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Fluorene-Based Materials and Their Supramolecular Properties


Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of
Technology, Den Dolech 2, 5612 AZ Eindhoven, The Netherlands

Received 18 March 2009; Accepted 4 May 2009

DOI: 10.1002/pola.23499
Published online in Wiley InterScience (

ABSTRACT: Fluorene-based p- emission colors. Furthermore, Polym Sci Part A: Polym Chem 47:
conjugated polymers and oligo- methods to control their supra- 4215–4233, 2009
mers combine several advanta- molecular organization will be
geous properties that make them discussed. In many cases, a deli- Keywords: p-conjugated oligo-
well-suited candidates for appli- cate interplay between the chem- mers; p-conjugated polymers; fluo-
cations in organic optoelectronic ical structure and the processing rene copolymers; morphology;
devices and chemical sensors. conditions are found, resulting in oligofluorenes; phase behavior;
This review highlights strategies a high sensitivity of both struc- polyaromatics, polyfluorenes; self-
to synthesize these materials and tural features and optical proper- assembly; self-organization; supra-
to tune their absorption and ties. VC 2009 Wiley Periodicals, Inc. J molecular structures; thin films

Robert Abbel studied chemistry at the Universities of Mainz, Germany

and Toronto, Canada. In 2004, he received the degree of Diplom-Chem-
iker after having finished a research project on rod-coil block copolymers
under the guidance of Dr. Andreas Kilbinger and Prof. Holger Frey.
Afterwards, he joined the group of Prof. E. W. Meijer at the Eindhoven
University of Technology, the Netherlands, as a PhD student, working on
fluorene-based polymers and oligomers and their supramolecular chemis-
try. He received his PhD degree in 2008 and is currently working at TNO
Robert Abbel Industries.

Correspondence to: A. P. H. J. Schenning (E-mail: a.p.h.j. or E. W. Meijer (E-mail: e.w.meijer@tue.
Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 47, 4215–4233 (2009)
C 2009 Wiley Periodicals, Inc.

4216 J. POLYM. SCI. PART A: POLYM. CHEM.: VOL. 47 (2009)

Albertus P. H. J. Schenning is associate professor at the Eindhoven Uni-

versity of Technology, the Netherlands. He received his PhD degree at
the Radboud University of Nijmegen in 1996 on supramolecular architec-
tures based on porphyrin and receptor molecules with Dr. M. C. Feiters
and Prof. R. J. M. Nolte. Between June and December 1996, he was a
postdoctoral fellow in the group of Prof. E. W. Meijer at the Eindhoven
University of Technology working on dendrimers. In 1997, he joined the
group of Prof. F. Diederich at the ETH in Zürich, where he investigated
Albertus P. H. J. Schenning p-conjugated triacetylenes. His current research interests are self-
assembled p-conjugated systems.

Prof. E. W. ‘‘Bert’’ Meijer is Distinguished University Professor in the

Molecular Sciences and Professor of Organic Chemistry at the Eindhoven
University of Technology, the Netherlands. After a PhD in 1982 from the
University of Groningen (Organic Chemistry with Prof. Hans Wynberg)
and a 10-year career in industry (Philips and DSM), he became head of
the Laboratory of Macromolecular and Organic Chemistry at the Eind-
hoven University of Technology. His research is focused on supramolec-
ular chemistry, functional organic materials, chemical biology, and
Prof. E. W. ‘‘Bert’’ Meijer stereochemistry.

INTRODUCTION tion of the aromatic system. In bare fluorene, the protons

at the sp3 carbon in the methylene bridge (9-position) ex-
p-Conjugated polymers and oligomers based on fluorene hibit a significant CH acidity (pKA ¼ 22.98) as the result-
building blocks have gained importance as the active ing aromatic fluorenyl anion is efficiently resonance sta-
materials in various types of organic optoelectronic de- bilized.9,10 Oxidation to 9-fluorenone is another fre-
vices, most notably organic light-emitting diodes1,2 and quently observed reaction,11–13 which is also favored by
organic photovoltaic cells.3 Recently, their use as sensing resonance stabilization because the p-conjugated system
and imaging agents has emerged as a growing second is extended. Such chemical reactions can be suppressed
field of application.4 The optical and electronic proper- by double alkylation11,14 or arylation11,15 of fluorene,
ties of fluorene-based materials highly depend on both which has the additional advantage of introducing side
the chemical structures and the supramolecular organiza- groups that enhance the solubility in organic solvents.2
tion.5,6 Here, an overview is presented highlighting sci- Whereas alkylation is easily achieved by reaction of the
entific literature on fluorene-based optoelectronic materi- fluorenyl anion with bromoalkanes, arylation requires
als such as oligomers, homo-, and copolymers. The most more elaborate synthetic procedures and is therefore less
common synthetic routes will be described together with frequently used.11
both their optical properties and phase behavior. Further- Fluorene monomers can be directly connected to each
more, the fields of application are introduced and some other via aromatic coupling at the 2 and 7 positions,
recent key developments concerning research in these yielding a series of oligofluorenes (OFs) with increasing
areas are depicted. Finally, strategies are highlighted that conjugation lengths.16 Because of the torsional freedom
have been successfully employed to gain understanding of the biphenyl bond, the planes of the fluorene units are
of and control over the supramolecular organization of usually tilted with respect to each other.5 This can be
fluorene-based materials. overcome by full planarization using the so-called


The fluorene molecule (C13H10) is an isocyclic aromatic

hydrocarbon composed of two benzene rings that are
connected via a direct carbon–carbon bond and an adja-
cent methylene bridge (Scheme 1). The methylene bridge
forces the two phenyl rings to be planar,7 which Scheme 1. Chemical structure and atomic numbering of
increases their orbital overlap and the degree of conjuga- fluorene.
Journal of Polymer Science: Part A: Polymer Chemistry
DOI 10.1002/pola

Scheme 2. Illustration of the two most commonly used synthetic strategies toward fluorene
polymers: PF homopolymer synthesis by (a) Yamamoto and (b) Suzuki polycondensation.
(c) APF synthesis by Suzuki polycondensation. R ¼ alkyl, R0 ¼ H or alkyl.

ladder-type materials,11,17 but these are not the subject of perfect regioselectivity.5,11 As in the case of OF synthe-
this highlight article. The first systematic study involving sis, the most prominent types of reactions used to prepare
a considerable number of well-defined fluorene oligo- PFs are the Ni(0)-mediated Yamamoto and the Pd-
mers (up to ten repeat units) used the Ni(0)-mediated catalyzed Suzuki condensations7,11,33–35 (Scheme 2).
Yamamoto coupling18 of 2,7-dibromo-9,9-dihexylfluo- With the appropriate reaction conditions applied, high-
rene in the presence of 2-bromofluorene as an end capper molecular-weight PF (Mn [ 100,000 g mol1) can be
(Scheme 2).19 Monodisperse molecules were obtained obtained with both strategies.28,29,36
from the oligomer mixture by high-performance liquid PFs have been prepared with a wide variety of alkyl
chromatography. Later, several research groups20–26 have chains attached to the 9-position, both linear (methyl up
prepared OFs by stepwise approaches that also allowed to n-hexadecyl),30,37,38 branched (most notably 2-methyl-
variation of the alkyl substitution pattern along the butyl, 2-ethylhexyl and 3,7-dimethyloctyl),39–42 and
oligomer backbone in a defined manner (Scheme 2).23,25 spirocyclic.43 Poly(dimethylfluorene) and poly(diethyl-
The central carbon–carbon coupling step of all these fluorene) are poorly soluble, but the solubility of PFs
routes is the Pd-catalyzed Suzuki reaction of aromatic increases with the length of the alkyl chains and the
halogen compounds with boronic acids or esters.27 To degree of branching. When methylbutyl, hexyl, or longer
allow the synthetic strategy toward longer oligomers to substituents are attached to the 9-position, the resulting
proceed selectively, protective groups such as trimethyl- PFs are highly soluble in common apolar organic sol-
silyl units are required.22,23,26 Alternatively, the higher vents.17,44 Arylated OFs and PFs most commonly bear
reactivity of aromatic iodine compounds20 or diazonium (substituted) phenyl groups at the 9-position,15,45 but
salts21 in Suzuki couplings compared to bromine deriva- other groups such as spirolinked fluorenes46,47 have also
tives has been exploited. been used.
Connection of fluorene monomers with two reactive Metal-catalyzed aryl–aryl cross couplings are also
sites in a one-step synthesis produces polydisperse very useful for the synthesis of fluorene copolymers.
oligomer mixtures or, when no endcappers are present, These polymers are of particular interest due to the possi-
polyfluorenes (PFs).2,5,7,11,28,29 Although insoluble poly- bility to tune the electronic band gap and thus the emis-
(dimethylfluorene) has been obtained by electropolymeri- sion colors of the materials by an appropriate choice of
zation in 1987,30 the first example of a synthetic the comonomers (vide infra). Although statistical copoly-
approach toward soluble PFs was the oxidative coupling mers can be prepared via the Yamamoto route,48 the
of dihexylfluorene with FeCl3 published in 1989.31 The Suzuki polycondensation is the standard procedure used,
material obtained, however, had a low-molecular weight because it allows the synthesis of strictly alternating fluo-
(Mn up to 500032) and additionally contained structural rene copolymers (APFs49; Scheme 2), which have espe-
defects, as the oxidative coupling does not proceed cially advantageous materials properties.3,28,44 As with
strictly regioselectively.5,11 An enormous synthetic PF homopolymers, the most commonly used solubilizing
improvement was the introduction of metal-catalyzed side chain in APFs is n-octyl, followed by n-hexyl,50–52
aryl–aryl coupling reactions that require monomers func- but also n-decyl,53 ethylhexyl,54 or trimethyldodecyl55
tionalized in the 2 and 7 positions, since they guarantee are occasionally used.
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Figure 1. Chain-length dependence of absorption and fluorescence maxima and energies in

OFs in chloroform solution (data taken from refs. 22 and 24).

OPTICAL PROPERTIES in solution and in the solid state.58,59 Because the 9-

position is not conjugated to the fluorene p-system and is
OFs, starting from the dimer, absorb in the UV region and far away from the aryl coupled 2- and 7-positions, the
emit blue light when excited at their absorption maximum. influence of the alkyl side chain architecture on the opti-
A narrowing of the electronic band gaps56,57 and thus red cal properties of PFs is negligible in good solvents under
shifts in both absorption and fluorescence are observed dilute conditions.2,16 Strong influences have, however,
with increasing conjugation length19–23 (Fig. 1). Con- been found on the aggregation behavior in poor
stancy of the spectral properties is reached at about 12 solvents37,60–62 and in the solid state,62–64 which are
repeat units for the absorption, but already at six repeat reflected in distinct differences in the optical proper-
units for the emission,19 indicating distinct differences in ties.65,66 For example, certain thermal treatments65,67,68
the geometries of the ground and the excited states.7,11 or solvent annealing69,70 have been found to induce
Similar to OFs, PFs absorb UV (p-p* transition at poly(dioctylfluorene) and poly(dihexylfluorene) to adopt
about 380 nm2) and emit blue light, with two photolumi- a conformation in which the fluorene repeat units are pla-
nescence maxima around 420–425 and 445 nm.7,11 The narized with respect to each other (the so-called b-phase;
reported fluorescence quantum yields exceed 50% both Fig. 2), giving rise to significant red shifts in the optical

Figure 2. Absorption (dotted line) and fluorescence (solid line) spectra of amorphous (top) and
b-phase (bottom) of a low-molecular-weight poly(dialkyl)fluorene film with a schematic repre-
sentation of the fluorene backbone in a twisted and planarized conformation. (Reproduced with
permission from ref. 69. Copyright 2008 Wiley – VCH Verlag GmbH & Co. KGaA).
Journal of Polymer Science: Part A: Polymer Chemistry
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Scheme 3. Position of the fluorescence colors of several APFs in the visible spectrum (top;
emission from solution). Values are taken from refs. 50–55 and 75–81. Chemical structures of
three frequently used APFs (bottom).

spectra.71–73 No such phase has been observed when the tion of the emission color by energy transfer to the aro-
side chains were branched.5,60,74 matic acceptor moieties.87
In contrast to fluorene homopolymers, which are re-
stricted to a rather high band gap,1,11 copolymerization
with appropriate aromatic moieties allows easy adjust- MORPHOLOGY
ment of the frontier orbital energies. If the comonomers
have a sufficiently high electron acceptor character, i.e., At elevated temperatures, PFs generally develop nematic
a low-lying LUMO, orbital mixing between the donor mesophases,2,5 which can become chiral (cholesteric) in
(fluorene) and the acceptor parts occurs, by which the the case of enantiomerically pure branched side chains.88
effective band gap is decreased.3 Alternatively, this phe- Another important structural parameter that governs the
nomenon can also be explained in terms of the valence solid state phase behavior is the average molecular
bond theory, where copolymerization with acceptor weight.89,90 For example, for poly(di(2-ethylhexyl)fluo-
materials increases the contribution of quinoid resonance rene), a transition from a nematic to a hexagonal order-
structures, thereby decreasing the degree of bond length ing has been found at a threshold molecular weight of
alternation, which also reduces the band gap energy by 10 kg/mol90 (Fig. 3). As usually observed for liquid-
suppression of the Peierls effect.3 This effect is most pro- crystalline polymers, the transition temperatures increase
nounced when the acceptor and donor moieties regularly with chain length.5
alternate in the polymer backbone, and therefore the fol- In the case of PF homopolymers with enantiomeri-
lowing discussion will be restricted to APFs. These have cally pure chiral side chains, circular dichroic (CD) spec-
been prepared with an impressive range of aromatic troscopy can be used as a sensitive tool to study phase
comonomers,3,29,44,50–55,75–81 and their emission colors behavior as they exhibit extraordinarily high CD effects
span the entire visible range, extending even into the in thermally annealed thin films40,91–93 [Fig. 4(a,b)]. In
near IR region81,82 (Scheme 3). case of (S)-3,7-dimethyloctyl chains, the degree of circu-
Band gap tuning by incorporation of electron-accept- lar polarization in absorption (gabs), defined as gabs ¼
ing comonomers has also been applied in oligofluorene 2(AL  AR)/(AL þ AR), increases with film thickness,
derivatives, although not all of them can strictly be called corresponding to a nonlinear rise of CD [Fig. 4(c)].93
alternating.83–86 Alternatively, bis(difluorenyl)amino sub- This demonstrates that the optical activity of chiral PFs
stituted aromatics with low band gap energies (e.g., py- is not only an intrinsic property of the material but is
rene and perylene) have been reported that allowed varia- also related to a mesoscopic phenomenon. Circular
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Figure 3. Chemical structure and phase diagram of poly(di(2-ethylhexyl)fluorene) with sche-

matic representation of the supramolecular chain packing. (Reproduced with permission from
ref. 89. Copyright 2005 American Physical Society).

differential scattering88 or selective reflection due to a units.21,23,95 Comparable observations have also been
cholesteric mesophase23,25 or a helical arrangement of made for some fluorene ‘‘co-oligomers.’’84,85
the polymer chains in the film41,91 have been proposed as Similar to PFs, several APFs are also liquid crystal-
the cause. line,51,79,96–99 but not much detailed information about
The solid-state phase behavior of OFs has been dem- the nature of the mesophases is available. Only few sys-
onstrated to depend strongly on chain length, but also on tematic studies have been published on the influence of
the architecture of the alkyl substituents at the 9-posi- the side chain architecture on the aggregation behavior.
tions.16 Short linear side chains, such as propyl, generally In one example, the spectral properties of thin films of
give rise to crystalline materials, whereas longer residues poly(fluorene-alt-dithienylbenzothiadiazole) (PFDTBT;
such as pentyl chains lead to an amorphous glassy Scheme 3) have been found to vary moderately with the
state.26 By contrast, partial or full replacement of linear length of the alkyl substituents,80,100 which might point
with branched side chains such as methylbutyl,23,25,26,94 to different degrees of aggregation. The influence of sub-
ethylhexyl,21,26,95 or dimethyloctyl23,25,26 generates liq- stituents attached to the comonomers has also been
uid crystalline phases whose structures are preserved investigated and found to have a significant effect on the
upon cooling by vitrification into a nematic21,24,95,96 or transition temperatures to the liquid crystalline state51
cholesteric23 glassy state. Furthermore, it is of impor- and the degree of aggregation in thin films.101 The molec-
tance whether racemic26 or enantiomerically pure23 ular weight has been demonstrated to exert a decisive
branched alkyl chains are used. Within one series of OFs impact on the melting temperature, the alignment speed,
with identical side chain architecture, the transition tem- the degree of alignment and the chain packing in
peratures increase with the number of fluorene repeat the liquid crystalline poly(fluorene-alt-benzothiadiazole)

Figure 4. (a) Chemical structure of poly(di-(S)-3,7-dimethyloctyl)fluorene). (b) CD spectra of a

film of this chiral PF after annealing at various temperatures. (Reproduced with permission from
ref. 40. Copyright 2000 Elsevier). (c) Film thickness dependence of the degree of circular polar-
ization in absorption of an annealed chiral PF film. (Reproduced with permission from ref. 93.
Copyright 2003 Wiley – VCH Verlag GmbH & Co. KGaA).
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Figure 5. (a) Chemical structure of a chiral PFDTBT. (b) CD spectra of annealed films of this
polymer with various molecular weights. (c) Molecular weight dependence of the circular polar-
ization in absorption of annealed films of this chiral PFDTBT. (Reproduced with permission
from ref. 99. Copyright 2008 American Chemical Society).

(PFBT; Scheme 3).97,102 Besides chiral PF homopolymer, align them on rubbed substrates, resulting in polarized
two chiral APFs have also been shown to develop intense blue photo-107,108 and electroluminescence2,36 with di-
CD effects after annealing of thin spin-coated films99 chroic ratios up to 21 for poly(di(2-ethylhexyl)fluorene)
[Fig. 5(a,b)]. The CD intensities were strongly depended (Fig. 6). The formation of monodomain nematic glasses
on the values of various parameters, such as the applied by a set of OFs containing five to ten repeat units has
temperatures and annealing times and the film thick- also been used with comparable results.26,94 Application
nesses. Interestingly, also a dependence on the molecular of chiral PFs in PLEDs led to circularly polarized elec-
weight was obtained, with an optimum at intermediate troluminescence with degrees of circular polarization
chain lengths [Fig. 5(c)]. (gCPEL)109 up to 0.25,40,41 thereby exceeding those
reported for other chiral p-conjugated polymers.110
OPTOELECTRONIC APPLICATIONS The alternating fluorene copolymers (APFs;49 vide su-
pra) share with PF homopolymers many of their advanta-
PFs combine a number of advantageous properties mak- geous properties, such as good solubility and thus con-
ing them attractive materials for use in polymer venient processability, mechanical flexibility, and ther-
electronic devices.1 High-molecular-weight samples are mal stability. Because of their more complex chemical
easily accessible via metal-mediated polymerization structures, some are synthetically less easily accessible,
reactions. Their good solubility in organic solvents especially if the comonomers require elaborate multistep
allows simple processing techniques such as spin coating preparation. A crucial advantage of APFs compared to
and ink jet printing, whereas small molecules have to be
deposited by technologically more demanding techniques
such as high vacuum deposition.103 Furthermore, thin
films are flexible and resistant to decomposition until
temperatures above 400  C.2 OFs lack some of these
advantages because of their low-molecular weights, but
on the other hand can be prepared in a monodisperse
fashion and purified by high-performance purification
techniques.16,104 Because of the rather large band gap of
both classes of materials (3.0–3.2 eV for PF1,28,105), their
main field of application are blue polymer light-emitting
diodes (PLEDs).1,2,16,28,59 The first example of a blue
PLED based on PF was published in 1991, contained
poly(dihexylfluorene) and had a rather poor perform-
ance.106 Since then, however, impressive improvements
have been achieved2 and PF-based optoelectronic de-
vices are now believed to have the potential of intermedi-
ate-term commercialization.103 The color of the electro-
luminescent light depends on the energy difference Figure 6. Polarized electroluminescence from aligned
between the excited and the ground state28 and thus blue poly(di(2-ethylhexyl)fluorene). (Reproduced with permission
emission occurs when PF is used as the active layer. The from ref. 2. Copyright 2001 Wiley – VCH Verlag GmbH &
nematic liquid crystallinity of many PFs has been used to Co. KGaA).
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Figure 7. Chemical structures of blue (top) and yellow (bottom) emissive fluorene based
oligomers and polarized white electroluminescence form their aligned nematic blends. The arrow
indicates spectral changes upon increasing the relative amount of yellow emissive oligomer.
(Reproduced with permission from ref. 86. Copyright 2004 Wiley – VCH Verlag GmbH & Co.

PFs is the almost unrestricted tuneability of their band wavelengths shorter than 550 nm. More promising candi-
gap energies by the appropriate choice of the comonomer dates for efficient organic solar cells are so-called low-
(Scheme 3), making them attractive for a manifold of band-gap polymers that are able to absorb far into the
applications. red and even near infrared part of the visible spectrum.
The use of APFs has allowed to extend the range of To achieve this goal, fluorene-based polymers were
electroluminescence colors far beyond blue, eventually designed that at the same time contain strong electron
encompassing the entire visible spectrum. With purely acceptor and donor units. An impressive number of
isocyclic or nitrogen-containing comonomers, the emis- APFs has been prepared, using mainly thiophene as the
sion is usually restricted to blue and cyan,50,51,76 but a donor moiety and various acceptors, most notably benzo-
higher stability of the spectra toward fluorenone emission thiadiazole, thienopyrazine, and thiadiazoloquinoxaline.
(vide infra) has been reported using dialkylbenzenes or In these polymers, which are generally applied as inti-
carbazole as comonomers.111,112 APFs with triaryl mately mixed blends with [60] PCBM in so-called bulk
amines as copolymers, such as poly(fluorene-alt-bis- heterojunction devices,126–128 band gap energies as low
(alkylphenyl)-bisphenyl-phenylenediamine) (PFB; Sch- as 1.3 eV80 made light collection possible down to 800
eme 3), combine deep blue emission44 with good hole nm.129,130 An especially interesting material is PFDTBT,
mobilities.75 Increasing the electron acceptor character
of the comonomers resulted in green,50,79,113,114 yel-
low,50,115,116 orange,116,117 or red118,119 PLEDs. White
electroluminescence has been achieved by partial energy
transfer in blends of blue emitting matrices and lower
band gap APFs.120,121 Similar results have been obtained
with fluorene co-oligomers, which additionally could be
aligned due to their liquid crystallinity, allowing the gen-
eration of polarized white light86 (Fig. 7).
Although some examples are known of APFs that are
applied in polymer field effect transistors,81,82 their sec-
ond main field of application is organic photovoltaics,3
either in combination with other polymers or with [6,6]-
phenyl-C61-butyric acid methyl ester ([60]PCBM).
Because of the broad shape of the solar emission that
reaches far into the IR region of the electromagnetic
Figure 8. External (EQE) and calculated internal (IQE)
spectrum, efficient solar cells have to collect radiation quantum efficiencies of a bulk heterojunction solar cell con-
over a wide range of wavelengths. PFBT blended with taining PFDTBT and PCBM. Inset: current-voltage measure-
PFB has been used in organic solar cells,122–124 but due ment in the dark (squares) and under simulated solar illumi-
to the rather large band gaps of PFBT (2.3 eV50) and nation (solid line). (Reproduced with permission from ref.
PFB (2.8 eV125), these devices only collected light of 131. Copyright 2007 American Institute of Physics).
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Figure 9. (a) Increasing green electroluminescence from a PF containing PLED after thermal
treatment (130  C) in air. (Reproduced with permission from ref. 136. Copyright 2007 Wiley –
VCH Verlag GmbH & Co. KGaA). (b) Simplified depiction of two competing suggestions for
the mechanism of fluorenone formation from monosubstituted fluorene repeat units. (c) Proposed
mechanism for the formation of fluorene defects in a fully alkylated model oligofluorene.
(Reproduced with permission from ref. 104. Copyright 2009 Wiley – VCH Verlag GmbH & Co.

which is not an extremely low band gap polymer (1.8 dation of active components in existing devices is critical
eV80), but still absorbs until 700 nm and gives excellent for the long-term success of the emerging field of plastic
power conversion efficiencies of above 4% (Fig. 8).131 electronics. Poor device lifetimes are especially problem-
atic for blue PLEDs103 that require high operation
voltages and are therefore especially susceptible to the
CHEMICAL DEGRADATION formation of chemical defects. Additionally, transfer of
PROCESSES IN PF excitation energy is especially likely to occur in the
emissive materials in blue PLEDs due to their high band
A major obstacle toward successful introduction of PF- gap energies. For example, this is a well-known problem
based light-emitting devices into the markets is their lim- in PF-based PLEDs, whose desired blue electrolumines-
ited stability during processing and device operation.132 cence frequently changes into an unwanted green emis-
Consequently, an improved understanding of the degra- sion band at 500–550 nm132 [Fig. 9(a)]. Originally, this
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Figure 10. Schematic representation of the interplay between chemical structure, solid state
morphology and macroscopic properties of p-conjugated materials and the resulting importance
of control over the supramolecular ordering processes.

has been explained as a result of excimer forma- tance6,62,142 (Fig. 10). Morphological control at these
tion,133,134 but more recent research has identified energy dimensions is difficult to achieve and is largely domi-
transfer from fluorene to 9-fluorenone defects as the nated by noncovalent interactions. As has been shown
main reason.5,135,136 Despite the consensus concerning earlier, OFs, PFs, and APFs by themselves exhibit al-
the chemical nature of the defect, the mechanism of its ready a richly varied phase behavior, especially as their
formation is still uncertain.132 Incomplete dialkylation of liquid crystallinity is concerned. Advanced manipulation
fluorene units in the pristine PFs has been suggested as of solid state and solution structures is possible when
the main source of oxidation to fluorenone, either by special sample preparation procedures are applied or
deprotonation and subsequent reaction of fluorenyl when a fluorene-based conjugated segment is combined
anions with oxygen5,135 or via radical reactions [Fig. with additional chemical moieties that further influence
9(b)].47,136,137 Several strategies have been employed to its supramolecular organization.
circumvent these color instabilities, e.g., the preparation Because a high contact area of the components in an
of defect-free PFs, either by careful monomer purifica- electroactive blend promotes desirable electronic pro-
tion,138 or by applying a special synthetic route to the cesses, such as exciton dissociation, several strategies
monomers, that ensure complete double alkylation.139 have been developed to create nanoparticles from fluo-
Although these materials display higher stabilities, com- rene-based materials. An early approach was the produc-
plete stability in the solid state has turned out to be diffi- tion of core-shell particles through layer-by-layer deposi-
cult to achieve. This is further supported by the recent tion of anionic PSS and a cationic precursor polymer on
observation that even defect-free OFs obtained by high- colloidal substrates.143 As the precursor contained non-
performance purification techniques are prone to photo- conjugated fluorene units, oxidative coupling stabilized
oxidative degradation via the formation of carboxylic these structures by the formation of oligomeric cross-
intermediates in the side chains [Fig. 9(c)].104 Spirosub- links. Afterwards, removal of the core templates by
stituted PFs,136 replacement of the saturated side chains chemical decomposition left back blue fluorescent hol-
by aromatic substituents47,140 or using the 9-silicon ana- low capsules of about 2 lm diameter. Alternatively,
logues of fluorene141 seem to be more promising microemulsions consisting of water, a surfactant, and a
approaches to avoid oxidative degradation. PF solution in chloroform have been prepared by ultraso-
nication, and after evaporation of the organic solvent, an
artificial latex remained with an average particle size of
SUPRAMOLECULAR APPROACHES TOWARD about 100 nm.144,145 In a more recent approach, it has
SOLID-STATE ORGANIZATION been shown that even smaller nanoparticles of PFs or
APFs (diameter 5–50 nm) can be produced without the
‘‘Classical’’ covalent chemistry offers excellent structural addition of surfactants, when a water-miscible solvent is
control up to a length scale of several nanometres, but used146,147 [Fig. 11(a)]. Their size could be controlled by
for the performance optimalization of optoelectronic the concentration of the injected stock solution, and in
devices, the supramolecular order in the nanometer up to PF particles, the internal chain organization could be
the micrometer regime is also of paramount impor- changed from a glassy state to the b-phase by improving
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Figure 11. (a) AFM height image of poly(dioctylfluorene) nanoparticles. The scale bar corre-
sponds to 100 nm. (Reproduced with permission from ref. 146. Copyright 2006 American Chem-
ical Society). (b) Aqueous dispersions of nanoparticles from PF and a mixture of PF and PFBT
under UV illumination (375 nm). (c) Absorption (dashed line) and fluorescence excitation and
emission spectra (solid lines) of pure PF (top) and mixed (bottom) nanoparticles in water. Exci-
tation wavelength 375 nm. (Reproduced with permission from ref. 149. Copyright 2006 Ameri-
can Chemical Society).

the solvent quality.148 In the case of mixed nanoparticles, ble blocks is known to trigger the formation of several
their emission properties were tuned by energy transfer different solid state morphologies.6,150,151 Because of the
processes from PF to APFs149 [Fig. 11(b,c)]. limited motional freedom of the PF backbone, it is
Several strategies have been developed to control the rather rigid (persistence length 8–10 nm152–154) and
ordering of fluorene-based materials by chemical modifi- serves as a rod block. It has been combined with a wide
cations instead of only relying on their inherent supra- variety of flexible polymers such as poly(meth)acry-
molecular properties, such as liquid crystallinity. The lates,155–158 polystyrene,157 poly(ethylene glycol)
most frequently applied approach is the synthesis of (PEG),159,160 and polyglutamate161 to prepare rod-coil
block copolymers with PF or OF as one of the blocks, di- and triblock copolymers. Distinct differences in the
because microphase separation of chemically incompati- solid state order have been found when PF-PEG diblock

Figure 12. (a) Solid state organization of PF-PEG diblock copolymers with different volume
fractions of the PEG segment (fPEG; left 0.1, right 0.3) and corresponding chemical structures
(Reproduced with permission from ref. 159. Copyright 2004 Wiley – VCH Verlag GmbH & Co.
KGaA). (b) Solid state organization of a PA-PF-PA block copolymer spin coated from THF and
toluene and corresponding chemical structure. (Reproduced with permission from ref. 168. Copy-
right 2007 Wiley – VCH Verlag GmbH & Co. KGaA).
Journal of Polymer Science: Part A: Polymer Chemistry
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Figure 13. (a) Chemical structure of a hydrogen bonding oligofluorene. (b) Schematic repre-
sentation of the principle of white emission by partial energy transfer within a hydrogen bonded
supramolecular polymer containing energy donor (blue) and energy acceptor (green, red) moi-
eties. (c) White emission from a thin film of a fluorene-based hydrogen bonded polymer. (Repro-
duced with permission from ref. 171. Copyright 2009 American Chemical Society).

and PEG-PF-PEG triblock copolymers with varying vol- strong differences in polarity. The aggregation processes
ume fractions of coil to rod were studied by atomic could be easily followed by fluorescence spectroscopy
force microscopy (AFM; Fig. 12a).159 A low percentage due to energy transfer from the PF to the PT block in
of PEG gave rise to well-defined organization into nano- the aggregated state.169
ribbons due to p-p stacking of the PF blocks and inter- Supramolecular approaches different from PF or OF
actions of the PEG with the substrate. At higher coil-to- block copolymers include the use of noncovalent interac-
rod ratios, p-p stacking was prevented and untextured tions such as hydrogen bonding,22,170,171 metal-ligand
aggregates were found. The combination of PFs with coordination,172,173 or hydrophobic interactions.83,174 For
thermoresponsive N-isopropylacrylamide blocks in coil- example, in OFs replacement of alkyl by polar 9-
rod-coil triblock copolymers has allowed the preparation substituents such as oligo(ethylene glycol) led to collapse
of thermochromic assemblies in aqueous solution.162 A of the apolar parts in water and the formation of nanopar-
well-defined oligomer composed of two 3,4-ethylene- ticles.174 A similar result has also been achieved with
dioxythiophene units linked by dihexylfluorene has been bolaamphiphilic fluorene oligomers, in which addition-
equipped with PEG side chains of different lengths, ally the emission colors of the individual particles could
resulting in the formation of various types of self- be tuned by adjustment of their chemical structures and
assembled micelles in water.163 PFs have also been com- composition.83 Supramolecular polymers with high vir-
bined with other conjugated polymers, such as polyani- tual degrees of polymerization and high solution viscos-
line164–166 (PA) and polythiophene,167 to create rod-rod ities have been obtained by disubstitution of OFs with
block copolymers. PA-PF-PA triblock copolymers have endfunctionalities that are able to dimerize via strong
been found to microphase separate into different kinds and directional quadruple hydrogen bonds.171 These
of structures depending on the solvent from which they compounds combined the advantages of well-defined
were deposited (Fig. 12b).168 In solution, PF-PT diblock small molecules (e.g., high-performance purification)
copolymers could be self-assembled by adjusting the with those of covalent polymers (e.g., processing from
solvent composition, because the two blocks exhibited solution) and could be applied in electroluminescent
Journal of Polymer Science: Part A: Polymer Chemistry
DOI 10.1002/pola

Figure 14. (a) AFM height images of a 1:1 blend of PFB and PFBT spin coated from xylene
(left) or chloroform (center) solution and corresponding EQE spectra (left). (Reproduced with
permission from ref. 124. Copyright 2001 American Chemical Society). (b) AFM height images
of a 3:1 blend of [60]PCBM and PFDTBT spin coated from chloroform containing 1.2% xylene
(left) or 1.2% chlorobenzene (center) and corresponding EQE spectra (left). The relevant spectra
are marked with an arrow. (Reproduced with permission from ref. 126. Copyright 2006 Wiley –
VCH Verlag GmbH & Co. KGaA).

devices. Mixing in other hydrogen bonded conjugated SENSING AND IMAGING APPLICATIONS
oligomers allowed tuning of the emission color covering
the entire visible range, including white without any sign Except for their manifold use in organic and polymer
of phase separation (Fig. 13). electronics, fluorene-based p-conjugated materials have
The solid-state organization of APFs have been stud- recently found widespread applications as sensors.4 Also
ied especially intensely in blends with other electroactive here, the sensing process is dominated by noncovalent
materials due to the importance of these mixtures in or- interactions between the analyte and sensor molecules. A
ganic solar cells, where the correct thin film morphology high sensitivity toward subtle changes in the environ-
is indispensable for good charge separation, transport, ments is made possible due to signal enhancement
and extraction.6,175–177 In the scope of device optimaliza- because of the conjugation via the polymer or oligomer
tion, the influence of different processing conditions has backbones. Furthermore, fluorescence spectroscopy often
been investigated. In bulk heterojunction solar cells con- allows an easy and sensitive detection. When metal bind-
taining blends of PFB and PFBT, a more intimate mixing ing ligands such as bipyridine derivatives are used as
of the components in the active layer has been reached comonomers, APFs are obtained that display different
by an increased evaporation rate during the deposition sensitivities toward transition metal ions, depending on
process, accomplished either by heating, solvent choice, the complexation strength178,179 (Fig. 15a). Similar
or variation of the deposition technique122–124 (Fig. 14a). observations have been made for PFs containing ligands
In all cases, phase separation on a smaller scale resulted attached to the side chains, such as imidazole, showing a
in an increased device performance. Similar results have high selectivity for Cu(II)180 or phosphonates, which
also been obtained in blends of PFDTBT with selectively bind to Fe(III).181 A similar approach has
[60]PCBM, when the degree of mixing was adjusted by been published with a (statistical) copolymer of fluorene
the solvent composition126 (Fig. 14b). and dibenzoborole, which showed fluorescence
Journal of Polymer Science: Part A: Polymer Chemistry
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4228 J. POLYM. SCI. PART A: POLYM. CHEM.: VOL. 47 (2009)

Figure 15. (a) Fluorescence titration of an APF with MnCl2 in THF. The arrow indicates spectral
changes upon increasing Mn(II) concentration from 0 to 10 ppm. (Reproduced with permission
from ref. 178. Copyright 2001 American Chemical Society). (b) Fluorescence titration of a statisti-
cal fluorene copolymer with tetrabutylammonium iodide in THF. The arrow indicates spectral
changes upon increasing iodide concentration from 0 to 1.3 mM. (Reproduced with permission
from ref. 182. Copyright 2008 Wiley – VCH Verlag GmbH & Co. KGaA). (c) Schematic illustra-
tion of the detection principle of DNA with fluorescently labeled PNA and a cationic APF. (Repro-
duced with permission from ref. 195. Copyright 2002 National Academy of Sciences, USA).

quenching in the presence of halide anions182 (Fig. 15b). nism is usually based on the electrostatic attraction
PFs and APFs have also been widely applied as sensors between the oppositely charged analyte and probe mole-
for biologically interesting analytes, such as DNA or pro- cules. In one strategy, the hybridization of single strand
teins, which are only soluble in water.4 Since conven- DNA with complementary peptide nucleic acids (PNAs)
tional fluorene-based materials only dissolve in rather has been used to discriminate the base sequence of target
apolar organic solvents, they require special adaptations DNA strands195,196 (Fig. 15c). In an aqueous solution of
of their chemical structures to be used in aqueous a cationic APF and PNA functionalized with a fluores-
media.183 The most commonly used strategy to achieve cent label, no energy transfer was observed because PNA
this goal is the attachment of ionic side chains to is neutral and does not interact strongly with the poly-
the 9-positions of the fluorenes, such as ammonium electrolyte. Upon addition of single strand DNA, hybrid-
salts,184–186 sulfonates,187,188 or carboxylates.189 These ization with the PNA occurred when the strands were
PF polyelectrolytes have been found to electrostatically complementary. The resulting negatively charged DNA-
attract oppositely charged substrates in solution, which PNA hybrid formed a complex with the APF, which
gave rise to aggregation of the PF backbone, and the therefore came into close spatial proximity to the fluores-
resulting shifts in the fluorescence spectra were followed cent label. Since this label was chosen such that good
in time to monitor enzyme activity.188 Especially intense spectral overlap of its absorption with the fluorescence
research has been done on interactions of DNA and cati- spectrum of the APF was ensured, energy transfer was
onic OFs.190–194 Also in this case, the detection mecha- observed, resulting in emission of the label. By contrast,
Journal of Polymer Science: Part A: Polymer Chemistry
DOI 10.1002/pola

no such interactions were detected when DNA and PNA 4. Thomas, S. W.; Joly, G. D.; Swager, T. M. Chem
were not complementary. Similar strategies have also Rev 2007, 107, 1339–1386.
been applied that do not require PNA, but work solely 5. Scherf, U.; List, E. J. W. Adv Mater 2002, 14,
with DNA.191–193 477–487.
6. Chen, P.; Yang, G.; Liu, T.; Li, T.; Wang, M.;
Except for sensing, PFs and APFs have also been pro-
Huang, W. Polym Int 2006, 55, 473–490.
posed for biological imaging applications, for example in
7. Grimsdale, A. C.; Müllen, K. Macromol Rapid
the form of nanoparticles (vide supra).146–149 A first suc- Commun 2007, 28, 1676–1702.
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easy synthetic availability and their advantageous opto- 12. Gutmann, R. H.; Burtle, J. G.; Fenton, S. W. J
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14. Kelley, C. J.; Ghiorghis, A.; Kauffman, J. M. J
such as light-emitting diodes and photovoltaic cells.
Chem Res S 1997, 12, 446–447.
Color tuning can be easily achieved by copolymerization 15. Wong, K.-T.; Chien, Y.-Y.; Chen, R.-T.; Wang,
with appropriate comonomers, resulting in emission col- C.-F.; Lin, Y.-T.; Chiang, H.-H.; Hsieh, P.-Y.;
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advances, research in this field is limited, especially
31, 2007–2009.
when oligomers are concerned. Therefore, the supra- 20. Anéniam, R.; Mulatier, J.-C.; Andraud, C.; Sté-
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The authors acknowledge the many discussions with and contri- 22. Dudek, S. P.; Pouderoijen, M.; Abbel, R.; Schen-
butions from all our former and current colleagues. Their names ning, A. P. H. J.; Meijer, E. W. J Am Chem Soc
are given in the references cited. The research in our laboratory 2005, 127, 11763–11768.
has been supported by the Eindhoven University of Technol- 23. Geng, Y.; Trajkovska, A.; Katsis, D.; Ou, J. J.;
ogy, the Royal Netherlands Academy of Sciences (KNAW), the Culligan, S. W.; Chen, S. H. J Am Chem Soc
Netherlands Organisation for Scientific Research (NWO) and 2002, 124, 8337–8347.
the European Young Investigators Awards (EURYI). 24. Katsis, D.; Geng, Y. H.; Ou, J. J.; Culligan, S.
W.; Trajkovska, A.; Chen, S. H.; Rothberg, L. J
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