HIGHLIGHT

Fluorene-Based Materials and Their Supramolecular Properties
ROBERT ABBEL, ALBERTUS P. H. J. SCHENNING, E. W. MEIJER 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 (www.interscience.wiley.com).

ABSTRACT: Fluorene-based pconjugated polymers and oligomers combine several advantageous properties that make them well-suited candidates for applications in organic optoelectronic devices and chemical sensors. This review highlights strategies to synthesize these materials and to tune their absorption and

emission colors. Furthermore, methods to control their supramolecular organization will be discussed. In many cases, a delicate interplay between the chemical structure and the processing conditions are found, resulting in a high sensitivity of both structural features and optical properC ties. V 2009 Wiley Periodicals, Inc. J

Polym Sci Part A: Polym Chem 47: 4215–4233, 2009

Keywords: p-conjugated oligomers; p-conjugated polymers; fluorene copolymers; morphology; oligofluorenes; phase behavior; polyaromatics, polyfluorenes; selfassembly; self-organization; supramolecular structures; thin films

Robert Abbel

Robert Abbel studied chemistry at the Universities of Mainz, Germany and Toronto, Canada. In 2004, he received the degree of Diplom-Chemiker 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 chemistry. He received his PhD degree in 2008 and is currently working at TNO Industries.

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

4215

3 Recently. yielding a series of oligofluorenes (OFs) with increasing conjugation lengths. E. tion of the aromatic system.7 which increases their orbital overlap and the degree of conjuga- Scheme 1.98) as the resulting aromatic fluorenyl anion is efficiently resonance stabilized. H. Prof. Schenning Albertus P. most notably organic light-emitting diodes1. In 1997. POLYM. the protons at the sp3 carbon in the methylene bridge (9-position) exhibit a significant CH acidity (pKA ¼ 22.5. 47 (2009) Albertus P. J.: VOL. he became head of the Laboratory of Macromolecular and Organic Chemistry at the Eindhoven University of Technology. homo-. J. Prof. arylation requires more elaborate synthetic procedures and is therefore less frequently used. Feiters and Prof.15 of fluorene. Journal of Polymer Science: Part A: Polymer Chemistry DOI 10. Schenning is associate professor at the Eindhoven University of Technology.9.1002/pola . F. Such chemical reactions can be suppressed by double alkylation11. E. the fields of application are introduced and some recent key developments concerning research in these areas are depicted.2 and organic photovoltaic cells. J. ‘‘Bert’’ Meijer INTRODUCTION p-Conjugated polymers and oligomers based on fluorene building blocks have gained importance as the active materials in various types of organic optoelectronic devices. W. W. The most common synthetic routes will be described together with both their optical properties and phase behavior. the Netherlands. he was a postdoctoral fellow in the group of Prof.5 This can be overcome by full planarization using the so-called SYNTHETIC PROCEDURES 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 adjacent methylene bridge (Scheme 1). His research is focused on supramolecular chemistry.16 Because of the torsional freedom of the biphenyl bond. Hans Wynberg) and a 10-year career in industry (Philips and DSM). chemical biology. R. His current research interests are selfassembled p-conjugated systems. and copolymers. M. M. W. Between June and December 1996. In bare fluorene. The methylene bridge forces the two phenyl rings to be planar. ‘‘Bert’’ Meijer is Distinguished University Professor in the Molecular Sciences and Professor of Organic Chemistry at the Eindhoven University of Technology. their use as sensing and imaging agents has emerged as a growing second field of application. which has the additional advantage of introducing side groups that enhance the solubility in organic solvents.14 or arylation11. CHEM. and stereochemistry. the planes of the fluorene units are usually tilted with respect to each other. the Netherlands. Diederich at the ETH in Zurich.10 Oxidation to 9-fluorenone is another frequently observed reaction.4 The optical and electronic properties of fluorene-based materials highly depend on both the chemical structures and the supramolecular organization. Nolte.4216 J. After a PhD in 1982 from the University of Groningen (Organic Chemistry with Prof. where he investigated p-conjugated triacetylenes. H.11 Fluorene monomers can be directly connected to each other via aromatic coupling at the 2 and 7 positions. C. E. Chemical structure and atomic numbering of fluorene. Meijer at the Eindhoven University of Technology working on dendrimers. functional organic materials. an overview is presented highlighting scientific literature on fluorene-based optoelectronic materials such as oligomers. SCI. Finally.6 Here. he joined the ¨ group of Prof. PART A: POLYM. He received his PhD degree at the Radboud University of Nijmegen in 1996 on supramolecular architectures based on porphyrin and receptor molecules with Dr.2 Whereas alkylation is easily achieved by reaction of the fluorenyl anion with bromoalkanes. strategies are highlighted that have been successfully employed to gain understanding of and control over the supramolecular organization of fluorene-based materials.11–13 which is also favored by resonance stabilization because the p-conjugated system is extended. Furthermore.

.2. With the appropriate reaction conditions applied. Illustration of the two most commonly used synthetic strategies toward fluorene polymers: PF homopolymer synthesis by (a) Yamamoto and (b) Suzuki polycondensation.30.9-dihexylfluorene in the presence of 2-bromofluorene as an end capper (Scheme 2).11. Although statistical copolymers can be prepared via the Yamamoto route.000 g molÀ1) can be obtained with both strategies.11. because it allows the synthesis of strictly alternating fluorene copolymers (APFs49.3.28.50–52 but also n-decyl.11.5.31 The material obtained.22. however. ladder-type materials.7-dibromo-9. but the solubility of PFs increases with the length of the alkyl chains and the degree of branching. (c) APF synthesis by Suzuki polycondensation. Connection of fluorene monomers with two reactive sites in a one-step synthesis produces polydisperse oligomer mixtures or. the higher reactivity of aromatic iodine compounds20 or diazonium salts21 in Suzuki couplings compared to bromine derivatives has been exploited.11 As in the case of OF synthesis.19 Monodisperse molecules were obtained from the oligomer mixture by high-performance liquid chromatography.36 PFs have been prepared with a wide variety of alkyl chains attached to the 9-position. These polymers are of particular interest due to the possibility to tune the electronic band gap and thus the emission colors of the materials by an appropriate choice of the comonomers (vide infra).25 The central carbon–carbon coupling step of all these routes is the Pd-catalyzed Suzuki reaction of aromatic halogen compounds with boronic acids or esters.1002/pola perfect regioselectivity. several research groups20–26 have prepared OFs by stepwise approaches that also allowed variation of the alkyl substitution pattern along the oligomer backbone in a defined manner (Scheme 2). 2-ethylhexyl and 3. Later. which have especially advantageous materials properties.54 or trimethyldodecyl55 are occasionally used.29 Although insoluble poly(dimethylfluorene) has been obtained by electropolymerization in 1987.28. the resulting PFs are highly soluble in common apolar organic solvents. had a low-molecular weight (Mn up to 500032) and additionally contained structural defects.38 branched (most notably 2-methylbutyl.53 ethylhexyl. as the oxidative coupling does not proceed strictly regioselectively.23.45 but other groups such as spirolinked fluorenes46. polyfluorenes (PFs). the most prominent types of reactions used to prepare PFs are the Ni(0)-mediated Yamamoto and the Pdcatalyzed Suzuki condensations7.44 Arylated OFs and PFs most commonly bear (substituted) phenyl groups at the 9-position.7-dimethyloctyl). When methylbutyl.17. highmolecular-weight PF (Mn [ 100.11 An enormous synthetic improvement was the introduction of metal-catalyzed aryl–aryl coupling reactions that require monomers functionalized in the 2 and 7 positions.44 As with PF homopolymers.28.33–35 (Scheme 2).43 Poly(dimethylfluorene) and poly(diethylfluorene) are poorly soluble.5.7. or longer substituents are attached to the 9-position.39–42 and spirocyclic.15.30 the first example of a synthetic approach toward soluble PFs was the oxidative coupling of dihexylfluorene with FeCl3 published in 1989.23. hexyl.47 have also been used. protective groups such as trimethylsilyl units are required. since they guarantee Journal of Polymer Science: Part A: Polymer Chemistry DOI 10. Metal-catalyzed aryl–aryl cross couplings are also very useful for the synthesis of fluorene copolymers.27 To allow the synthetic strategy toward longer oligomers to proceed selectively.48 the Suzuki polycondensation is the standard procedure used. when no endcappers are present.26 Alternatively. the most commonly used solubilizing side chain in APFs is n-octyl.29.37. R ¼ alkyl. R0 ¼ H or alkyl.17 but these are not the subject of this highlight article. followed by n-hexyl.5.HIGHLIGHT 4217 Scheme 2. Scheme 2). both linear (methyl up to n-hexadecyl). The first systematic study involving a considerable number of well-defined fluorene oligomers (up to ten repeat units) used the Ni(0)-mediated Yamamoto coupling18 of 2.

Fig. with two photoluminescence maxima around 420–425 and 445 nm. 69. starting from the dimer.7. absorb in the UV region and emit blue light when excited at their absorption maximum. CHEM. however.11 The reported fluorescence quantum yields exceed 50% both in solution and in the solid state.2. certain thermal treatments65. but already at six repeat units for the emission.66 For example. POLYM. KGaA). OPTICAL PROPERTIES OFs.62–64 which are reflected in distinct differences in the optical properties. Chain-length dependence of absorption and fluorescence maxima and energies in OFs in chloroform solution (data taken from refs.65. been found on the aggregation behavior in poor solvents37. 22 and 24). 2). A narrowing of the electronic band gaps56. 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 representation of the fluorene backbone in a twisted and planarized conformation.4218 J.59 Because the 9position is not conjugated to the fluorene p-system and is far away from the aryl coupled 2.57 and thus red shifts in both absorption and fluorescence are observed with increasing conjugation length19–23 (Fig. (Reproduced with permission from ref. Constancy of the spectral properties is reached at about 12 repeat units for the absorption. Copyright 2008 Wiley – VCH Verlag GmbH & Co. PFs absorb UV (p-p* transition at about 380 nm2) and emit blue light.11 Similar to OFs.67.and 7-positions.58.19 indicating distinct differences in the geometries of the ground and the excited states.: VOL.1002/pola .60–62 and in the solid state. SCI. 1).68 or solvent annealing69. PART A: POLYM. 47 (2009) Figure 1.7.16 Strong influences have. Journal of Polymer Science: Part A: Polymer Chemistry DOI 10.70 have been found to induce poly(dioctylfluorene) and poly(dihexylfluorene) to adopt a conformation in which the fluorene repeat units are planarized with respect to each other (the so-called b-phase. giving rise to significant red shifts in the optical Figure 2. the influence of the alkyl side chain architecture on the optical properties of PFs is negligible in good solvents under dilute conditions.

In case of (S)-3.HIGHLIGHT 4219 Scheme 3. PFs generally develop nematic mesophases.75–81 and their emission colors span the entire visible range.3 Alternatively.3 This effect is most pronounced when the acceptor and donor moieties regularly alternate in the polymer backbone.74 In contrast to fluorene homopolymers.88 Another important structural parameter that governs the solid state phase behavior is the average molecular weight.93 This demonstrates that the optical activity of chiral PFs is not only an intrinsic property of the material but is also related to a mesoscopic phenomenon.5 which can become chiral (cholesteric) in the case of enantiomerically pure branched side chains.b)].7-dimethyloctyl chains. thereby decreasing the degree of bond length alternation. which also reduces the band gap energy by suppression of the Peierls effect.1002/pola tion of the emission color by energy transfer to the aromatic acceptor moieties. emission from solution). These have been prepared with an impressive range of aromatic comonomers. which are restricted to a rather high band gap.3. by which the effective band gap is decreased. the degree of circular polarization in absorption (gabs).44. circular dichroic (CD) spectroscopy can be used as a sensitive tool to study phase behavior as they exhibit extraordinarily high CD effects in thermally annealed thin films40. Band gap tuning by incorporation of electron-accepting comonomers has also been applied in oligofluorene derivatives. although not all of them can strictly be called alternating.50–55. a transition from a nematic to a hexagonal ordering has been found at a threshold molecular weight of $10 kg/mol90 (Fig.87 MORPHOLOGY At elevated temperatures.60.91–93 [Fig.5 In the case of PF homopolymers with enantiomerically pure chiral side chains. defined as gabs ¼ 2Á(AL À AR)/(AL þ AR). and therefore the following discussion will be restricted to APFs. 3). spectra. extending even into the near IR region81. Values are taken from refs.e.11 copolymerization with appropriate aromatic moieties allows easy adjustment of the frontier orbital energies.2. Position of the fluorescence colors of several APFs in the visible spectrum (top. corresponding to a nonlinear rise of CD [Fig.29. 50–55 and 75–81. i.1. 4(a. the transition temperatures increase with chain length. where copolymerization with acceptor materials increases the contribution of quinoid resonance structures. a low-lying LUMO.89.71–73 No such phase has been observed when the side chains were branched.83–86 Alternatively.5. orbital mixing between the donor (fluorene) and the acceptor parts occurs.g.. this phenomenon can also be explained in terms of the valence bond theory. pyrene and perylene) have been reported that allowed variaJournal of Polymer Science: Part A: Polymer Chemistry DOI 10. If the comonomers have a sufficiently high electron acceptor character. Circular .. Chemical structures of three frequently used APFs (bottom). increases with film thickness. for poly(di(2-ethylhexyl)fluorene). bis(difluorenyl)amino substituted aromatics with low band gap energies (e. As usually observed for liquidcrystalline polymers.90 For example.82 (Scheme 3). 4(c)].

partial or full replacement of linear with branched side chains such as methylbutyl.23. such as propyl. the degree of alignment and the chain packing in the liquid crystalline poly(fluorene-alt-benzothiadiazole) Figure 4.26.21. In one example. Copyright 2000 Elsevier). PART A: POLYM. generally give rise to crystalline materials.95 or dimethyloctyl23. (a) Chemical structure of poly(di-(S)-3. Scheme 3) have been found to vary moderately with the length of the alkyl substituents. (Reproduced with permission from ref. 47 (2009) Figure 3.16 Short linear side chains.96 or cholesteric23 glassy state. Only few systematic studies have been published on the influence of the side chain architecture on the aggregation behavior.26. Copyright 2003 Wiley – VCH Verlag GmbH & Co. (b) CD spectra of a film of this chiral PF after annealing at various temperatures. 89. SCI. whereas longer residues such as pentyl chains lead to an amorphous glassy state. the transition temperatures increase with the number of fluorene repeat units. Copyright 2005 American Physical Society). the alignment speed.25 or a helical arrangement of the polymer chains in the film41.’’84.85 Similar to PFs.24. The solid-state phase behavior of OFs has been demonstrated to depend strongly on chain length. the spectral properties of thin films of poly(fluorene-alt-dithienylbenzothiadiazole) (PFDTBT. (Reproduced with permission from ref. 40. (Reproduced with permission from ref.7-dimethyloctyl)fluorene).1002/pola . POLYM. it is of importance whether racemic26 or enantiomerically pure23 branched alkyl chains are used.101 The molecular weight has been demonstrated to exert a decisive impact on the melting temperature. differential scattering88 or selective reflection due to a cholesteric mesophase23.91 have been proposed as the cause. several APFs are also liquid crystalline. Journal of Polymer Science: Part A: Polymer Chemistry DOI 10.95 Comparable observations have also been made for some fluorene ‘‘co-oligomers.96–99 but not much detailed information about the nature of the mesophases is available.23. but also on the architecture of the alkyl substituents at the 9-positions.26 generates liquid crystalline phases whose structures are preserved upon cooling by vitrification into a nematic21.51. KGaA). Within one series of OFs with identical side chain architecture.95.: VOL.4220 J. The influence of substituents attached to the comonomers has also been investigated and found to have a significant effect on the transition temperatures to the liquid crystalline state51 and the degree of aggregation in thin films.21.94 ethylhexyl. CHEM. Chemical structure and phase diagram of poly(di(2-ethylhexyl)fluorene) with schematic representation of the supramolecular chain packing. Furthermore.79.80.26 By contrast.100 which might point to different degrees of aggregation.25. (c) Film thickness dependence of the degree of circular polarization in absorption of an annealed chiral PF film.25. 93.

(c) Molecular weight dependence of the circular polarization in absorption of annealed films of this chiral PFDTBT. Because of their more complex chemical structures.1. (PFBT. (Reproduced with permission from ref. 2. KGaA). 5(c)]. also a dependence on the molecular weight was obtained. mechanical flexibility. The CD intensities were strongly depended on the values of various parameters. with an optimum at intermediate chain lengths [Fig.40. 99. .110 The alternating fluorene copolymers (APFs.25.59 The first example of a blue PLED based on PF was published in 1991. whereas small molecules have to be deposited by technologically more demanding techniques such as high vacuum deposition. such as good solubility and thus convenient processability.2.36 with dichroic ratios up to 21 for poly(di(2-ethylhexyl)fluorene) (Fig. The formation of monodomain nematic glasses by a set of OFs containing five to ten repeat units has also been used with comparable results. A crucial advantage of APFs compared to Figure 6. resulting in polarized blue photo-107.HIGHLIGHT 4221 Figure 5. Copyright 2001 Wiley – VCH Verlag GmbH & Co. OPTOELECTRONIC APPLICATIONS PFs combine a number of advantageous properties making them attractive materials for use in polymer electronic devices. Their good solubility in organic solvents allows simple processing techniques such as spin coating and ink jet printing. Scheme 3).49 vide supra) share with PF homopolymers many of their advantageous properties. Polarized electroluminescence from aligned poly(di(2-ethylhexyl)fluorene). two chiral APFs have also been shown to develop intense CD effects after annealing of thin spin-coated films99 [Fig. impressive improvements have been achieved2 and PF-based optoelectronic devices are now believed to have the potential of intermediate-term commercialization. (Reproduced with permission from ref.105).2 eV for PF1.41 thereby exceeding those reported for other chiral p-conjugated polymers.b)].94 Application of chiral PFs in PLEDs led to circularly polarized electroluminescence with degrees of circular polarization (gCPEL)109 up to 0. Interestingly. Copyright 2008 American Chemical Society).97.0–3. such as the applied temperatures and annealing times and the film thicknesses. 5(a.28. some are synthetically less easily accessible.26. contained poly(dihexylfluorene) and had a rather poor performance. (a) Chemical structure of a chiral PFDTBT.108 and electroluminescence2. especially if the comonomers require elaborate multistep preparation.28. The nematic liquid crystallinity of many PFs has been used to Journal of Polymer Science: Part A: Polymer Chemistry DOI 10. and thermal stability.106 Since then.103 The color of the electroluminescent light depends on the energy difference between the excited and the ground state28 and thus blue emission occurs when PF is used as the active layer. thin films are flexible and resistant to decomposition until temperatures above 400  C. 6).16. (b) CD spectra of annealed films of this polymer with various molecular weights. but on the other hand can be prepared in a monodisperse fashion and purified by high-performance purification techniques.104 Because of the rather large band gap of both classes of materials (3.1 High-molecular-weight samples are easily accessible via metal-mediated polymerization reactions. however.1002/pola align them on rubbed substrates.102 Besides chiral PF homopolymer.16.103 Furthermore. their main field of application are blue polymer light-emitting diodes (PLEDs).2 OFs lack some of these advantages because of their low-molecular weights.

120.50.3 eV80 made light collection possible down to 800 nm. combine deep blue emission44 with good hole mobilities.115. 7). thienopyrazine. PART A: POLYM.50. the emission is usually restricted to blue and cyan. Copyright 2004 Wiley – VCH Verlag GmbH & Co. 86.81.3 eV50) and PFB (2. 47 (2009) Figure 7.: VOL.111. and thiadiazoloquinoxaline. The use of APFs has allowed to extend the range of electroluminescence colors far beyond blue. most notably benzothiadiazole. Although some examples are known of APFs that are applied in polymer field effect transistors. PFs is the almost unrestricted tuneability of their band gap energies by the appropriate choice of the comonomer (Scheme 3).129. eventually encompassing the entire visible spectrum. fluorene-based polymers were designed that at the same time contain strong electron acceptor and donor units. Journal of Polymer Science: Part A: Polymer Chemistry DOI 10. which are generally applied as intimately mixed blends with [60] PCBM in so-called bulk heterojunction devices. To achieve this goal.112 APFs with triaryl amines as copolymers.119 PLEDs. With purely isocyclic or nitrogen-containing comonomers. allowing the generation of polarized white light86 (Fig. making them attractive for a manifold of applications. such as poly(fluorene-alt-bis(alkylphenyl)-bisphenyl-phenylenediamine) (PFB.76 but a higher stability of the spectra toward fluorenone emission (vide infra) has been reported using dialkylbenzenes or carbazole as comonomers. using mainly thiophene as the donor moiety and various acceptors. PFBT blended with PFB has been used in organic solar cells.50.117 or red118. Inset: current-voltage measurement in the dark (squares) and under simulated solar illumination (solid line). which additionally could be aligned due to their liquid crystallinity. Copyright 2007 American Institute of Physics).6]phenyl-C61-butyric acid methyl ester ([60]PCBM).114 yellow.126–128 band gap energies as low as 1. The arrow indicates spectral changes upon increasing the relative amount of yellow emissive oligomer. these devices only collected light of wavelengths shorter than 550 nm. (Reproduced with permission from ref. 131.122–124 but due to the rather large band gaps of PFBT (2.130 An especially interesting material is PFDTBT.8 eV125).113. POLYM. KGaA).4222 J. Scheme 3).51. efficient solar cells have to collect radiation over a wide range of wavelengths.116.82 their second main field of application is organic photovoltaics.75 Increasing the electron acceptor character of the comonomers resulted in green.3 either in combination with other polymers or with [6. An impressive number of APFs has been prepared.116 orange. In these polymers. (Reproduced with permission from ref. CHEM. Chemical structures of blue (top) and yellow (bottom) emissive fluorene based oligomers and polarized white electroluminescence form their aligned nematic blends. Because of the broad shape of the solar emission that reaches far into the IR region of the electromagnetic spectrum. White electroluminescence has been achieved by partial energy transfer in blends of blue emitting matrices and lower band gap APFs. More promising candidates for efficient organic solar cells are so-called lowband-gap polymers that are able to absorb far into the red and even near infrared part of the visible spectrum.79. External (EQE) and calculated internal (IQE) quantum efficiencies of a bulk heterojunction solar cell containing PFDTBT and PCBM. Figure 8.1002/pola .121 Similar results have been obtained with fluorene co-oligomers. SCI.

131 CHEMICAL DEGRADATION PROCESSES IN PF A major obstacle toward successful introduction of PFbased light-emitting devices into the markets is their limited stability during processing and device operation.1002/pola dation of active components in existing devices is critical for the long-term success of the emerging field of plastic electronics. (c) Proposed mechanism for the formation of fluorene defects in a fully alkylated model oligofluorene.HIGHLIGHT 4223 Figure 9. this . (a) Increasing green electroluminescence from a PF containing PLED after thermal treatment (130  C) in air. 9(a)].8 eV80). an improved understanding of the degraJournal of Polymer Science: Part A: Polymer Chemistry DOI 10. 104. (Reproduced with permission from ref.132 Consequently. KGaA). For example. (b) Simplified depiction of two competing suggestions for the mechanism of fluorenone formation from monosubstituted fluorene repeat units. but still absorbs until 700 nm and gives excellent power conversion efficiencies of above 4% (Fig. this is a well-known problem in PF-based PLEDs. 8). transfer of excitation energy is especially likely to occur in the emissive materials in blue PLEDs due to their high band gap energies. Additionally. 136. Poor device lifetimes are especially problematic for blue PLEDs103 that require high operation voltages and are therefore especially susceptible to the formation of chemical defects. (Reproduced with permission from ref. Originally. KGaA). Copyright 2007 Wiley – VCH Verlag GmbH & Co. whose desired blue electroluminescence frequently changes into an unwanted green emission band at 500–550 nm132 [Fig. which is not an extremely low band gap polymer (1. Copyright 2009 Wiley – VCH Verlag GmbH & Co.

104 Spirosubstituted PFs.144. PART A: POLYM. but for the performance optimalization of optoelectronic devices. the mechanism of its formation is still uncertain. and APFs by themselves exhibit already a richly varied phase behavior. 9(b)].1002/pola .g. the supramolecular order in the nanometer up to the micrometer regime is also of paramount impor- tance6.135. either by careful monomer purification. OFs. complete stability in the solid state has turned out to be difficult to achieve. an artificial latex remained with an average particle size of about 100 nm. it has been shown that even smaller nanoparticles of PFs or APFs (diameter 5–50 nm) can be produced without the addition of surfactants. 47 (2009) Figure 10. As has been shown earlier.140 or using the 9-silicon analogues of fluorene141 seem to be more promising approaches to avoid oxidative degradation.135 or via radical reactions [Fig. that ensure complete double alkylation. when a water-miscible solvent is used146. oxidative coupling stabilized these structures by the formation of oligomeric crosslinks. PFs.62. has been explained as a result of excimer formation. the preparation of defect-free PFs. and in PF particles. especially as their liquid crystallinity is concerned. Their size could be controlled by the concentration of the injected stock solution.142 (Fig. 11(a)].145 In a more recent approach. An early approach was the production of core-shell particles through layer-by-layer deposition of anionic PSS and a cationic precursor polymer on colloidal substrates. Advanced manipulation of solid state and solution structures is possible when special sample preparation procedures are applied or when a fluorene-based conjugated segment is combined with additional chemical moieties that further influence its supramolecular organization.5. removal of the core templates by chemical decomposition left back blue fluorescent hollow capsules of about 2 lm diameter. and a PF solution in chloroform have been prepared by ultrasonication.. POLYM. SCI. the internal chain organization could be changed from a glassy state to the b-phase by improving Journal of Polymer Science: Part A: Polymer Chemistry DOI 10.136 replacement of the saturated side chains by aromatic substituents47. such as exciton dissociation. SUPRAMOLECULAR APPROACHES TOWARD SOLID-STATE ORGANIZATION ‘‘Classical’’ covalent chemistry offers excellent structural control up to a length scale of several nanometres.47. Afterwards. a surfactant. e.134 but more recent research has identified energy transfer from fluorene to 9-fluorenone defects as the main reason. CHEM.: VOL. solid state morphology and macroscopic properties of p-conjugated materials and the resulting importance of control over the supramolecular ordering processes. Morphological control at these dimensions is difficult to achieve and is largely dominated by noncovalent interactions.139 Although these materials display higher stabilities.136. Because a high contact area of the components in an electroactive blend promotes desirable electronic processes.147 [Fig. either by deprotonation and subsequent reaction of fluorenyl anions with oxygen5.138 or by applying a special synthetic route to the monomers. 10).136 Despite the consensus concerning the chemical nature of the defect. and after evaporation of the organic solvent.132 Incomplete dialkylation of fluorene units in the pristine PFs has been suggested as the main source of oxidation to fluorenone. 9(c)]. Schematic representation of the interplay between chemical structure. microemulsions consisting of water. This is further supported by the recent observation that even defect-free OFs obtained by highperformance purification techniques are prone to photooxidative degradation via the formation of carboxylic intermediates in the side chains [Fig.137 Several strategies have been employed to circumvent these color instabilities. Alternatively.4224 J.133.143 As the precursor contained nonconjugated fluorene units. several strategies have been developed to create nanoparticles from fluorene-based materials.

159.160 and polyglutamate161 to prepare rod-coil di.1002/pola . It has been combined with a wide variety of flexible polymers such as poly(meth)acrylates. KGaA). Excitation wavelength 375 nm.6. (a) AFM height image of poly(dioctylfluorene) nanoparticles.151 Because of the limited motional freedom of the PF backbone. (b) Solid state organization of a PA-PF-PA block copolymer spin coated from THF and toluene and corresponding chemical structure.1. KGaA).159. left 0. Copyright 2004 Wiley – VCH Verlag GmbH & Co. Distinct differences in the solid state order have been found when PF-PEG diblock Figure 12. 146. such as liquid crystallinity. 11(b.and triblock copolymers.3) and corresponding chemical structures (Reproduced with permission from ref. their emission properties were tuned by energy transfer processes from PF to APFs149 [Fig. the solvent quality. Journal of Polymer Science: Part A: Polymer Chemistry DOI 10. (Reproduced with permission from ref.150. The scale bar corresponds to 100 nm. (c) Absorption (dashed line) and fluorescence excitation and emission spectra (solid lines) of pure PF (top) and mixed (bottom) nanoparticles in water. Copyright 2006 American Chemical Society). Copyright 2007 Wiley – VCH Verlag GmbH & Co. (a) Solid state organization of PF-PEG diblock copolymers with different volume fractions of the PEG segment (fPEG. because microphase separation of chemically incompati- ble blocks is known to trigger the formation of several different solid state morphologies.c)]. (b) Aqueous dispersions of nanoparticles from PF and a mixture of PF and PFBT under UV illumination (375 nm). 149.155–158 polystyrene. (Reproduced with permission from ref. 168.157 poly(ethylene glycol) (PEG). The most frequently applied approach is the synthesis of block copolymers with PF or OF as one of the blocks. it is rather rigid (persistence length 8–10 nm152–154) and serves as a rod block.148 In the case of mixed nanoparticles.HIGHLIGHT 4225 Figure 11. Copyright 2006 American Chemical Society). Several strategies have been developed to control the ordering of fluorene-based materials by chemical modifications instead of only relying on their inherent supramolecular properties. right 0. (Reproduced with permission from ref.

1002/pola .168 In solution.4226 J. The combination of PFs with thermoresponsive N-isopropylacrylamide blocks in coilrod-coil triblock copolymers has allowed the preparation of thermochromic assemblies in aqueous solution. (c) White emission from a thin film of a fluorene-based hydrogen bonded polymer.167 to create rod-rod block copolymers.g. PART A: POLYM. POLYM.22. PA-PF-PA triblock copolymers have been found to microphase separate into different kinds of structures depending on the solvent from which they were deposited (Fig.162 A well-defined oligomer composed of two 3. Fig.174 A similar result has also been achieved with bolaamphiphilic fluorene oligomers.171 metal-ligand coordination. p-p stacking was prevented and untextured aggregates were found. red) moieties. 47 (2009) Figure 13.170. CHEM.g..171 These compounds combined the advantages of well-defined small molecules (e. 171. high-performance purification) with those of covalent polymers (e. and PEG-PF-PEG triblock copolymers with varying volume fractions of coil to rod were studied by atomic force microscopy (AFM. SCI. resulting in the formation of various types of selfassembled micelles in water. (a) Chemical structure of a hydrogen bonding oligofluorene.. 12b). The aggregation processes could be easily followed by fluorescence spectroscopy due to energy transfer from the PF to the PT block in the aggregated state.4-ethylenedioxythiophene units linked by dihexylfluorene has been equipped with PEG side chains of different lengths. (Reproduced with permission from ref.169 Supramolecular approaches different from PF or OF block copolymers include the use of noncovalent interactions such as hydrogen bonding. PF-PT diblock copolymers could be self-assembled by adjusting the solvent composition.172. At higher coil-torod ratios.83 Supramolecular polymers with high virtual degrees of polymerization and high solution viscosities have been obtained by disubstitution of OFs with endfunctionalities that are able to dimerize via strong and directional quadruple hydrogen bonds. (b) Schematic representation of the principle of white emission by partial energy transfer within a hydrogen bonded supramolecular polymer containing energy donor (blue) and energy acceptor (green.: VOL. because the two blocks exhibited strong differences in polarity.174 For example. in OFs replacement of alkyl by polar 9substituents such as oligo(ethylene glycol) led to collapse of the apolar parts in water and the formation of nanoparticles. in which additionally the emission colors of the individual particles could be tuned by adjustment of their chemical structures and composition. Copyright 2009 American Chemical Society).173 or hydrophobic interactions.163 PFs have also been combined with other conjugated polymers.159 A low percentage of PEG gave rise to well-defined organization into nanoribbons due to p-p stacking of the PF blocks and interactions of the PEG with the substrate. such as polyaniline164–166 (PA) and polythiophene. processing from solution) and could be applied in electroluminescent Journal of Polymer Science: Part A: Polymer Chemistry DOI 10. 12a).83.

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. 14a).1002/pola SENSING AND IMAGING APPLICATIONS Except for their manifold use in organic and polymer electronics. or variation of the deposition technique122–124 (Fig. 14b). fluorescence spectroscopy often allows an easy and sensitive detection.6. (Reproduced with permission from ref. a more intimate mixing of the components in the active layer has been reached by an increased evaporation rate during the deposition process. 124. 126. such as imidazole. In bulk heterojunction solar cells containing blends of PFB and PFBT. Copyright 2006 Wiley – VCH Verlag GmbH & Co. The solid-state organization of APFs have been studied especially intensely in blends with other electroactive materials due to the importance of these mixtures in organic solar cells. depending on the complexation strength178.179 (Fig. the sensing process is dominated by noncovalent interactions between the analyte and sensor molecules. KGaA). The relevant spectra are marked with an arrow. When metal binding ligands such as bipyridine derivatives are used as comonomers. fluorene-based p-conjugated materials have recently found widespread applications as sensors. showing a high selectivity for Cu(II)180 or phosphonates. devices. Similar results have also been obtained in blends of PFDTBT with [60]PCBM. Similar observations have been made for PFs containing ligands attached to the side chains. In all cases. 15a). solvent choice.2% xylene (left) or 1. phase separation on a smaller scale resulted in an increased device performance.181 A similar approach has been published with a (statistical) copolymer of fluorene and dibenzoborole. the influence of different processing conditions has been investigated. accomplished either by heating. Mixing in other hydrogen bonded conjugated oligomers allowed tuning of the emission color covering the entire visible range.4 Also here. which selectively bind to Fe(III). which showed fluorescence . APFs are obtained that display different sensitivities toward transition metal ions.175–177 In the scope of device optimalization.HIGHLIGHT 4227 Figure 14. including white without any sign of phase separation (Fig. (Reproduced with permission from ref. transport.2% chlorobenzene (center) and corresponding EQE spectra (left). (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). Journal of Polymer Science: Part A: Polymer Chemistry DOI 10. when the degree of mixing was adjusted by the solvent composition126 (Fig. A high sensitivity toward subtle changes in the environments is made possible due to signal enhancement because of the conjugation via the polymer or oligomer backbones. 13). where the correct thin film morphology is indispensable for good charge separation. and extraction. Furthermore.

(Reproduced with permission from ref. hybridization with the PNA occurred when the strands were complementary. 195. resulting in emission of the label. no energy transfer was observed because PNA is neutral and does not interact strongly with the polyelectrolyte. which therefore came into close spatial proximity to the fluorescent label. 182. (Reproduced with permission from ref. In an aqueous solution of a cationic APF and PNA functionalized with a fluorescent label. 15b). PART A: POLYM. such as ammonium salts. Copyright 2002 National Academy of Sciences.: VOL. (c) Schematic illustration of the detection principle of DNA with fluorescently labeled PNA and a cationic APF. By contrast.189 These PF polyelectrolytes have been found to electrostatically attract oppositely charged substrates in solution. which are only soluble in water.188 Especially intense research has been done on interactions of DNA and cationic OFs. such as DNA or proteins. The resulting negatively charged DNAPNA hybrid formed a complex with the APF. In one strategy. Copyright 2008 Wiley – VCH Verlag GmbH & Co.1002/pola .184–186 sulfonates. (a) Fluorescence titration of an APF with MnCl2 in THF. quenching in the presence of halide anions182 (Fig. The arrow indicates spectral changes upon increasing iodide concentration from 0 to 1. Upon addition of single strand DNA. SCI. 178. POLYM. the hybridization of single strand DNA with complementary peptide nucleic acids (PNAs) has been used to discriminate the base sequence of target DNA strands195. CHEM.4228 J.3 mM.187. (b) Fluorescence titration of a statistical fluorene copolymer with tetrabutylammonium iodide in THF. (Reproduced with permission from ref. the detection mecha- nism is usually based on the electrostatic attraction between the oppositely charged analyte and probe molecules. The arrow indicates spectral changes upon increasing Mn(II) concentration from 0 to 10 ppm.190–194 Also in this case. they require special adaptations of their chemical structures to be used in aqueous media.188 or carboxylates. Copyright 2001 American Chemical Society). Since this label was chosen such that good spectral overlap of its absorption with the fluorescence spectrum of the APF was ensured. which gave rise to aggregation of the PF backbone.4 Since conventional fluorene-based materials only dissolve in rather apolar organic solvents. and the resulting shifts in the fluorescence spectra were followed in time to monitor enzyme activity. USA).196 (Fig. 15c). Journal of Polymer Science: Part A: Polymer Chemistry DOI 10. KGaA). energy transfer was observed.183 The most commonly used strategy to achieve this goal is the attachment of ionic side chains to the 9-positions of the fluorenes. PFs and APFs have also been widely applied as sensors for biologically interesting analytes. 47 (2009) Figure 15.

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