January 1998

ELSEVIER

Optical Materials 9 (1998) 34-42

Grafting of buckminsterfullerene onto polythiophene: intramolecular donor-acceptor polymers

John P. Ferraris
Department

novel

*,

Abderrahim

Yassar , David C. Loveday, Mohamed Hmyene 2

7X 75083-0688, USA

of Chemistry,

The University of Texas at Dallas, P.O. Box 830688, Richardson,

Abstract
Conjugated polymer-fullerene composites have shown efficient photoinduced charge transfer. The attachment of a fullerene moiety to the conducting polymer backbone is expected to lead to materials with more intimate association of the donor/acceptor sites. Two approaches to the attachment of fullerenes onto polythiophene derivatives have been explored. In

the first case, fullerene has been bonded to a bithiophene derivative which can be electropolymerized. In the second, solvent processable polythiophene copolymers were prepared and functionalized with fullerene. Both these systems exhibit electrochemical and optoelectrochemical properties for fullerene and the conducting polymer. 0 1998 Elsevier Science B.V.

1. Introduction Functionalized conducting polymers constitute an interesting class of materials which can specifically interact with external physical or chemical quantities, depending on the nature of the functional group. In these systems, the electrically conducting polymer chains serve as molecular wires to which receptors are covalently attached, and these chains allow reversible transport of information from these groups to the electrode. Recent work has shown that electrical, optical and electrochemical properties of conducting polymers can vary by several orders of magnitude in response to minor interactions with external quantities [l-3]. Strong electron donating or * Corresponding author. Tel.: + l-972-8832905; fax: + l-9728832925; e-mail: ferraris@utdallas.edu. Present address: Laboratoire des Materiaux Moleculaire, CNRS, 2 rue Henry Dunant, 94 320 Thiais, France. Present address: Department of Chemistry, University of Marrakech, Morroco.
00925-3467/98/$19.00

electron withdrawing groups can be used to tailor these properties [4-71. However, electron withdrawing groups often inhibit electropolymerization when substituted directly onto thiophenes [S,9]. A chemical route has been developed by which conjugated polymers substituted with electron withdrawing groups are prepared by Knoevenagel base condensation [lo]. More recently, a copolymer based on butylthiophene and 1-(4-nitrophenyl-2-(3-thiophene)ethene has been synthesized by oxidative FeCl, polymerization [l I]. In these systems an intramolecular dipole moment is induced by photoexcitation, leading to a bipolar excited state through a quasi-charge transfer mechanism. The photoconductivity of these copolymers increased with increased concentration of the high electronic affinity group. Conjugated polymers that respond to photons are the subject of considerable attention since they can serve as the basis for devices with ultrafast response [12-151. Buckminsterfullerene (C,,) is an acceptor capable of accommodating as many as six electrons

0 1998 Elsevier Science B.V. All rights reserved.

PII SO925-3467(97>00063-3

J.P. Ferraris et al. /Optical

Materials 9 (1998) 34-42

35

and when fullerene or its derivatives are mixed with semiconducting polymers, the composites show efficient photoinduced charge transfer [16]. A small degree of charge transfer has even been reported to occur in the ground state between fullerene and certain poly 3-alkylthiophenes [ 171. For other conducting polymers such as poly(2,5-dioctyloxy-ponly photoinduced charge phenylene-vinylene), transfer occurs between the conducting polymer and C,, [ 18,191. Photoinduced charge transfer can result in enhancement in the photoconductivity, and photovoltaic effects in thin film fullerene/conducting polymer junctions [20] have been reported. Such device applications have motivated many of the studies on macromolecular donor-acceptor systems based on r-conjugated polymer-fullerene composites. A major problem which arises in the fabrication of these composite films is the immiscibility of the two materials. In composites heavily loaded with fullerene partial phase segregation occurs due to its low solubility and the tendency of fullerene to crystallize [21,22]. In anticipation that the physical properties of these systems might be enhanced by more intimate mixing of the donor and acceptor moieties, an approach has been proposed based on the use of fullerene derivatives with a solubilizing side chain. Although the redox properties of fullerene are modified by this chemical modification, it seems that such substituted fullerenes provide an interesting route for their use as acceptors in composites with conjugated polymers [23]. However, these composite systems still lack long term stability. Another elegant approach involves the functionalization of conducting polymers with fullerenes. Zotti

et al. have reported the synthesis, electrochemistry and electropolymerization of a system where C,, is covalently attached to a fused bithiophene moiety [24]. The electrochemical response observed indicated that the fullerene had been incorporated in the polymer. Unfortunately, since these materials are prepared by electropolymerization, they tend to be insoluble and intractable which limits their use in real applications. Therefore we have investigated two alternative methodologies for introducing the fullerene group onto a conjugated polythiophene backbone in such a way as to increase the prospects of compatibility and processibility. In the first, we synthesized a bithiophene molecule with C,, attached via an alkyl chain spacer (I).

The rationale behind shift the monomer s

its design follows. In order to oxidation potential to values

NaN, DMSO

&I
Chlorobenzene

Monomer Scheme 1. Reaction scheme for preparation

I
(monomer I).

of bithienyl-Cc0

36

J.P. Ferraris et al. /Optical

Materials 9 (1998) 34-42

OH 2) Br-(CH,),-Br >

Monomer

I/

Scheme 2. Reaction

scheme for the preparation

of monomer II.

processibility in the final polymer. Total synthesis of monomer I is shown in Scheme 1. The second approach consisted of derivatizing regioregular headto-tail co-polyalkylthiophenes containing functional groups such as azide and amine to yield processable materials with C,, attached. The synthesis of the copolymers involved a three step process. The first step was the synthesis of an ( w-bromoalkyl)thiophene monomer. The second was the synthesis of the prefunctionalized copolymer and the third step introduced the fullerene onto the functionalized conjugated backbone. The synthetic route which leads to structurally homogenous poly[(3-alkylthiophene)-wbromoalkylthiophene] is shown in Schemes 2 and 3.

lower than C,, [25] and thus facilitate electrooxidative polymerization, the 2,2 -bithienyl (BT) monomer unit was selected. A hexyl spacer was incorporated between the BT and C,, to reduce the latter s steric and electron withdrawing effects and to facilitate

2. Results and discussion 2.1. Approach I: Bithiophene-C,, polymer

Monomer II
LDA, -78 to -45 C MgBr,-ether, -45 to 0 C

BrMg

--cc
\ Br S H

G Ni(ll) dppp Cl,

owBr
I \
S

copoiy copoly

II Ill

x:y = 1:1 x:y = 13

?I

Scheme 3. Regio-controlled

synthesis of random copolymers.

The bithiophene-C 60 monomer (I) was prepared as follows. 3-(6-Bromohexyl)thiophene (A, Scheme 1) was prepared using the method described in the literature [26] and 2-bromo, 3-(6bromohexyl)thiophene (B) was obtained in good yield by bromination with NBS in chloroform/acetic acid solution. 3 -(6-Bromohexyl) 2-2 -bithienyl (C) was prepared by coupling the Grignard reagents derived from 2-bromothiophene and 2-bromo, 3-(6bromohexyl)thiophene. The desired monoazide (D) was obtained in quantitative yield by reaction of C with sodium azide in DMSO. Reaction of D and fullerene in refluxing chlorobenzene gave the monoadduct I after purification by chromatography while eluting with dichloromethane. Monomer I was soluble in common organic solvents such as chloroform, dichloromethane, THF etc., in marked contrast to fullerene which is essentially insoluble in these solvents [27]. A noticeable difference in the UV-VIS spectrum between I and C,, occurs in the 450 nm - 700 nm range. Whereas C,, displays a broad absorption in this region which is marked by fine structure, this feature is absent in I. The disappearance of the C,, signature is highly diagnostic of substituted fullerenes [28]. Cyclic voltammetry of I in acetonitrile/toluene (1:5 V/V) reveals four reversible electrochemical reduction waves with potentials close to the values reported for

J.P. Ferraris et al./Optical

Materials

9 (1998) 34-42

37

azafulleroids [29]. These are shifted negative when compared to C,, due to a loss of conjugation [30,31]. In the anodic region I shows a wave at 1.0 V vs. Ag/Ag+ corresponding to the irreversible oxidation of 3 -alkyl-2,2 -bithienyl moiety. The oxidation potential of the bithienyl in I appears unaffected by the presence of fullerene. Repetitive potential scans in an electrolytic medium containing I (0.005 and 0.1 M BF; in CH,Cl;?) shows the oxidation of the monomer in the first scan, followed in the reverse scan by a reduction at 0.51 V vs. Ag/Ag , attributable to the first polymer nucleates formed on the electrode. Repetitive cycling leads to an intensification of the electrochemical waves at 0.77 and 0.51 V, indicating that electropolymerization of the monomers takes place on the electrode. Fig. 1 displays the cyclic voltammogram (CV) in a monomer free electrolyte solution of poly-I deposited on Pt. In the anodic region, the CV shows one distinct, nearly symmetrical wave, with an oxidation potential at 0.74 V vs. Ag/Ag+ and a reduction wave at 0.54 V vs. Ag/Agf which arises from the polythiophene backbone. In the cathodic region poly-I shows a series of reversible electrochemical waves at -0.58, - 1.03, - 1.47, - 1.87, and -2.25 V vs. Ag/Ag+. We ascribe the four least negative reduction waves to fullerene redox processes based on the similarity of their potentials to those reported for fullerene and its derivatives. The solution reduction potentials of the monomer also display these waves. We attribute the most cathodic wave in Fig. 1 to the n-doping of polythiophene. Hence it appears that the PT back-

E
s a 8 2 d

0.1 0.08 0.06 0.04 0.02 0 -0.02 I 400 I I. 600 I, 800 Wavelength I 1000 (nm) . a, 1200 , 1400

Fig. 2. UV-VIS spectra of poly-I at different potentials. are difference spectra relative to the spectrum at 0 V.

Spectra

bone and C,, fragments preserve their own electrochemical properties. In situ spectroelectrochemistry of a poly-I film deposited onto IT0 coated Mylar was performed as previously described [32]. Neutral poly-I exhibits an absorption maximum in the visible range around 480 nm which is comparable to polythiophene s. With increasing levels of oxidation, peaks at 900 and 1500 nm grow at the expense of the 480 nm absorption. These spectra are typical for the p-doping of polythiophene-type conducting polymers. In the cathodic region only small changes are observed as a function of applied potential. These are shown in Fig. 2 as difference spectra relative to the spectrum obtained at -0.4 V. As the applied potential becomes progressively more negative, 3 peaks appear and increase gradually in intensity. At - 1.4 V a bigger change starts to occur. The spectra share many of the features that have been reported for the singly, doubly and triply charged reduction products from tetrahydroazulenofullerene [33] and are remarkably different from those reported for unsubstituted fullerene [341. Poly-I retains the electronic properties of the fullerene moiety and conjugated system. Although similar behavior has been reported by Zotti et al. for a related bithiophene-C,, material, their system consisted of only short chains due to the material s insolubility in the electrolytic medium. [24] Our results indicate that this is probably not the case for poly-I which behaves like other thiophene polymers. In addition to the reduction peaks due to the C,, we

In

I1

50
I

PA

I,

-2.5

-2

1
1

-1.5

-1

-0.5 (V vs. AglAg )

0.5

Potential

Fig. 1. Cyclic voltammogram rate = 50 mV/s.

of electropolymerized

poly-I.

Scan

38

J.P. Ferraris et al./ Optical Materials 9 (1998) 34-42

also observe the reduction wave due to the n-doping of the polymer. Unfortunately, poly-I produced by electrochemical techniques was insoluble.

2.2. Approach
mers

ZZ: Polyfalkylthiophene-C,,

copoly-

The most common synthetic pathway for the production 3-( &bromoalkyl)thiophenes is the multi-step Bauerle method [35], with overall yields up to 2030%. We have developed a new higher yield synthetic strategy for the synthesis of the 3-( obromoalkyl)thiophenes that affords in one step products that can be readily purified by distillation (Scheme 2). The regiospecific bromination of 3-alkylthiophenes and compound F with NBS leads to the bromination in the 2-position. The copolymerization relies on the metallation of 2-bromo-3-alkylthiophene and the 2-bromo-3-( obromoalkyl)thiophene (II) with LDA at their 5-position, followed by trapping the lithium species by magnesium bromide etherate to afford the respective bromomagnesium derivatives G and H shown in Scheme 3. The in-situ treatment of this mixture with Ni(dppp)Cl, affords regiochemically defined headto-tail random copoly(3-alkylthiophene,3-( wbromoalkyl)thiophene) [36,37]. The key to the success of this procedure is the ability to metallate 3-( w-bromoalkyl)thiophene with LDA, without exchange of the lithium for halogen in the tbiophene ring or the alkyl chain. The cross-coupling of 2bromomagnesium-thienyl with organohalides in the presence Ni(dppp)Cl, catalysis is very chemoselective and affords only aromatic C-C bond formation [38]. When stabilized Grignard reagents are used, the coupling reaction proceeds faster at low temperatures than the metal-halogen exchange. Bauerle and coworker [39] have used this approach to build whalogenoalkyl substituted oligothiophenes. We have applied McCullough s method to prepare two random copolymers, copoly-II and copoly-III by using (1: 1) and (1:3) ratios of monomer II and 2-bromo3-octylthiophene, respectively. The copolymers were precipitated in methanol and isolated by centrifugation. The resulting copolymers were purified by soxhlet extraction with methanol, hexane and chloroform. The yields of chloroform soluble fractions

were 36-47%. The molecular weight and distributions were determined by gel permeation chromatography (GPC) analysis in THF or chloroform, versus polystyrene standards. Although polystyrene has been found to be an appropriate standard for molecular weight determination for poly(substituted thiophene), we have observed some M, differences when determined in chloroform and THF. Chloroform GPC results sometime show a small peak with elution times much shorter than that of the main peak in GPC chromatogram. This small peak may be attributed to the formation of polymer aggregates in solution, possibly due to a small degree of oxidation in this solvent. The molecular weight is monomodal for both copolymers. The copoly-II had higher molecular weight and narrower distribution than copoly-III. The M, and corresponding polydispersity index are M, = 107,000, Pd = 1.65, M, = 73,000, Pd = 4.06 for copoly-II and copoly-III, respectively. These copolymers have similar M, as McCullough s HT-poly(3-substituted-thiophenes) and this method is known to lead to polymers with higher regioregularity and higher molecular weight than other synthetic methods [40]. Since Sato and co-worker [41,42] have deduced from proton NMR that 54% of electropolymerized alkylthiophene consisted of HT-HT coupling, H NMR has become a routine technique for the characterization of the regioregularity of poly(alkylthiophene)s. The H NMR of the CHCl, soluble fraction shows a singlet at 4.59 ppm, associated with the methylene protons cx to the aromatic ring (ArCH,-0), a triplet at 3.57 ppm for OCH,, a triplet at 3.39 ppm for BrCH,, a triplet at 2.77 ppm for the CH, CY to the thiophene for 3-octyl moiety and a triplet at 0.8 ppm for the CH,. The integration gives the ratio of the monomer II and octylthiophene in the bulk polymer and closely corresponds to the feed ratios used in the copolymerization. In the aromatic region copoly-II shows four singlets with equal intensity at 6.98, 7.06, 7.16 and 7.22 ppm. In contrast, copoly-III has one intense singlet and three small singlets. The aromatic proton in copoly II sees four different chemical environments resulting from four trimeric sequences. On the basis of the shielding effect of the thiophene ring and the comparison with the spectrum of regioregular polyalkythiophene, the peak at 6.98 was assigned to

J.P. Ferraris et al. / Optical Materials 9 (1998) 34-42

39

Triad

Triad II

&yBr okYB

s\s
H

s
4

%
Triad Ill

Triad IV

Fig. 3. Schematic

the four triads of

the HT-HT polyalkythiophene. (Triad I, Fig. 3) The peak at 7.22 has the same shift as the aromatic proton in HT-HT homopolymer obtained from the monomer II, HT-HT poly(3-(2,5,8,trioxanonyl)thiophene) (Triad II, Fig. 3). The peaks at 7.16 and 7.06 arise from the other two triads in Fig. 3. The equal intensities of the 4 peaks indicates that the distribution of the comonomer in copoly-II is random. In copoly-III where the ratio of octylthiophene is three times that of monomer II, the peak assignable to triad I is the most intense. The H NMR shows clearly that the structure of both copolymers is regioregular. The copolymers have similar IR spectra. The aliphatic CH stretching vibrations appear at 2926 cm- and 2855 cm- and the ring stretching vibrations are at 1510 cm- . The aromatic out of plane CH, which is characteristic of IY-_(ylinked thiophene appears at 830 cm- for both the copolymers. The intensity ratio of symmetric ring stretching at 1457 cm- to the asymmetric ring stretch at 15 10 cm- has been used as a measure of the conjugation length and the regioregularity of thiophene polymers and oligothiophenes used as model compounds. Thus a small ratio of Zsym/Zasymindicates a long conjugation length of the polymer. In the same way regioregular polymers have a smaller ratio than random polymers. The ratio of Zsym/Zasymfor copoly-II and copoly-III

ranges between 1.1 and 1.3, which is considerably lower compared to 6-9 obtained for other regioregular materials [41,42]. These observations are in agreement with the GPC data, which shows that copoly-II and copoly-III have high molecular weights. The azide group, which is thermally and photochemically labile, provides an easy and efficient route to a number of other useful derivatives, such as reactive amine groups which can in turn readily form covalent bonds with many other chemical groups. Several examples of alkylazide derivatives produced by chemical modification of polymers have been reported [43,44]. Normally, azide groups are introduced onto polymers containing haloalkyl groups by reaction with NaN,. Recently the Cambridge group has prepared copoly(alkyl,azidoalkyl-thiophene) by chemical modification of an alcohol into azide [45]. We have recently found that the reaction of NaN, with wbromoalkyloligothienyl is quantitative under mild conditions. This observation led us to attempt the introduction of azide groups onto copoly-II and copoly-III. The azido substituted copolymers were prepared by treating these copolymers with an excess of NaN, in THF. This leads to essentially complete substitution of the bromine groups by azide groups according to Scheme 4. The FTIR spectra of all copolymers showed clearly the characteristic strong

J.P. Ferraris et al. /Optical

Materials 9 (1998) 34-42

copoiy Copoly

II

x:y

= 1:l = 1:3

Copoly Copoly

IV v

x:y x:y

= I:1 = 1:3

Copoly Copoly

VIII IX

x:y x:y

= I:1 = 1:3

111 x:y

LiAIH, THF

Copoly Copoly Scheme 4.

VI VII

x:y x:y

= 1:l = 1:3 Copoly x x:y = I:3

Reaction scheme for the functionalization

of copoly(w-bromoalkyl,alkyl-thiophene).

azide band, at 2100 cm- and essentially complete disappearance of the C-Br absorption at 723 cm- . The decomposition of the azide was achieved by exposing copoly-IV to UV light at 365 nm. The azide decomposition results in the loss of nitrogen and the formation of highly reactive nitrene which reacts with the conjugated backbone. The reaction leads to some loss of the conjugation length in the polymer, as is indicated by a blue shift in the absorption maximum in the UV-VIS spectrum. This effect increases with increasing exposure times. The reduction of polymeric azide precursors to primary amines was achieved by using LiAlH, in THF [46]. The FTIR spectra of reduced azides show no azide absorptions and exhibit new absorption characteristics of primary amines around 1625 cm- (NH, deformation), and a broad absorption at 3503 cm- (N-H stretching). The reduction of copoly-IV with high azide content resulted in an insoluble material, copoly-VI. The copoly-V, which has only one azide group per four thiophene units gave a soluble material, copoly-VII, that could be characterized. Its UV-VIS absorption spectrum displayed a maximum at 438 nm, the profile being similar to that of the starting copoly-IV and copoly-V. Comparative GPC profiles of copoly-V and copoly-VII showed that no change occurred in M, during the reduction of the azide into the amine.

Buckministerfullerene and its derivatives exhibit peculiar optical, electrical and magnetic properties and the combination of these molecules with conjugated systems such as polythiophene is very challenging. In order to realize this concept we envisioned two approaches: (a) the reaction of the copoly(octyl,alkylazide-thiophene)s, copoly-IV and copoly-V, with C,,, via 1,3-dipolar addition and subsequent elimination of nitrogen from the resultant triazoline adduct [47,48] and (b) the reaction of the copoly(octy1, alkylamine-thiophene)s copoly-VI and via nucleophilic addition copoly-VII with C,, [49,50]. It has already been established that the reaction of C,, with alkyl azide in boiling chlorobenzene overnight leads to open fulleroid 5-6 as the major compound. This reaction proceeds primarily through monoaddition accompanied by small amounts of higher addition products. The reaction of copoly-IV and copoly-V with a slight excess of C,, in refluxing chlorobenzene overnight led to dark brown solutions. After removal of the solvent, the crude reaction mixture was extracted with THF to separate the product from unreacted C,,. Since unsubstituted C,, is completely insoluble in THF, the THF fraction contained only C,, covalently linked to polymer. Fig. 4 shows representative examples of the electronic absorption spectra of copoly-VIII and copolyIX. The 7~-rr * absorption of conjugated polythio-

J.P. Ferraris et al. / Optical Materials 9 (1998) 34-42

0.08

41

0.06

iti
j 5 9 0.02 0.04

a
0

-0.02

1
400

600

800

1000

1200

1400

300 Fig. 4. UV-VIS

400

500

600 A. nm

700

so0 in solution.

Wavelengthlnm

spectra of copoly-VIII and copoly-X

Fig. 6. UV-VIS spectra of copoly-IX at different potentials as indicated. Spectra are difference spectra relative to the spectrum at 0 v.

phene backbone, at 438 nm is clearly observed along with the first dipole allowed transition of fullerene at 332 nm. The spectrum is a simple superposition of the two components with no absorptions below the T-T * gap of the polymer, indicating little or no interaction between the two moieties in the ground state. The cyclic voltammetric data of the various copolymers show redox waves corresponding to the oxidation of the conjugated backbone and a series of reversible reduction waves due to the fullerene. The CV for copoly-IX (Fig. 5) exhibits an anodic peak at 0.66 V and a reduction wave at 0.55 V, which is comparable to substituted polythiophene [5 I]. The potential peak values for the reduction waves observed for fullerene for copoly-IX and copoly-X are substantially more negative than the values for the reduction of unmodified fullerene [52]. These shifts

are consistent with the formation of a bond between the nitrogens in the precursor polymer and fullerene. Films of copoly-IX cast onto IT0 coated Mylar were characterized by in-situ optoelectrochemistry. Neutral copoly-IX shows an absorption maximum at 438 nm. Small spectral changes are observed for the reduction processes of C,, and are displayed in Fig. 6 as difference spectra normalized to the spectrum at 0 V. As the potential becomes progressively more negative, a peak grows at 1075 nm. This is the peak for C, anion. This peak then diminishes and a new one grows at 942 nm, which is due to the C,, dianion. These peak positions are consistent with those observed for azafulleroids [53] and fullerene. The spectra obtained for the reduction between - 0.9 and - 1.4 V are similar to what has been reported for polythiophene bearing fullerene [54].

3. Conclusion Synthetic routes to conducting polymers containing fullerenes have been described. In the first case a molecule was synthesized that could subsequently be electropolymerized to yield a polymer containing a fullerene moiety. In the second case a solvent processable conducting polymer bearing fullerene was synthesized. Both polymers were characterized electrochemically and showed redox waves characteristic of the thiophene polymer and the fullerene which appear unperturbed by the presence of the other.

E
0

e
2

I
1.6 -1.2 -0.8 -0.4 Potential (V 0 vs. 0.4 Ag/Ag+) 0.8 1.2 1.6

Fig. 5. Cyclic voltammogram

of copoly-IX

film.

42

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