-color of BDB used as CTA, was
degassed by three freeze-evacuate-thaw cycles. The ampule
was flame-sealed off under vacuum, and it was stirred at 80 °C
for desired time. The characteristic orange color solution was
changed gradually into a heterogeneous system, in which yellow
precipitate was formed during the polymerization. The reaction
was stopped by rapid cooling with liquid nitrogen. After the
reaction mixture was cooled to room temperature, the precipi-
tate, which correspond to unfavorable side product obtained by
dimerization, was filtered off and the filtrate was precipitated in
a large excess of diethyl ether and isolated by filtration. The
resulting product was finally dried under vacuum at room
temperature to give an orange-tinged yellow solid. The polymer
yield determined gravimetrically from the diethyl ether-insolu-
ble polymer sample was 42%. For the determination of the
monomer conversion, the 1H NMR spectrum of the polymeri-
zation mixture was measured in CDCl3. The monomer conver-
sion determined by a comparison of the integration of the
monomer CH2dC resonance (2H) at around 5.6 ppm to the
intensity of the methylene and methine peaks (CH2CHCH2) of
the polymer at 3.3-4.2 ppm was 72%.
A solution of 10-diazoanthrone (4.40 g, 0.0194 mol) and 25.4
mL of p-chlorostyrene (27.7 g, 0.200 mol) in toluene (200 mL) was
refluxed for 24 h. After the reaction mixture was cooled to room
temperature, the solvent was removed under reduced pressure to
give a yellow viscous product. The crude product was dissolved in
a small amount of THF, then it was precipitated into methanol,
and the precipitate, which corresponds to polymerized product,
was removed by filtration. After the filtrate was evaporated under
reduced pressure, the product was finally purified by recrystalliza-
tion from ethanol/CH2Cl2 (v/v = 5/1) to give a yellow solid (2.44 g,
1
55%); mp =152 °C. H NMR (CDCl3): δ (ppm) 2.57 (m, 2H,
CH2CH-Ar), 3.08 (t, 1H, CH2CH-Ar), 6.47-7.66 (m, 10H, Ar),
8.30-8.45 (dd, 2H, CH-C-CdO in Ar).
The cyclic monomer was prepared by Wittig reaction of
anthrone-9-spirophenylcyclopropane derivative according to a
method reported previously with some modifications.33 Methyl-
triphenylphosphonium bromide (4.35 g, 12.1 mmol) and dry
THF (40 mL) were placed in a 200 mL three-necked flask. The
hexane solution of n-BuLi (2.6M, 4.19 mL, 10.8 mmol) was
added dropwise to the mixture at 0 °C by external ice-bath
cooling, and then the resulting mixture was stirred at room
temperature for 30 min. Then, anthrone-9-spiro-p-chlorophe-
nylcyclopropane (3.00 g, 9.1 mmol) in dry THF (40 mL) was
added gradually to the reaction mixture, and it was continued at
room temperature for 1.5 h. After the reaction, the mixture was
dropped into a large excess of diethyl ether. The precipitate,
which corresponds to phosphonium oxide, was filtered off and
the filtrate was evaporated under reduced pressure to give a
The resulting polymer was soluble in chloroform, THF, and
DMF, while insoluble in acetonitrile, diethyl ether, hexane,
methanol, and water. 1H NMR (CDCl3): δ (ppm) 3.3-4.2
(broad, 5H, CH2-CH-CH2), 6.5-8.5 (broad, 12H, Ar).
The theoretical number-average molecular weight on conver-
sion is defined as follows:
½monomerꢀ0
MnðtheorÞ ¼
ꢁ Mmonomer ꢁ yield þ MCTA ð1Þ
½CTAꢀ0
where MCTA and MMonomer are molecular weights of chain
transfer agent and monomer, and [monomer]0 and [CTA]0 are
the initial concentrations of monomer and chain transfer agent,
respectively.

7014 Macromolecules, Vol. 43, No. 17, 2010
Mori et al.
Table 1. Radical Polymerization of 10-Methylene-9,10-dihydroanthryl-9-spiro-halophenylcyclopropane with 2,20-Azobis(isobutyronitrile) (AIBN)
in Toluene in the Presence and Absence of Chain Transfer Agent (CTA) a
run
monomerb
[M]/[CTA] /[I]
yieldc (%)
Mnd (theory)
Mne (SEC)
Mw/Mne (SEC)
1
2
3
4
5
MDS-Cl
100/0/1
100/2/1
100/5/1
100/0/1
100/2/1
45
42
33
38
32
14 600
7500
4900
10 900
6500
1.52
1.25
1.39
1.92
1.85
7100
2400
MDS-Br
6200
a Conditions: solvent = toluene, temperature = 80 °C, time =20 h, [M] = 0.335 mol/L, and chain transfer agent (CTA) = benzyl dithiobenzoate
(BDB). b MDS-Cl = 10-methylene-9,10-dihydroanthryl-9-spiro-p-chlorophenylcyclopropane, and MDS-Br = 10-methylene-9,10-dihydroanthryl-9-
spiro-p-bromophenylcyclopropane. c Diethyl ether insoluble part. d The theoretical molecular weight (Mn, theory) = (MW of M) ꢁ [M]0/[CTA]0 ꢁ yield þ
(MW of CTA). e Number-average molecular weight (Mn) and molecular weight distribution (Mw/Mn) were measured by size-exclusion chromatography
(SEC) using polystyrene standards in THF.
Postmodifications. A typical reaction procedure is as follows.
Poly(MDS-Br) (0.0573 g, Mn = 12400, Mw/Mn = 2.00, 0.154
unit-mmol), diphenylamine (DPA, 0.761 g, 4.5 mmol), sodium
tert-butoxide (NaO-t-Bu, 0.216 g, 2.25 mmol), and Pd2(dba)3
(0.034 g, 0.038 mmol) were placed in a 100 mL flask under
nitrogen atmosphere. Then, 1,4-dioxane (25 mL) and tri-tert-
butylphosphine (P(t-Bu)3, 1.63 M 1,4-dioxane solution, 0.138
mL, 0.23 mmol) were added to the solution at room tempera-
ture. The reaction mixture was stirred at 100 °C for 24 h. After
cooling to room temperature, the mixture was quenched by the
addition of aqueous ammonia (100 mL), and the product was
extracted three times with CHCl3. The product was purified by
two times reprecipitation into acetonitrile, and two times into
diethyl ether. The resulting product was finally dried under
vacuum at room temperature to give poly(MDS-DPA) as a
brownish gray solid (0.0555 g, 80%). Similarly, the palladium-
catalyzed reactions of carbazole (CZ) and phenothiazine (PTZ)
into the bromostyrene unit in poly(MDS-Br) afforded poly-
(MDS-CZ) and poly(MDS-PTZ) as a brownish gray solid
and navy blue solid, respectively. These resulting polymers were
soluble in chloroform, THF, and DMF, while insoluble in
acetonitrile, diethyl ether, methanol, and water.
The same palladium-catalyzed reaction was also employed
for the preparation of model compounds, N-phenylcarbazole and
N-phenylphenothiazine, which were prepared by the reaction of
bromobenzene with carbazole and phenothiazine, respectively.
Instrumentation. 1H and 13C NMR spectra were recorded
with a JEOL JNM-ECX400. Elemental analysis was carried out
on a Perkin-Elmer 2400 II CHNS/O analyzer. Number-average
molecular weight (Mn) and molecular weight distribution (Mw/
radical polymerization of 10-methylene-9,10-dihydroanthryl-9-spiro-p-
Figure 1. 1H NMR spectra (CDCl3) of polymers obtained by (a) free
Mn) were estimated by size-exclusion chromatography (SEC)
chlorophenylcyclopropane (MDS-Cl), (b) reversible addition-frag-
using a Tosoh HPLC HLC-8220 system equipped with refractive
index and ultraviolet detectors at 40 °C. The column set was as
RAFT polymerization of 10-methylene-9,10-dihydroanthryl-9-spiro-p-
mentation chain transfer (RAFT) polymerization of MDS-Cl, and (c)
bromophenylcyclopropane (MDS-Br).
follows: four consecutive columns [Tosoh TSK-GELs (bead size,
exclusion limited molecular weight): G4000HXL (5 μm, 4 ꢁ 105),
G3000HXL (5 μm, 6 ꢁ 104), G2000HXL (5 μm, 1 ꢁ 104), 30 cm
each] and a guard column [TSK-guardcolumn HXL-L, 4 cm]. The
system was operated at a flow rate of 1.0mL/min, using THF as an
eluent. Polystyrene standards were employed for calibration.
The UV-vis spectra were recorded using a JASCO V-630BIO
UV-vis spectrophotometer. Fluorescence spectra were ob-
tained from a JASCO FP-6100 spectrofluorophotometer. Ther-
mogravimetric analysis (TGA) was performed on a SEIKO
SSC/5200 at a heating rate of 10 °C/min under N2.
1
of MDS-Cl. The comparison of the H NMR spectra of
MDS-Cl (see Figure S1b, Supporting Information) and poly-
(MDS-Cl) reveals that the signals of the cyclopropane ring
observed at 2.2-2.4 ppm disappear after the polymerization.
The characteristic peaks at 3.3-4.2 ppm are clearly visible,
which are attributed to the methylene and methine protons of
the backbone formed by ring-opening polymerization of
MDS-Cl. In addition to these peaks, broad peaks around
6.0-8.5 ppm are observed, which correspond to the aromatic
protons of the anthracene unit. Similar 1HNMR spectrumwas
observed in the polymer prepared by the free radical polym-
erization of the nonsubstituted cyclic monomer, MDS.25 The
13C NMR spectrum of poly(MDS-Cl) obtained by the free
radical polymerization is presented in Figure 2a. In addition to
the peaks attributed to the aromatic carbons at 123-145 ppm,
two characteristic peaks are clearly observed at 49.0 and
33.7 ppm, which are attributable to two different aliphatic
carbons in the polymer backbone formed by the ring-opening
process of MDS-Cl. More importantly, the signals of the
cyclopropane ring at 39.0 and 12.6 ppm, which were observed
Results and Discussion
Polymerization of Cyclic Monomers. Free radical poly-
merization of the cyclic monomers, MDS-Cl and MDS-Br,
was carried out with AIBN as an initiator in toluene at 80 °C
for 20 h, and the results are summarized in Table 1. When the
polymerization of MDS-Cl was conducted at [M]0/[AIBN]0 =
100/1, the polymer yield was 45%, and the resulting polymer
had Mn = 14600 and Mw/Mn = 1.52 according to SEC in THF
1
using polystyrene calibration. Figure 1a shows the H NMR
spectrum of the polymer obtained by the free radical polymerization

Article
Macromolecules, Vol. 43, No. 17, 2010 7015
Figure 3. Size-exclusion chromatography (SEC) traces of (a) poly-
(MDS-Cl)s and (b) poly(MDS-Br)s prepared by free radical polym-
erization (dotted line) and RAFT polymerization at [monomer]/[chain
transfer agent]/[initiator] = 100/2/1 (solid line). See Table 1 for detailed
polymerization conditions.
MDS-Cl and MDS-Br, the same side reactions may occur,
regardless of the substituent group on the benzene ring.
RAFT polymerization of the cyclic monomers were con-
ducted using benzyl dithiobenzoate (BDB), which proved
efficient as a chain transfer agent (CTA) for obtaining the
polymer with relatively low polydispersity by radical polym-
erization of MDS.25 The results are summarized in Table 1.
When the polymerization of MDS-Cl was carried out using
BDB with AIBN at [M]0/[CTA]0/[AIBN]0 = 100/2/1 in
toluene at 80 °C for 20 h, the soluble polymer was obtained
as an orange-tinged yellow solid. Note that the orange-tinged
yellow color may be originated from red-color of the frag-
ments of CTA mixed with pale yellow color of the anthra-
cene-based polymer, even if RAFT polymers using BDB
mediator generally appear reddish after precipitation. The
polymer yield was 42%, which is comparable to that in the
case of free radical polymerization. The number-average
molecular weight, measured by a SEC, was Mn=7500,
Figure 2. 13C NMR spectra (CDCl3) of polymers obtained by (a) free
radical polymerization of 10-methylene-9,10-dihydroanthryl-9-spiro-p-
chlorophenylcyclopropane (MDS-Cl), (b) reversible addition-frag-
mentation chain transfer (RAFT) polymerization of MDS-Cl, and (c)
RAFT polymerization of 10-methylene-9,10-dihydroanthryl-9-spiro-p-
bromophenylcyclopropane (MDS-Br).
in the spectrum of the cyclic monomer (MDS-Cl, see Figure
S3, Supporting Information), are invisible in the resulting
polymer. These results suggest that the ring-opening of
MDS-Cl proceeds predominantly during radical polymeriza-
tion, which should be due to the strain release of the cyclopro-
pane ring, aromatization, and the formation of a stable benzyl
radical. The resulting poly(MDS-Cl) can be regarded as an
alternating copolymer composed of the anthracene and chlor-
ostyrene units in the main chain.
The free radical polymerization of MDS-Br under the
same conditions afforded a polymer having a lower molec-
ular weight and broader molecular weight distribution, with
a slight decrease in the polymer yield (Table 1). The polymers
obtained from both MDS-Cl and MDS-Br were soluble in
chloroform, THF, DMF, while insoluble in diethyl ether,
acetonitrile, and water. Relatively low polymer yields in both
cases may be due to unfavorable side reactions. In a previous
communication,25 we reported that unfavorable side reac-
tions, such as dimerization, may take place during the free
radical homopolymerization of the nonsubstituted cyclic
monomer, MDS, which led to the decrease in the polymer
yield. In the cases of the free radical polymerizations of
which is comparable to the theoretical value (Mn,theory
=
7100) calculated from the monomer/CTA molar ratio and
the polymer yield. The molecular weight distribution was
relatively narrow (Mw/Mn = 1.25), even if a shoulder peak at
lower molecular weight region could be detected in SEC trace
of poly(MDS-Cl) prepared by RAFT polymerization
(Figure 3a). In contrast, poly(MDS-Cl) prepared by free
radical polymerization showed a broad tailing at lower
molecular weight region. Figure 1b shows the 1H NMR
spectrum of the polymer obtained by RAFT polymerization
of MDS-Cl at [M]0/[CTA]0/[AIBN]0 = 100/2/1. The char-
acteristic peaks corresponding to the methylene and methine
protons of the backbone and the aromatic protons of the
anthracene unit are clearly visible at 3.3-4.2 and 6.5-8.5 ppm,
respectively. The 13C NMR spectrum of the resulting polymer
(Figure 2b) shows resonances attributed to aromatic carbons
at 123-145 ppm and two different aliphatic carbons in the
1
polymer backbone at 48.9 and 33.6 ppm. These H and 13C
NMR analyses suggest that the ring-opening reaction of MDS-
Cl predominantly takes place during the polymerization of

7016 Macromolecules, Vol. 43, No. 17, 2010
Mori et al.
Table 2. Palladium-Catalyzed Modification of Poly(MDS-Cl) and Poly(MDS-Br) with Optoelectronic Compound Having Secondary Amino
Group a
run
polymerb
reactant
N content (%)c
conversion (%)d
yield (%)e
1
2
3
4
5
6
poly(MDS-Cl)
poly(MDS-Br)
poly(MDS-Cl)
poly(MDS-Br)
poly(MDS-Cl)
poly(MDS-Br)
diphenyl amine
diphenyl amine
carbazole
carbazole
phenothiazine
phenothiazine
0.63
2.86
0.27
2.62
1.50
2.94
15
90 (>99f)
6.3
52
80
36
58
74
54
83 (88f)
41
>99 (>99f)
a Reaction was conducted in the presence of NaO-t-Bu (15 equiv for the p-halostyrene unit), Pd2(dba)3 (25 mol % for the p-halostyrene unit), and
ligand (P(t-Bu)3, P/Pd ratio =3/1) in 1,4-dioxane at 100 °C for 24 h. b Poly(MDS-Cl) = poly(10-methylene-9,10-dihydroanthryl-9-spiro-p-
chlorophenylcyclopropane) and Poly(MDS-Br) = poly(10-methylene-9,10-dihydroanthryl-9-spiro-p-bromophenylcyclopropane). c Determined by
elemental analysis. d Conversion of the postmodification (degree of the substitution) was calculated from the N content. e Acetonitrile-insoluble part.
The yield of the product was calculated on the basis of the amount of the poly(MDS-Cl) or poly(MDS-Br) in the feed and the conversiondetermined by
elemental analysis. f Measured by 1H NMR.
MDS-Cl, regardless of the presence and absence of CTA. These
results also suggest that RAFT polymerization of MDS-Cl
under suitable conditions proceeded smoothly to afford well-
defined alternating copolymer composed of the anthracene and
chlorostyrene units in the main chain.
predominantly proceeds via the radical ring-opening process,
independent of the substituent group on the benzene ring.
Postmodifications. Incorporations of photoactive chro-
mophores on the halogen moieties of the alternating copo-
lymers were conducted by postmodifications. Palladium-
catalyzed reactions of the halostyrene unit with photoactive
compounds having an N-H bond were conducted using
bis(dibenzylidene acetone)palladium (Pd2(dba)3) as a cata-
lyst, sodium tert-butoxide (NaO-t-Bu) as a base, and tri-tert-
butylphosphine (P(t-Bu)3) as a ligand according to proce-
dures reported previously.50,51 These reactions can be re-
garded as Pd-catalyzed amination of the aryl halides with an
arylamine (Scheme 2a) and heteroarenes containing N-H bond
(Scheme 2b). Table 2 summarizes the results of the palladium-
catalyzed reactions of poly(MDS-Cl) and poly(MDS-Br)
using diphenylamine (DPA), carbazole (CZ), and phenothia-
zine (PTZ) under several conditions. The conversion of the
postmodification was calculated from elemental analysis
The polymerization of MDS-Cl was also conducted under
various conditions. As shown in Table 1, the polymerization at
higher CTA-to-initiator ratio ([CTA]0/[AIBN]0 = 5/1) gave a
polymer having a lower molecular weight with a slight decrease
in the polymer yield. We also investigated the influences of the
solvent (toluene, DMF, chlorobenzene, 1,4-dioxane), monomer
concentration (0.168 - 0.335 M), the CTA-to-initiator ratio in
different solvents, and stabilizer (triethylenediamine) in terms of
the monomer conversion, yield, molecular weights, and the
polydispersity of the resulting poly(MDS-Cl)s (see Tables
S1-3, Figures S4-6 in Supporting Information). In many
cases, a small shoulder peak at high molecular weight region
and/or a shoulder peak at low molecular weight region were
detected in the SEC traces. The peak at high molecular weight
region is most probably attributed to species arising from
bimolecular termination reactions of the growing polymer
chains. Another possible explanation is the formation of high
molecular weight polymer with different structure or mixed
structure, in which some units may have fast polymerization
rate, forming the higher molecular weight polymers. From these
preliminary experimental results, we concluded that the polym-
erization of MDS-Cl at [M]0/[CTA]0/[AIBN]0 = 100/2/1 in
toluene ([M] = 0.335 mol/L) at 80 °C was the most efficient to
obtaining poly(MDS-Cl) having low polydispersity.
1
(nitrogen content) and H NMR. The yield of the product
was calculated on the basis of the amount of the p-halostyrene
unit in the feed and the conversion.
When the reaction was conducted at [diphenylamine]0/
[MDS-Br unit]0/[NaO-t-Bu]0/[Pd2(dba)3]0/[P(t-Bu)3]0 = 300/
10/150/2.5/15 in dioxane at 100 °C for 24 h, the introduc-
tion of the diphenylamine (DPA) on the bromostyrene unit
proceeded smoothly with a relatively high conversion to
afford alternating copolymer composed of the anthracene
unit in the main chain and triphenyl amine unit in the side
chain (Scheme 2a). The 1H NMR spectrum of the product,
poly(MDS-DPA), is shown in Figure 4a. All characteristic
proton signals from the methylene and methine main chain
(3.5-4.5 ppm) and phenyl and anthryl groups (6.5-8.5 ppm)
can be identified. The comparison of the 1H NMR spectra of
the poly(MDS-DPA) and poly(MDS-Br) used as a starting
polymer reveals the increase in the peak intensity of the
aromatic signals after the postmodification. The conversion
calculated by comparison of the signals at 3.5-4.5 ppm
corresponding to the methine and methylene protons in the
main chain to the signal at 6.5-8.5 ppm corresponding to
aromatic protons is >99%, which is in fair agreement with
the value determined by the elemental analysis. Palladium-
catalyzed reactions of other optoelectronic compounds,
carbazole (CZ) and phenothiazine (PTZ), into the bromos-
tyrene unit proceeded with high conversion. The structures
of the resulting polymers, poly(MDS-CZ) and poly(MDS-
PTZ), were also confirmed by 1H NMR measurements
(Figure 4). In contrast, the conversions of the postmodifica-
tions were relatively low in the cases of the modifications on the
chlorostyrene unit of poly(MDS-Cl). These results indicate
that the Pd-catalyzed reaction is effective to introduce addi-
tional optoelectronic component into the bromostyrene unit
of the anthracene-based polymer to produce novel alternating
RAFT polymerization of MDS-Br was also conducted with
BDB under the suitable conditions. As shown in Table 1, the
resulting polymer had an Mn = 6500, which is comparable to
the theoretical value (Mn,theory = 6200), and Mw/Mn =1.85.
The comparison of the conventional radical polymerization and
RAFT polymerization of MDS-Br reveals that the addition of
CTA leads to the decreases in the molecular weight and polymer
yield, which is consistent with the general tendency. As shown in
Figure 3b, a small peak at high molecular weight region and a
shoulder peak at low molecular weight region can be seen in the
SEC trace. Nevertheless, the characteristic resonances at
3.5-4.5 (methylene and methine protons) and 6.5-8.5 ppm
1
(phenyl and anthryl) are clearly observed in the H NMR
spectrum of the poly(MDS-Br), as can be seen in Figure 1.
In the 13C NMR spectrum of the resulting polymer (Figure 2c),
in addition to the resonances attributed to aromatic carbons at
123-145 ppm, two characteristic resonances are clearly ob-
served at 49.1 and 33.6 ppm, which are attributable to two
different aliphatic carbons in the polymer backbone. There is no
significant difference in the 13C NMR signals between the
polymers obtained by RAFT polymerizations of MDS-Cl
and MDS-Br. This indicates that the most of the cyclopropane
ring in these cyclic monomers are opened and the polymerization

Article
Macromolecules, Vol. 43, No. 17, 2010 7017
copolymers having two distinct electronic functionalities with
high conversions (degrees of the substitution) and recoveries.
Optical and Thermal Properties. For the investigation of
characteristic optoelectronic properties, we employed three
polymers having different substituent groups, poly(MDS-
DPA), poly(MDS-CZ), and poly(MDS-PTZ), which were
modified with diphenylamine (DPA), carbazole (CZ), and
phenothiazine (PTZ), respectively. Three modified polymers
and original poly(MDS-Br) having similar molecular
weights were employed for the evaluation (Table 3). Figure
5a depicts the absorbance spectra of the poly(MDS-Br) and
modified polymers in CHCl3. All anthracene-containing
polymers exhibit the first absorption band around 260 nm
assigned to the anthracene moiety and second absorption at
330-430 nm. The latter band may stem from the adjacent
anthracene moieties. The peak intensities of the first band in
the modified polymers are apparently higher than those of
original poly(MDS-Br). The modified polymers also exhibit
first absorption band around 260 nm and second absorption
at 330-430 nm, indicating sufficient incorporation of the
anthracene group in the modified polymers. In addition to
the peaks attributed to anthracene units, an additional peak
is visible at 306 nm for poly(MDS-DPA), 294 nm for
poly(MDS-CZ), and 320 nm for poly(MDS-PTZ), respec-
tively. These additional absorptions were also employed for
the excitation.
445 nm. In addition to these peaks, a shoulder peak is visible
at 470 nm and a broad tailing of the peak is detected until
around 550 nm. In fact, the absorbance and fluorescence of
poly(MDS-Br) were comparable to those of the poly(MDS)
and poly(MDS-Cl) (Figure S7, see Supporting Informa-
tion), indicating sufficient incorporation of the anthracene
group in the polymers obtained from MDS-Cl and MDS-
Br. These fluorescent peaks of poly(MDS-Br) are almost
the same as those of poly(MDS-CZ) with slight difference in
The fluorescence spectra of the anthracene-containing
polymers excited at 384 nm, corresponding to the absorption
wavelength of the anthracene unit, are shown in Figure 5b.
The emission of the poly(MDS-Br) is observed at 420 and
Figure 5. (a) Absorption spectra (concentration = 3.4 ꢁ 10-5 anthra-
cene unit mol/L) and (b) fluorescence spectra in CHCl3 (concentration =
1.7 ꢁ 10-6 anthracene unit mol/L, λex = 384 nm) of poly(MDS-Br)
(black line) and the anthracene-containing polymers modified with
diphenylamine (poly(MDS-DPA), red line), carbazole (poly(MDS-
CZ), blue line), phenothiazine (poly(MDS-PTZ), green line), respec-
tively. See Table 3 for detailed sample information.
Figure 4. 1H NMR spectra (CDCl3) of the products, (a) poly(MDS-
DPA), (b) poly(MDS-CZ), (c) poly(MDS-PTZ), obtained by the
postmodifications with diphenylamine (DPA), carbazole (CZ), phe-
nothiazine (PTZ), respectively, and (d) poly(MDS-Br) used as a starting
material.
Table 3. Summary of Alternating Polymers a
solubilitye
CHCl3
run
polymerb
Mnc (Mw/Mn)c
Td10d (°C)
DMF
THF
acetonitrile
Et2O
1
2
3
4
poly(MDS-DPA)
poly(MDS-CZ)
poly(MDS-PTZ)
poly(MDS-Br)
8100 (1.50)
7000 (1.76)
7900 (1.52)
12400 (2.00)
368
354
382
335
þ
þ
þ
þ
þ
þ
þ
þ
þ
þ
þ
þ
-
-
-
-
-
-
-
-
a Prepared by radical polymerization of 10-methylene-9,10-dihydroanthryl-9-spiro-p-bromophenylcyclopropane (MDS-Br) and postmodifications.
b The anthracene-containing polymers, poly(MDS-DPA), poly(MDS-CZ), and poly(MDS-PTZ), modified with diphenylamine, carbazole, and
phenothiazine, respectively. c Number-average molecular weight (Mn) and molecular weight distribution (Mw/Mn) were measured by size-exclusion
chromatography (SEC). d Determined by TGA; heating rate: 10 °C/min, N2 atmosphere. e “þ” = soluble at room temperature; “-” = insoluble at room
temperature.

7018 Macromolecules, Vol. 43, No. 17, 2010
Mori et al.
the peak intensities (Figure 5b). In contrast, poly(MDS-
DPA) and poly(MDS-PTZ) show extremely low peak
intensities, which are apparently different from those of the
original poly(MDS-Br). We also conducted absorbance and
fluorescence measurements in different solvents (DMF and
THF), suggesting no significant influence of the solvent on
the optoelectronic properties of poly(MDS-Br), as shown in
Figure S8 (see Supporting Information). On the basis of
these absorbance and fluorescence spectra, it is reasonable to
consider that the interaction of the anthracene unit and
phenylcarbazole unit in poly(MDS-CZ) is different from
those of the anthracene/triphenylamine units in poly(MDS-
DPA) and the anthracene/phenylphenothiazine units in
poly(MDS-PTZ).
Figure 6a shows the fluorescence spectra of poly(MDS-
DPA) obtained by irradiation of the CHCl3 solution at 306 nm,
corresponding to the absorption wavelength of the triphe-
nylamine unit in the poly(MDS-DPA). As comparisons,
fluorescent peaks of poly(MDS-Br) used as a staring ma-
terial and triphenylamine were measured independently
under the same conditions. A model compound, triphenyla-
mine, shows a broad peak from 400 to 600 nm with a maxi-
mum at 530 nm in the fluorescent spectrum. In contrast,
poly(MDS-DPA) exhibits peaks at around 420, 445, and
470 nm, which are attributed to the anthracene unit. In the
case of poly(MDS-Br), the intensities of the peaks attrib-
uted to the anthracene unit decrease apparently, which is due
to the absence of triphenylamine unit.
These behaviors could be explained by fluorescence reso-
nance energy transfer (FRET). In general, FRET is referred
to as an energy transfer between FRET donor and acceptor,
and the efficiency of FRET is very sensitive to the distance
between fluorescent donor and acceptor. In our system, the
anthracene unit and optoelectronic unit formed by postmo-
dification are close enough to interact, because of the non-
conjugated main chain with a predominantly alternating
structure. In order to achieve successful FRET efficiency,
both donor and acceptor do not significantly overlap with
each other, and the emission spectrum of FRET donors
overlaps sufficiently with the absorption spectrum of FRET
acceptor. As shown in Figure 5a, the maximum absorptions
of the anthracene unit at 330-430 nm do not significantly
overlap with those at 290-330 nm, which are attributed to
the optoelectronic group formed after the postmodification.
In the case of poly(MDS-DPA), the increases in the inten-
sities of the anthracene-based peaks, compared with those of
the original poly(MDS-Br), are apparently observed with
the decrease in the intensity of the triphenylamine-based
peak by the excitation at 306 nm. It means that successful
FRET occurs from the triphenylamine unit to the anthracene
unit. In the case of the excitation at 384 nm, corresponding to
the absorption wavelength of the anthracene unit, the energy
transfer may take place from the anthracene unit to the
triphenylamine unit without emission, resulting in the drastic
decrease in the anthracene-based fluorescent peaks. Similar
behavior was reported in a series of silylene-spaced diviny-
larene copolymers having alternating donor-acceptor chro-
mophores that exhibit efficient intrachain energy or electron
transfer.52,53 Luh et al. demonstrated efficient photoinduced
electron transfer from amino styrene moiety to anthracene
chromophore in the nonconjugated copolymers having a
silylene moiety as an insulating spacer.52
Figure 6. Fluorescence spectra of the modified polymers, model com-
pounds, original poly(MDS-Br) in CHCl3. (a) poly(MDS-DPA)
(concentration = 1.5 ꢁ 10-6 triphenylamine unit mol/L, λex = 306 nm),
(b) poly(MDS-CZ) (concentration = 1.4 ꢁ 10-6 N-phenylcarbazole
unit mol/L, λex = 294 nm), and (c) poly(MDS-PTZ) (concentration =
1.7 ꢁ 10-6 N-phenylphenothiazine unit mol/L, λex = 320 nm). The
concentrations of the anthracene unit of the modified polymers were
adjusted to the same to that of poly(MDS-Br) (concentration = 1.7 ꢁ
10-6 anthracene unit mol/L). See Table 3 for detailed sample information.
is seen in the fluorescent spectrum of a model compound,
phenylcarbazole, whereas the peak is invisible in the spectrum
of poly(MDS-CZ). The poly(MDS-CZ) exhibits strong
peaks at 400-570 nm, corresponding to the anthracene unit,
which are apparently higher than those of poly(MDS-Br).
These results suggest that FRET occurs effectively from the
phenylcarbazole unit to the anthracene unit. Similar energy
transfer between phenylcarbazole donor and anthracene-based
acceptor was observed in Langmuir-Blodgett (LB) films, in
which the donor and acceptor could be separately precisely by
inert spaces.20 In contrast, the strong peaks attributed to the
anthracene unit are detected in the fluorescent spectrum exited
at 384 nm (Figure 5b), indicating negligible energy transfer
from the anthracene unit to the phenylcarbazole unit.
When poly(MDS-PTZ) was excited at 320 nm, correspond-
ing to the absorption wavelength of the phenylphenothiazine
unit in the poly(MDS-PTZ), the emission in the range of 450
and 600 nm with a maximum at 530 nm is seen (Figure 6c). The
emission maxima at around 420, 445, and 470 nm are hard to
detect in poly(MDS-PTZ), suggesting that peak intensities
ascribed to the anthracene unit decreases drastically after the
The fluorescence spectra of poly(MDS-CZ),poly(MDS-Br),
and phenylcarbazole were observed by irradiation of the
CHCl3 solution at 294 nm, corresponding to the absorption
wavelength of the phenylcarbazole unit in the poly(MDS-
CZ). As can be seen in Figure 6b, a broad peak at 340-400 nm

Article
Macromolecules, Vol. 43, No. 17, 2010 7019
and an additional optoelectronic unit, involving triphenylamine,
N-phenylcarbazole, and N-phenylphenothiazine, in the side
chain. Ring-opening radical polymerization of the cyclic mono-
mers and subsequent palladium-catalyzed modification of the p-
bromostyrene unit were applied for the purpose. The vinylcyclo-
propane derivatives with the halophenyl groups were found to
predominantly undergo a ring-opening polymerization, regard-
less of the conventional radical polymerization or RAFT polym-
erization. Nearly monodispersed polymer with anthracene
moieties incorporated into the main chain was prepared by the
polymerization of MDS-Cl in the presence of benzyl dithio-
benzoate (BDB) under suitable polymerization conditions. The
palladium-catalyzed reaction was found to be effective to intro-
duce additional optoelectronic component into the bromostyrene
unit of the anthracene-based polymer to produce novel alternat-
ing copolymers having two distinct electronic functionalities. The
UV absorption and fluorescent spectra of the modified polymers
indicated that the characteristic fluorescence resonance energy
transfer took place, depending on the combination of two distinct
electronic functionalities.
Figure 7. Thermogravimetric analysis (TGA) thermograms of poly-
(MDS-Br) (black solid line), poly(MDS-Cl) (black dotted line) and
the anthracene-containing polymers modified with diphenylamine
(poly(MDS-DPA), red line), carbazole (poly(MDS-CZ), blue line),
phenothiazine (poly(MDS-PTZ), green line), respectively.
introduction of the phenothiazine moiety on poly(MDS-Br).
From these results, it is reasonable to consider that only energy
transfer occurs from the anthracene unit to the phenylphe-
nothiazine unit without emission. By the excitation at 384 nm,
the energy transfer may take place from the anthracene unit to
the triphenylamine unit without emission, resulting in the drastic
decrease in the anthracene-based fluorescent peaks (Figure 5b).
To obtain the information on the energy transfer behaviors,
we conducted control experiments using model mixtures of
poly(MDS) with the optoelectronic molecules, triphenylamine,
N-phenylcarbazole, and N-phenylphenothiazine, respectively.
Fluorescent spectra of the model mixtures were compared with
those of the modified polymers, poly(MDS-DPA), poly-
(MDS-CZ), and poly(MDS-PTZ) (Figures S9 and S10, see
Supporting Information). As expected, the fluorescent spectra
of the model mixtures exited at 384 nm, corresponding to the
absorption wavelength of the anthracene unit, were almost the
same to those of poly(MDS), which were apparently different
from those of poly(MDS-DPA) and poly(MDS-PTZ). When
the measurements were conducted upon the excitation at 306,
294, 320 nm, corresponding to the absorption wavelengths of
the triphenylamine, N-phenylcarbazole, and N-phenylphe-
nothiazine, the fluorescent spectra of the model mixtures were
consistent with those of the corresponding optoelectronic mo-
lecules. These results indicate that the energy transfer is hard to
occur in the model mixtures, which may be due to the fact that
the anthracene unit in poly(MDS) is far apart from the optoe-
lectronic molecule in the dilute solution. In other words, the
energy transfers take place only in the modified polymers, in
which the anthracene unit is close enough to the optoelectronic
unit in the nonconjugated main chain with a predominantly
alternating structure.
Acknowledgment. This work has been supported by a Grant-
in-Aid for Scientific Research from the Ministry of Education,
Culture, Sports, Science, and Technology, Japan (215501111).
This research was also supported by Japan Regional Innovation
Strategy Program by the Excellence (Creating international
research hub for advanced organic electronics of Japan Science
and Technology Agency).
Supporting Information Available: Figures showing 1H and
13C NMR spectra of the cyclic monomers, SEC traces of poly-
(MDS-Cl)s obtained by RAFT polymerization under various
conditions, and absorption and fluorescent spectra of the poly-
mers and model compounds observed under various conditions
and tables summarizing the results of RAFT polymerization
under various conditions. This material is available free of
charge via the Internet at http://pubs.acs.org.
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