PROGRESS REPORT

The Versatile Thiophene: An Overview

of Recent Research on Thiophene-Based
Materials**
By Giovanna Barbarella,* Manuela Melucci,
and Giovanna Sotgiu

In the last few years, thiophene-based materials, which are semiconductor

and fluorescent compounds, have become a highly interdisciplinary field of
research, with diverse studies ranging from the fabrication of electronic and
optoelectronic devices to the selective detection of biopolymers. This article
presents a survey of the papers published in the last two years and concludes
with the authors' views on future developments.

1. Introduction extremely varied functionalizations can be prepared,[12] oligo-

mers can be linear, branched, or star-shaped, and even all-
Thiophene is one of the most studied heterocycles: it is easy thiophene dendrimers can be prepared.[13±15] The driving force
to process, chemically stable, and its synthetic applications behind the continuous creation of new thiophene-based struc-
have been a constant matter of investigation for the last six or tures is that they allow fine-tuning of desirable properties
seven decades. The interest in this heterocycle has spread and, more importantly, that understanding of the structure±
from early dye chemistry[1] to modern drug design,[2] electron- property relationship is still dramatically scarce, particularly
ic and optoelectronic devices,[3,4] biodiagnostics,[5] block co- in the solid state.
polymer self-assembled superstructures, and conductivity- Last but not least, thiophene is not an expensive starting
based sensory devices.[6,7] Curiously, some fundamental material, and is even obtainable as a by-product of petroleum
aspects, such as the aromaticity' of thiophene and similar distillation. Property-specific synthesis and functionalization
heterocycles, are still a matter of debate.[8] create a remarkable added value and thiophene-based inter-
Thousands of papers on thiophene-based compounds have mediates, building blocks, and materials are increasingly pres-
been published in the last few years, many of them related to ent in commercial catalogues following improvement in syn-
the field of materials science. Thiophene oligomers and poly- thetic methodologies.
mers are investigated mainly for their semiconductor, lumi- This review will highlight work published over the last two
nescence, and sensing properties.[9,10] years. Of course our choice will inevitably (but unintention-
The versatility of thiophene chemistry allows great diversity ally) be biased towards topics and publications that are of
in thiophene-based chemical structures. Thiophene can be greater interest to us. We apologize in advance to all those
functionalized in positions a and b to sulfur or at the sulfur who will be disappointed by our choice. The point we wish to
atom itself,[11] regioregular oligomers and polymers with make by presenting such a broad overview is that, no matter
what the type of application, thiophene-based materials be-
long to the same chemical family, and therefore advances in
one direction are of benefit to the entire research field. For
example, the fluorescence properties of oligo- and polythio-
± phenes are important for applications in light-emitting diodes
[*] Dr. G. Barbarella, Dr. M. Melucci, Dr. G. Sotgiu (LEDs) and in biodiagnostics; charge-transport properties are
Consiglio Nazionale Ricerche (ISOF), Area di Ricerca CNR important in LEDs and in field-effect transistors (FETs); in
Via Gobetti 101, I-40129 Bologna (Italy)
E-mail: [email protected] all cases purity is of primary importance and purity is related
[**] This work was partially supported by projects FIRB RBNE01YSR8 to synthetic methodologies, and so on. Furthermore, a global
and EU-NMP IP-NAIMO. overview enables interconnections to be established between

Adv. Mater. 2005, 17, 1581±1593 DOI: 10.1002/adma.200402020  2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1581
 G. Barbarella et al./Overview of Recent Research on Thiophene-Based Materials
PROGRESS REPORT

different research topics, which is necessary in order to materials in amounts that would make them easily available
achieve real breakthroughs. to those interested in investigating their properties. Research
The review is arranged into five short sections: synthesis, has also included the development of new molecular struc-
supramolecular organization, devices, applications in biodiag- tures of various shapes and dimensions, designed for specific
nostics, and theoretical calculations. This subdivision is arbi- applications.
trary, since there is considerable overlap among the different The most exploited reaction for the preparation of thio-
topics, and is intended only to simplify the reading. phene-based oligomers and polymers remains the coupling of
halogenated thienyls with metalated counterparts in the pres-
ence of palladium or nickel complexes.[16] Recently, there has
2. Synthesis been a growing application of the Suzuki reactionÐemploy-
ing thiophene boronic acids or esters[17a]Ðowing to the great
Recent improvements in synthesis concern both small mole- variety of experimental conditions tolerated by this reaction
cules, i.e., short oligomers, and polymers. In both cases, one of and the low toxicity of boron derivatives compared to that of
the main objectives is to obtain reproducible and high-purity the tin derivatives employed in Stille coupling.[17b] Using

Giovanna Barbarella received her degree in Organic Chemistry at the University of Bologna, Italy,
and her Ph.D. degree (Doctorat ›s Sciences Physiques) at the University of Grenoble, France, in
1974. After a few years spent doing research in several countries, in both public institutions and
private companies, she took up a position at the Italian National Research Council (CNR).
Currently, she is working at the ISOF Institute in Bologna, CNR, as group leader of the Department
of Molecular Design project ªOrganic Functional Materials for High-Tech Applications.º The
current research interests of the group mainly include synthesis and multiscale, multiphase
characterization of thiophene-based materials for opto-electronics and biodiagnostics.

Manuela Melucci received her degree in Analytical Chemistry from the University of Bologna in
2000. After working for one year at the CNR-Institute for Microelectronics and Microsystems, she
did her Ph.D. in Barbarella's group. Currently she is working at ISOF within the UE research
project ªNanoscale integrated processing of self-organizing multifunctional organic materialsº
(NAIMO).

Giovanna Sotgiu studied Chemistry at the University of Bologna. After graduating in 1997, she
continued to work in Barbarella's group. In 2001 she obtained a permanent research position at
CNR in Bologna. Her current research focuses on the development of oligothiophenes as
fluorescent markers for biomolecules.

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PROGRESS REPORT
either Suzuki or Stille coupling, many new thiophene-based case of the less-reactive 1,5-dioctoxy-2,6-dibromonaphthalene
materials have been synthesized in the last two years, includ- monomer the use of MW resulted in an impressive increase in
ing thiophene±fluorene co-oligomers,[18] fluorocarbon-substi- polydispersity index (6.4 versus 2.8).
tuted oligothiophenes,[19,20] poly(fluorene-co-thiophene-S,S- Many new thiophene oligomers have been prepared with
dioxides),[11c] etc. Interesting prospects for rapid synthesis of the aim of making them suitable for solution-processing de-
thiophene-based materials in high yields and with high purity position techniques, in order to obtain highly organized thin
are offered by microwave (MW)-assisted methodologies in films by casting. In particular, A. R. Murphy et al. reported
both types of reaction.[21,22] MW assistance leads to accelera- the synthesis of a very soluble sexithiophene containing ther-
tion of reaction rates, and in many cases allows the formation mally removable ester groups in the a and x terminal posi-
of undesired by-products to be prevented. We have demon- tions (A, Fig. 1), which was solution-cast into thin films at
strated that the use of microwaves allows the synthesis of sol- room temperature.[25] Subsequent thermolytic removal of the
uble as well as poorly soluble thiophene oligomers in high terminal groups allowed the oligomer to self-assemble into
yields and in very high purity in short times by Suzuki cou- highly crystalline thin films with terraced structures and good
pling.[23a,b] Rate acceleration, from days to minutes, was ob- charge mobilities, potentially useful for FETs.
served by Nehls et al. in the MW-assisted preparation of alter- A new, interesting class of oligomers is that reported by
nating fluorene±bithiophene copolymers via Suzuki- and J. L. Fillaut et al., who described the synthesis of ruthenium
Stille-type reactions.[24] Most of the polymers were character- oligothienylacetylide complexes with high third-order non-
ized by molecular weights and polydispersity indexes similar linear optical activities, which could be tuned by changing the
to those obtained using conventional heating. However, in the size of the oligothiophene.[26] The first synthesis of a hybrid

Figure 1. Molecular structures of some of the recently synthesized thiophene-based materials featured in this review: A [25]; B [27]; C [23c]; D [32];
E [15]; F [34].

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PROGRESS REPORT

quaterthiophene coupled to a peptide sequence (B, Fig. 1) transducing a conformational modification induced by an ex-
was reported by P. Bäuerle and co-workers with the aim of ternal stimulus into mechanical work, the basis of sensing and
exploiting the self-assembly properties of the peptide to form actuating materials.
ordered nanometer-sized structures on surfaces.[27] Looking at the considerable structural variety of thiophene-
Concerning the synthesis of polymers, a very interesting im- based oligomers and polymers synthesized over the last few
provement in terms of control of polymer molecular weights years, progress towards high-yield and function-specific syn-
and polydispersities was reported by A. Yokoyama et al.,[28] who thesis strategies has clearly been made; however, one cannot
described the Ni-catalyzed polymerization of 2-bromo-5-chloro- help but remark that many aspects are still waiting for a better
magnesio-3-hexylthiophene via a chain-growth mechanism lead- elucidation. For example, there are still no clear-cut defini-
ing to narrower molecular-weight distribution and control of the tions of oligomer and polymer; the standard (polystyrene)
molecular weights via the feed ratio of monomer to nickel cata- generally used to establish the molecular weights of the poly-
lyst. The authors showed that for a [monomer]0/[Ni(dppp)Cl2]0 mers is clearly inappropriate in many cases. Reaction mecha-
ratio (where dppp is 1,3-bis[diphenylphosphino]propane) be- nisms remain a matter of debate.[35] Such inconsistencies
tween 10 and 108 the molecular weights increased linearly in make it difficult to master the reproducibility of the character-
proportion to the feed ratio. Achieving the control of polymer istics of the synthesized materials, which must be regarded as
molecular weights and polydispersities is of great importance the most stringent requirement for application in any field.
for their performance in devices, as shown by R. J. Kline et al.,
who reported that the charge mobility of poly(3-hexylthio-
phene) is related to the molecular weight.[29] With the purpose 3. Supramolecular Organization
of increasing the ordered deposition of polymers to improve
charge mobility, M. Jeffries et al. reported a new protocol for Recent research into supramolecular organization has fo-
controlling the end-group composition of regioregular poly(3-al- cused on the need to govern the great tendency of thiophene
kylthiophenes), functionalizing them with a variety of terminal oligomers and polymers to form self-organized aggregates in
groups to anchor the material on surfaces.[30] H. Meng et al. re- the solid state as well as in solution. The main objective is to
ported the solid-state, catalyst-free polymerization of 2,5-di- understand and direct this tendency, in order to optimize the
bromo-3,4-ethylenedioxythiophene (DBEDOT), demonstrating performance of any type of deviceÐfrom FETs, in which high
that just by storing DBEDOT for prolonged time in air or by molecular ordering is generally required in thin films, to sen-
heating it for few hours at a temperature of 60±120 C it was pos- sors based on the recognition of biological molecules in aque-
sible to transform the monomer into a highly conductive form of ous solution. However, this is not an easy task, since the as-
poly(3,4-ethylenedioxythiophene) (PEDOT).[31] tonishing ability of organic chemists to create covalent bonds
Spontaneous polymerization of solid 5-hexyl-5--vinyl- and new thiophene-based molecular structures does not cor-
2,2¢;5¢,2²;5²,2--quaterthiophene affording a side chain poly- respond to a comparable understanding of the non-covalent
mer was also demonstrated by our group.[23c] The polymer (C, forces driving these compounds to self-organize into one pat-
Fig. 1) had the same structure as that obtained by free radical tern or another, particularly in the solid state. Van der Waals',
polymerization. Casting from CS2 led to the formation of weak C±H_S and C±H_p intermolecular interactions, intra-
polymer single crystals of micrometer dimensions, which are and intermolecular sulfur±sulfur interactions, and p±p stack-
currently being tested for their semiconducting properties. A ing may all contribute to self-organization processes.[36]
regioregular zwitterionic polythiophene (D, Fig. 1), useful to Furthermore, most of these processes, for example those
monitor amyloid fibril formation of in bovine insulin, was occurring on surfaces, take place under non-equilibrium con-
obtained by A. Herland et al. via polymerization of the corre- ditions and are largely dependent on experimental parameters
sponding terthiophene with ferric chloride in chloroform.[32] such as solvent, the hydrophilic/hydrophobic nature of the
Several metallo-containing polythiophenes have also been surfaces, temperature, rates of heating and cooling, etc., which
described in the more general context of conducting metallo- may unpredictably affect the weak interactions between mole-
polymers.[33] cules. Thiophene derivatives can even give rise to polymorph-
Thiophene dendrons and dendrimers were prepared by ism, i.e., they possess the ability to pack in the solid state in
C. Xia et al. using the Stille coupling (E, Fig. 1).[15] The many different ways, characterized by different electrical and
authors studied the self-organization properties of these mole- optical properties.[37±39] As with all other conjugated materials,
cules on different substrates and showed their ability to form much systematic work is needed before real breakthroughs
nanostructures on surfaces, which has great potential for ap- due to rational design, and perhaps some serendipity, will al-
plications in organic electronics. A calixarene±quaterthio- low self-organization processes to be mastered and controlled,
phene-based polymer that became highly conductive upon opening the door to new concepts, ideas, ways of manufactur-
protonation was prepared by H. Yu et al.[34] A Stille coupling ing, and, in the end, obtaining usable nanotechnologies'
between di-iodocalixarene and the monostannyl derivative of based on organic materials.[40]
2,2¢-bithiophene afforded the monomeric unit which was then The self-organization of oligothiophenes in the solid state
electropolymerized (F, Fig. 1). The preparation of this poly- may occur in rather unexpected ways. For example, we have
mer was aimed at the development of materials capable of recently shown that thin films obtained by melt-quenching of

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PROGRESS REPORT
a b

Figure 2. Left: Atomic force microscopy (AFM) images of T5 on glass following melting±quenching cycles. The two images show the similarity in morphol-
ogy at different magnifications. a) Height range z: 0±940 nm. b) Height range z: 0±370 nm. Right: sketches of the organization of T5 molecules. Projection
on the glass plane (a) and projection on the (a¢,c) plane (b). Adapted from reference [41], with permission; copyright 2003, the American Chemical Society.

the semiconductor a-quinquethiophene (T5), exhibit a hier- Hydrogen-bond-driven self-assembly modalities of thiophene
archical self-affine organization that spans scales from tens of oligomers were demonstrated by P. Baüerle and co-workers
nanometers to hundreds of micrometers (Fig. 2).[41] This be- with the biohybrid oligothiophene B (Fig. 1).[27] Scanning tun-
havior is peculiarly different from that of the lower and higher neling microscopy (STM) images (Fig. 3) show that nano-
homologues of the series, quaterthiophene (T4) and sexithio- meter-sized, almost-parallel linear strands are formed, which
phene (T6), and undoubtedly has some relation to the differ- look promising for the optical and semiconducting properties
ent symmetry of oligomers with odd and even numbers of of the material in thin-film devices.
thiophene rings. Owing to its peculiar self-assembly proper-
ties, T5 forms very crystalline vacuum-evaporated thin films
with high FET charge mobilities.[41] However, minor structur-
al modifications cause a drop in FET charge mobility by sev-
eral orders of magnitude, even when the modified systems are
able to self-organize in highly crystalline thin films.[42] Re-
cently, we have also found that the electroluminescence prop-
erties of thiophene oligomers may be deeply affected by their
self-assembly modalities. Indeed, appropriate functionaliza-
tion of a thiophene-based compound allowed its supramolecu-
lar organization to be controlled in the solid state, leading to
the formation of new intermolecular emitting species and the
achievement of white electroluminescence.[43]
P. Lecl›re et al. reported that by choosing the appropriate
Figure 3. STM image of the supramolecular organization of the biohybrid
experimental conditions, it is possible to achieve control of quaterthiophene depicted in Figure 1B. Adapted from reference [27], with
the self-assembly of thiophene oligomers substituted at the permission; copyright 2003, the Royal Society of Chemistry.
terminal positions with a variety of functional groups.[44] Their
view is that understanding of molecular assembly can be
achieved via different complementary approaches: studies in It is well known that block copolymers containing thio-
solution of the aggregation behavior as a function of molecu- phene-based moieties may lead to a variety of morphologies
lar structure, solvent, temperature, etc.; studies of the self-or- (e.g., lamellar, spherical, cylindrical) associated with different
ganization of vacuum-evaporated films; and studies of cast electrical and optical properties.[47] One of the most recent re-
films, for which the nature of the deposition substrate is of sults in this field is the formation of large vesicles (up to
crucial importance. In relation to the latter point, they found 1.5 lm) from thiophene-containing rod±coil block copoly-
that nanowires of functionalized sexithiophene are sponta- mers, consisting of 40 styrene and 50 3-(isocyano-L-alanylami-
neously formed on hydrophobic surfaces such as graphite, noethylthiophene) units.[6,48] Thiophene can then be electro-
while platelets or fiber-like structures are generated on hydro- chemically polymerized forming vesicles able to include
philic surfaces. Moreover, they demonstrated by means of enzymes, thus opening up the possibility of creating stable mi-
atomic force microscopy (AFM) investigations that an enan- crometer-sized reaction vessels or conducting vesicles with
tiomerically pure sexithiophene, functionalized with chiral tunable properties. The role of thiophene in the vesicles prior
groups at both terminal positions, always forms left-handed to polymerization is to form self-assembled p-stacks that reg-
helices on silicon, whichever of the two enantiomers is used, ulate the organization of the bilayered vesicle membrane.[6,48]
indicating that the supramolecular organization is not gov- Recently, K. P. R. Nilsson et al. have obtained chiral hybrid
erned by molecular chirality.[45] H-bonding-directed self-as- supermolecules with the three-dimensionally ordered struc-
sembly has been widely explored in conjugated materials.[46] ture of a biomolecule and the properties of a semiconductor

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polymer by the non-covalent assembly of a positively charged polythiophenes in the presence of chiral biomolecules had
random-coil synthetic peptide and a negatively charged, opti- already been observed,[50] but this is the first time the phe-
cally inactive polythiophene.[49] Solutions of negatively nomenon has been seen to occur between an optically inactive
charged poly(thiophene acetic acid) (PTAA) and of a posi- polymer and a random-coil biological molecule. As remarked
tively charged synthetic peptide (JR2K) were mixed in var- by the authors,[49] these results pave the way to a wide range
ious proportions and their absorption, circular dichroism of applications in biomolecular devices, artificial enzymes,
(CD), and Raman spectra were analyzed and compared to biosensors, and biocatalysis.
separate solutions of polymer and peptide. The JR2K peptide In our opinion, although an increasing number of papers re-
(Fig. 4), with positively charged lysine groups, was initially de- port on self-organization properties of the most diverse range
signed to avoid the formation of homodimers due to electro- of thiophene-based molecular structures, what seems to be
static repulsions. Upon mixing, the positively charged lysine missing at the moment is a greater effort towards the under-
groups interact electrostatically with the negatively charged standing of the relationship between a given type of supramo-
carboxyl groups of polythiophene. The interaction forces the lecular organization, especially in the solid state, and the
polymer backbone to adopt a non-planar conformation on the effect that it has on the electrical and optical properties of the
one hand but, on the other, disrupts the electrostatic repul- materials. Such understanding will be critical to any future
sions between the peptide molecules, allowing peptide homo- advances towards directed self-organization.
dimers to be formed. At the same time, an intense bisignated
CD signal is induced in the spectral region, corresponding to
the p±p* transition of the polythiophene. According to the 4. Devices
authors, this is the result of polythiophene main-chain chirali-
ty induced by the interaction between the polymer and the Advances in the field of organic electronics in the last few
peptide. Induction of main-chain chirality in optically inactive years concern materials, device design, film-deposition proce-
dures, understanding of nucleation and growth processes,
device performance, device lifetime and stability, dielectric
substrates, and theoretical modeling, to name but a few.[51±53]
Pentacene still remains the benchmark semiconductor organic
material for FETs, and recently an organic LED driven by a
pentacene-based transistor has been described.[54]
With regards to thiophene derivatives, much work has been
devoted to oligo- and polythiophenes as semiconductors in
FETs.[55±64] New compounds have also been developed for
LEDs and lasers,[43,65±74] photovoltaic cells (PVDs), and elec-
trochromic devices,[75±86] which have produced better perfor-
mances in all the above types of devices. An increasing num-
ber of studies based on modern microscopy techniques have
been carried out on the morphology of the active films of
devices,[64] as researchers are becoming increasingly aware of
the fact that appropriate morphology of the active material is
one of the key factors in device performance. Various n-type
(electron-transporting) semiconductor oligomers have been
developed,[19±20] as well as new classes of p-type (hole-trans-
porting) materials (either small molecule or regioregular poly-
mers).[61±62] Ambipolar compounds have also been de-
scribed.[63] FET charge mobilities as high as 0.1±1 cm2 V±1 s±1
have been reported for p-type oligomers;[3] 0.01±0.1 cm2 V±1 s±1
for n-type oligomers;[19,20] and 0.01±0.1 cm2 V±1 s±1 for regio-
regular p-type polymers.[58,61] Charge-mobility values up to
0.02 cm2 V±1 s±1 and on/off current ratios of 106 have been
achieved for poly(3-hexylthiophene) nanofibers in top-contact
FETs prepared using nanoscale stencil shadow masks.[62b] To
our knowledge, no FET charge-mobility values have been
reported as yet for n-type polythiophenes.
Figure 4. Amino acid sequence for peptide JR2K (a), polythiophene struc- Thin-film FETs and integrated circuits based on quarter-,
ture (b), and schematic drawing of the chiral supermolecule formed
upon peptide±polymer interaction (c). Adapted from reference [49], with
quinque-, and sexithiophenes terminated with long alkyl
permission; copyright 2004, National Academy of Sciences of the United chains have been realized by thermal evaporation using an or-
States of America. ganic gate dielectric layer,[55] with charge-mobility values as

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G. Barbarella et al./Overview of Recent Research on Thiophene-Based Materials

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high as 0.5 cm2 V±1 s±1 and an on/off current ratio as large as
105. Thin-film transistors of solution-processable poly(9,9¢-
dioctylfluorene-co-bithiophene) and regioregular polyalkyl-
thiophenes with mobilities of 0.1 cm2 V±1 s±1, on/off current
ratios of nearly 106, and low threshold voltages have been fab-
ricated by inkjet printing onto patterned metal source±drain
contacts.[56] High-dielectric-constant gate insulator FETs were
fabricated with regioregular poly(3-hexylthiophene) with sat-
uration at low drive voltages (» ±2 V) and carrier mobilities
up to 1.3 ” 10±2 cm2 V±1 s±1, with the aim of demonstrating that Figure 5. Molecular structure of a highly electroluminescent V-shaped
gate insulators comprising a high-dielectric-constant material oligothiophene [70,71].
can at least partially compensate for the relatively low mobili-
ties of polymer semiconductors, and enable polymer-based
FETs to switch relatively large currents.[57] Improvement in
field-effect mobility of poly(3-hexylthiophene) was achieved
by casting films from 1,2,4-trichlorobenzene (caution: toxic),
which allowed the control of the microcrystalline order, as
measured by X-ray diffraction.[58]
Light-emitting devices with organic or organometallic com-
pounds as active materials are currently being intensively
studied; many commercial applications are being developed
and several major industries see great potential particularly
for lighting applications.[53] Current research is focused on
electrophosphorescent devices, including blue and white
ones,[65] mostly based on iridium complexes with small organic
molecules as emitters. A study on electrophosphorescence
from substituted poly(thiophenes) doped with iridium or plat-
inum complexes has been reported only very recently,[66] un-
derlining the difficulties connected to this field of research
and indicating new directions for the realization of electro-
phosphorescence from polythiophenes. Improvements have,
however, been reported in electroluminescent devices based
on a variety of new thiophene derivatives. Efficient blue elec-
troluminescence was obtained using blends of solution-pro-
Figure 6. White electroluminescence obtained from a single active mo-
cessable thiophene-containing dendrimers,[67] while microme- lecular material. Adapted from reference [43].
ter-wavelength electroluminescence was obtained from a
copolymer of fluorene with an electron-donating thiophene
ring bound to an electron withdrawing thiadiazolo-quinoxa- It has also been demonstrated that although oligothio-
line unit.[68] Copolymers of fluorene with incorporated thio- phene-S,S-dioxides are non-thermoplastic materials, they can
phene or phenylene units gave pure red electroluminescence be nanostructured by room temperature nanoimprint lithog-
with maximum luminance 3100 Cd m±2 and maximum exter- raphy with no degradation of their luminescence efficiency
nal quantum efficiency of 0.46 % at low voltage (4 V).[69] after patterning.[72] These compounds also display amplified
A bright electroluminescent diode exhibiting a record lumi- spontaneous emission and lasing properties, among the best
nance of 10 500 Cd m±2 was obtained by replacing the con- so far reported for organic compounds.[73] Random lasing was
ventional linear oligothiophene-S,S-dioxides structure with a also demonstrated in neat films, induced by sequential scatter-
branched benzo[b]thiophene-based structure with superior ing from 50 nm diameter holes in the film with an average
film-forming properties (Fig. 5).[70,71] spacing of 500 nm.[74]
Bright white-light-emitting devices from a single active mo- Current research into organic photovoltaic devices focuses
lecular material were obtained from spin-coated films of the on the combination of polythiophenes as electron donors with
boro-dithieno derivative shown in Figure 6, with a maximum inorganic elements of high electron affinity, such as nano-
luminance of 3800 Cd m±2 at 18 V and external quantum effi- structured CdSe or TiO2, as electron acceptors, in order to
ciency of 0.35 %.[43] White-light emission resulted from the facilitate charge transfer and transport in organic±inorganic
broad blue±green emission originating from the isolated mol- hybrid solar cells. For this purpose, colloidal nanorods of cad-
ecule and the red-shifted narrow emission arising from inter- mium selenide in conjunction with tail-to-tail poly(3-hexyl-
molecular interactions. thiophene) were the first reported to achieve good power con-

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 G. Barbarella et al./Overview of Recent Research on Thiophene-Based Materials
PROGRESS REPORT

version efficiency (1.7 %).[75] Enhanced performance in this 5. Thiophene-Based Materials for the Detection of
type of device was obtained with the use of end-functionalized Biological Molecules
polythiophenes, which allowed a better dispersion of the CdSe
nanorods and ensured a more efficient control of morphol- This section concerns oligo- and polythiophenes being uti-
ogy.[76] Similar results were also achieved using TiO2 and poly- lized as optical indicators (fluorimetric or colorimetric) for
thiophene with removable solubilizing groups.[77] recognition events involving proteins or DNA,[5,87±90] a rather
Concerning all-organic solar cells, devices based on poly(3- recent research field in which there have been significant im-
hexylthiophene) and a modified fullerene were shown to provements in the last two years. This research also concerns
achieve a power conversion efficiency of up to 3.5 % following charged polythiophenes as optical sensors for ions, including
post-production thermal treatment.[78] Good results were those of biological interest.[89±90]
obtained with a photovoltaic device based on a star-shaped Changes in size and functionalization types allow thiophene
oligothiophene as the electron donor and N,N¢-bistridecylper- oligomers to become fluorescent in the entire visible range.[91]
ylenedicarboxyimide as the electron acceptor and electron- This is also true for polythiophenes which, however, are more
transporting material.[79] Also in this case, the good results difficult to control in terms of composition (molecular weight
were ascribed to the appropriate morphology of the active and polydispersity).[92] In both types of materials, changes in
film, made possible by the particular molecular shape of the conformation induce changes in absorption and emission
electron-donor oligomer. Investigations aimed at elucidating wavelengths. Being small molecules of well-defined composi-
the photovoltaic properties of several classes of oligo- and tion, oligomers can be functionalized with groups that react
polythiophenes were also carried out.[80±82] spontaneously with specific functionalities present in proteins
Finally, recent improvements in the field of thiophene-based (for example, monoclonal antibodies) without altering their
electrochromic devices should be mentioned.[83±86] G. Sonmez biological activity and forming stoichiometrically well-defined
et al. reported the synthesis and electrochemical and optical bioconjugates that are both chemically and optically
properties of a low-bandgap thiophene-based polymer whose stable.[87,88,93] In turn, polythiophenes can easily be prepared
films on indium tin oxide (ITO) showed remarkable optical that bear positively or negatively charged substituents, capa-
properties upon both p- and n-doping.[84] The same authors ble of electrostatically interacting with oppositely charged
were also able to obtain three primary colors (blue, green, and DNA and proteins and revealing such interactions via a
red, see Fig. 7) of good quality, in terms of a chromaticity dia- color change.[5,89] To place things in the right context, mention
gram, from functionalized polythiophenes, allowing the reali- should be made of the fact that systems other than thiophene-
zation of many other colors by mixing the polymers in the right based ones are currently being developed for fluorimetric
proportions.[85] These results open the door to a new era for detection of biological events.[94±96]
electrochromic devices based on conducting polymers.[85] As fluorescent markers, oligothiophenes have many favor-
The above-reported results indicate that great steps forward able characteristics, since they have fluorescence frequencies
have been achieved in relative terms over the last few years. tunable across the entire visible range, high absorbancies,
However, it is difficult to assess the importance of these large differences between absorption and emission wave-
achievements on a more global scale. Improvements in device lengths, and high fluorescence efficiencies. Belonging to the
performance are related to both the synthesis of materials and same chemical family, all colors can be applied using the same
their supramolecular organization in the solid state, and im- standard methodologies. We have developed several classes of
provements in device design and manufacture. If materials thiophene-based fluorescent markers, functionalized with the
are not reproducible, and if each research group works with isothiocyanate group,[87,88] including those obtained from the
its own homemade devices, the field lacks a universal basis for highly fluorescent dithieno[3,2-b;2¢,3¢-d]thiophene-4,4-dioxide
comparison of the results of different groups, and therefore moiety.[93] Figure 8 shows some of the fluorescence emissions
sound criteria to define improvement cannot be established. that can be obtained from this class of compounds. This is a

R: Methyl, Hexyl R: H, Octyl

Figure 7. Structure of blue, green, and red electrochromic polythiophenes and colors achieved by mixing the polymers in the appropriate amounts.
Adapted from reference [85].

1588  2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.advmat.de Adv. Mater. 2005, 17, 1581±1593
G. Barbarella et al./Overview of Recent Research on Thiophene-Based Materials

PROGRESS REPORT
real color picture taken under irradia-
tion with a single light source, a UV
lamp exciting at k = 364 nm. All of these
compounds react spontaneously with
monoclonal antibodies, forming biocon-
jugates that are chemically and optically
stable in phosphate buffer solutions.
More recently, we have developed other
functionalization types for oligothio-
phenes, which allow a more-efficient
binding to monoclonal antibodies as
well as to oligonucleotides using simple
and standard modalities and are cur-
rently testing the sensitivity of oligo-
thiophene-marked oligonucleotides to Figure 9. Schematic drawing of the detection of proteins (BSA and human a-thrombin) by a cation-
specific DNA-sequence recognition.[97] ic polythiophene acting as a polymeric marker. Adapted from reference [89], with permission; copy-
Very recently, K. DorØ et al. reported right 2003, the American Chemical Society.
that a positively charged fluorescent
polythiophene can be used as an optical
transducer for the detection of very small amounts of genetic thiophenesÐshould create a new generation of useful tools in
material.[5] The recognition is based on the electrostatic inter- the areas of diagnostics, therapeutics, and drug screening.[98]
actions between the polymer and the negatively charged nu- All the authors involved in this type of research underline
cleic acid, which cause conformational changes in the polymer the tremendous potential of polythiophenes as optical sensors
backbone and consequent changes in the absorption and for applications in biodiagnostics. In view of that opinion, it
emission wavelengths of the polymer itself. The method was seems reasonable to extend efforts on one hand to better
employed, in particular, for the detection of a segment from characterize the polymers (see the remarks at the end of
the RNA genome of the Influenza virus. Concentrations as Sec. 2) and, on the other hand, to better define the stoichiom-
low as zeptomoles could be detected. In a further publication, etry of the non-covalently bonded conjugates formed by the
the authors reported that the same positively charged poly- polymers with the biomolecules of interest.
thiophene is capable of forming complexes with single-
stranded DNA sequences (aptamers) which can bind non-spe-
cific proteins such as BSA (bovine serum albumin) or human 6. Theoretical Calculations
a-thrombin.[89] The aptamer bound to the protein undergoes a
conformational transition from an unfolded to a folded struc- Theoretical modeling of thiophene-based materials is lim-
ture, which can be detected by adding a specific amount of the ited by the heavy computing demands related to the presence
water-soluble, positively charged polythiophene. In turn, the of the sulfur atoms. In the last few years, work focusing on
polymer transduces the new complex formation into a colori- two different directions has been published: understanding
metric or fluorometric signal. The process is illustrated in Fig- the ground-state aggregation mechanisms of thiophene oligo-
ure 9 for BSA (path B) and thrombin (path A). mers to establish a correlation between charge transport and
The transduction mechanism is based on the conforma- packing types, and understanding the nature of excited states
tional modifications of the backbone of the polymeric marker to interpret the light-emission properties in solution and in
induced from side-chain order/disorder transition due to the the solid state. Papers using a phenomenological approach as
interaction with the target object. Thus, it does not require well as those employing the most sophisticated modern com-
any labeling of the probe or of the target. According to the puting methodologies have been published.
authors, such bio-photonic toolsÐoptical transducing poly- The topic concerning the recognition processes that lead to
self-assembly in thiophene-based materialsÐwhich are driven
by a variety of intermolecular non-covalent interactions, the
relative importance of which can only be addressed by high-
level computational studiesÐwas first tackled by S. Tsuzuki
et al. by employing coupled cluster calculations with single
and double substitutions with non-iterative triple excitations
(CCSD(T)) with a very large basis set.[99] These authors stud-
ied the magnitude and directionality of interactions in thio-
Figure 8. Some fluorescence colors of oligothiophene-S,S-dioxide iso-
phene dimers in terms of electrostatic, induction, dispersion,
thiocyanates. Adapted from reference [93], with permission; copyright and charge-transfer interactions and used the results of calcu-
2003, the American Chemical Society. lations to interpret the single-crystal packing preferences of

Adv. Mater. 2005, 17, 1581±1593 www.advmat.de  2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1589
 G. Barbarella et al./Overview of Recent Research on Thiophene-Based Materials
PROGRESS REPORT

thiophene oligomers. Packing structures and packing effects

on excitation energies of thiophene oligomers of variable sizes
were studied by G. Zhang et al. by employing molecular
dynamic simulations and time-dependent density functional
theory (TDDFT)/6-311++G** ab initio calculations.[100] The
results underline the preference of the longer oligomers for
p-stacked structures. A phenomenological approach based on
the concept of lateral and angular deviations (pitch and roll') Figure 10. Molecular structure of 3,5-dimethyl-2,6-bis(3-methylthio-
phene)dithieno[3,2-b:2¢,3¢-d]thiophene-4,4-dioxide [106].
from an ideal p-stacked structure was used by M. D. Curtis et
al.[101] to rationalize the relationship of molecular packing to
charge-transport properties in a series of thiophene and car-
bazole oligomers. ciency. The authors underline that the light-emission mecha-
Several studies have addressed the properties of oligothio- nism of DTTOMe4 is very different from that of conven-
phene radical cations and anions. Thus, V. M. Geskin et al. tional, alkyl substituted, quarter- and sexithiophenes that they
compared the results of ab initio hybrid density functional had previously investigated.
theory (DFT) and MP2 (Mùller±Plesset) calculations on the
electronic and geometric structure of isolated oligothiophene
dications in their singlet and triplet states as a function of 7. Summary and Outlook
chain length.[102] G. Brocks et al. reported a DFT study on the
coulombic interactions between two holes in an oligothio- The great deal of work carried out in recent years on thio-
phene molecular crystal as a function of the oligomer phene-based functional materials indicates great potential for
length.[103] A theoretical DFT study on the radical cations and successful developments in many directions. There is no
anions of a sexithiophene bearing four beta alkylsulfanyl doubt, however, that before this promise can be completely
groups was reported by A. Alberti et al., and the results com- fulfilled, much systematic effort is required in order to better
pared experimental electrochemical, electron paramagnetic understand properties such as charge transport and light emis-
resonance, and NMR data.[104] sion and their relationship to molecular structure, molecular
A few theoretical investigations into the excited states of ordering, and morphology. No limits seem to have been
thiophene oligomers have been reported, aimed at gleaning reached as yet either in charge mobility or in light emission.
information on the nature of the states involved in the light- Apparently there is room to go much further, and industrial
emission process and on the influence of interchain interac- applications should follow.
tions on light-emission properties in the solid state. M. Rubio The chemical robustness of thiophene-based compounds
et al. carried out a study on the low-lying excited states of and the easy tunability of their properties via minor structural
2,2¢-bithiophene using multiconfigurational second-order per- modifications have allowed the realization of a great diversity
turbation theory (CASPT2) and extended atomic natural or- of chemical structures. It is likely that in the near future we
bitals (ANO) basis sets.[105] Vertical excitation and emission will witness the development of more and more intriguing
energies as well as adiabatic transition energies were com- compounds, and that in some cases there will be interesting
puted and related to experimental data. According to the applications of these materials. In particular, we believe that
authors, a noteworthy result of their study was the degeneracy given the rapidity of recent developments in the preparation
found for the 11Bu and 21Bu states of bithiophene, a feature of stable n-type (electron-transporting) materials,[19,20] the
supposed to play an important role in the understanding of realization of new, air-stable, ambipolar compounds, trans-
the photophysical properties of this compound and other thio- porting both holes and electrons, and perhaps even highly
phene oligomers. E. Tedesco et al. carried out an intermediate photoluminescent, will soon follow. As far as we can see, this
neglect of differential overlap with single configuration inter- should open the door to the realization of an all-thiophene'
action (INDO/SCI) investigation into the correlation between type of plastic electronics. From a fundamental point of view
photoluminescence (PL) properties and packing modalities in it is intellectually very stimulating to think in terms of using
the material displaying the highest PL efficiency measured so the same basic material, with different functionalities incorpo-
far for thiophene-based materials in the solid state, namely rated depending on the task to be accomplished, for the reali-
3,5-dimethyl-2,6-bis(3-methylthiophene)dithieno[3,2-b:2¢,3¢-d] zation of electronic and optoelectronic devices. It may also be
thiophene-4,4-dioxide (DTTOMe4, solid-state PL efficiency of interest with regards to easy manufacturing, low costs, and
48 %, Fig. 10).[106] The conformation and packing of materials compatibility. Looking even further ahead, we can
DTTOMe4 were determined directly from powder diffraction imagine that the all-thiophene' plastic electronics could be
data. The calculations showed that the high PL efficiency of realized by spontaneous self-organization of thiophene-based
this compound compared to that of the dithieno-S,S-dioxide materials. Indeed, even at the current, very rough stage of
rigid core, which packs forming co-facial dimers, is related to understanding, the self-assembly and self-organization prop-
the lower rate of formation of photoexcited charge transfer erties of these materials and their ability to create supramo-
pairs, which decay non-radiatively and then lower the PL effi- lecular hierarchical structures of many types spontaneously

1590  2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.advmat.de Adv. Mater. 2005, 17, 1581±1593
G. Barbarella et al./Overview of Recent Research on Thiophene-Based Materials

PROGRESS REPORT
appears impressive. These properties are certainly mostly due son Ranch, CA 2003. c) Semiconducting Polymers (Eds: G. Had-
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