6th Framework Programmemc


THREADed Molecular wIres as supramoLecularly engineered muLtifunctional materials

European Union Flagmc
LondonMons Strasbourg Oxford Milan Delft Lodz San Sebastian Catania Scriba Nanotecnologie BASF



The new book "Charge and Exciton Transport through Molecular Wires" (Wiley, January 2011) edited from two former Threadmillers: Laurens D. A. Siebbeles and Ferdinand C. Grozema has been reviewed by Paolo Samori and Emanuele Orgiu (LINK)



Highly-polarized emission from oriented films incorporating water-soluble conjugated polymers in a polyvinyl alcohol matrix
F. Di Stasio, P. Korniychuk, S. Brovelli, P. Uznanski, S. O. McDonnell, G. Winroth, H. L. Anderson, A. Tracz and F. Cacialli

Published online: 1 March 2011

Highly-oriented luminescent films were produced by stretching of a 30 mm-thick polyvinyl alcohol matrix doped with water-soluble polyrotaxanes and their unthreaded analogues. Polarization-resolved steady-state and time-resolved photoluminescence experiments reveal that over 95% of the emitted light is polarized along the orientation direction. A hybrid organic-inorganic light-emitting diode was built to investigate the possibility of using these films as polarizing filters for solid-state lighting and display technology.


Congratulations to Francesco Di Stasio for the "Best student poster presentation" Award at the European optical society Meeting 2010!

Local Current Mapping and Patterning of Reduced Graphene Oxide
Jeffrey M. Mativetsky, Emanuele Treossi, Emanuele Orgiu, Manuela Melucci, Giulio Paolo Veronese, Paolo Samorì, Vincenzo Palermo
Published Online: 22 July 2010
DOI: 10.1021/ja104567f

Conductive atomic force microscopy (C-AFM) has been used to correlate the detailed structural and electrical characteristics of graphene derived from graphene oxide. Uniform large currents were measured over areas exceeding tens of micrometers in few-layer films, supporting the use of graphene as a transparent electrode material. Moreover, defects such as electrical discontinuities were easily detected. Multilayer films were found to have a higher conductivity per layer than single layers. It is also shown that a local AFM-tip-induced electrochemical reduction process can be used to pattern conductive pathways on otherwise-insulating graphene oxide. Transistors with micrometer-scale tip-reduced graphene channels that featured ambipolar transport and an 8 order of magnitude increase in current density upon reduction were successfully fabricated.

High-Resolution Scanning Near-Field Optical Lithography of Conjugated Polymers
Dan Credgington, Oliver Fenwick, Ana Charas, Jorge Morgado, Klaus Suhling, Franco Cacialli
Published Online: 6 July 2010
DOI: 10.1002/adfm.2010000202

The fabrication of high-resolution nanostructures in both poly(p-phenylene vinylene), PPV, and a crosslinkable derivative of poly(9,9-dioctylfluorene), F8, using scanning near-field optical lithography, is reported. The ability to draw complex, reproducible structures with 65000 pixels and lateral resolution below 60 nm
(< λ/5) is demonstrated over areas up to 20 μm × 20 μm. Patterning on length-scales of this order is desirable for realizing applications both in organic nanoelectronics and nanophotonics. The technique is based on the site-selective insolubilization of a precursor polymer under exposure to the confined optical field present at the tip of an apertured near-field optical fiber probe. In the case of PPV, a leaving-group reaction is utilized to achieve insolubilization, whereas the polyfluorene is insolubilized using a photoacid initiator to create a crosslinked network in situ. For PPV, resolubilization of the features is observed at high exposure energies. This is not seen for the crosslinked F8 derivative, r-F8Ox, allowing us to pattern structures up to 200 nm in height.

White Electroluminescence from Single-Layer Devices of Nonresonant Polymer Blends
Sergio Brovelli, Hao Guan, Gustaf Winroth, Oliver Fenwick, Francesco Di Stasio, Rusli Daik, W. James Feast, Francesco Meinardi and Franco Cacialli
Published Online: 24 May 2010
DOI: 10.1063/1.3387816

Poly(9,9'-dioctyl fluorene) (F8) and poly(4,4'-diphenylene diphenylvinylene) (PDPV) are conjugated polymers with optical transitions that are nonresonant thanks to the particular structural features of PDPV that yield a very large Stokes’ shift (1.14 eV) between absorption and emission spectra. We present steady-state and time-resolved photoluminescence (PL) experiments showing that F8:PDPV blends are “optically disconnected” systems for which the emission spectra and PL quantum yields are the linear combination of the contributions of the individual constituents with weights given by the respective absorption coefficients and concentration in the films. Single-layer light-emitting diodes incorporating F8:PDPV blends show white electroluminescence resulting from the simultaneous exploitation of the spectral features of both blend constituents (Commission Internationale de l’Eclairage, CIE, coordinates: x=0.27 and y=0.36, in the case of 8:2 F8:PDPV molar ratio).

(a) EL EQE and (c) EL spectra for (ITO/PEDOT:PSS/polymer/Ca/Al) LEDs incorporating F8, PDPV and the relative binary blends. (b) Position of the HOMO and LUMO levels for the isolated materials with no applied field. (d) CIE chromaticity diagram of EL and PLspectra.

Enhanced Luminescence Properties of Highly Threaded Conjugated Polyelectrolytes with Potassium Counter-Ions upon Blending with Poly(ethylene oxide)
Gianluca Latini, Gustaf Winroth, Sergio Brovelli, Shane O. McDonnell, Harry L. Anderson, Jeffrey M. Mativetsky, Paolo Samorì and Franco Cacialli
Published Online: 22 June 2010
DOI: 10.1063/1.3372616

The photophysics and electroluminescence (EL) of thin films of unthreaded and cyclodextrin-encapsulated poly(4,4'-diphenylenevinylene) (PDV) with potassium countercations, blended with poly(ethylene oxide) (PEO) are investigated as a function of the PEO concentration.
We show that three main factors contribute to increasing the photoluminescence (PL) quantum efficiency as a result of suppressed intermolecular interactions, namely: the high degree of encapsulation of the polyrotaxanes, the relatively large countercation (e.g., compared to lithium), and the complexation of the rotaxanes with PEO. By facilitating cationic transport to the negative electrodes, PEO also leads to devices with enhanced electron injection and improved charge balance, whose operation therefore resembles that of “virtually unipolar” light-emitting electrochemical cells. This effect, together with the enhanced PL efficiency, leads to higher EL efficiency for both polyrotaxanes and unthreaded polymers, upon addition of the PEO.We show that the concurrent exploitation of the various strategies above lead to an overall EL efficiency that is approximately twice the value previously reported for Li-based PDV. A blueshift of the EL spectrum during the devices turn-on is also reported and analyzed in terms of interference and doping effects.

A schematic band diagram for an LED device incorporating polyelectrolytes
as active layer. At zero applied voltage (a), the mobile countercations migrate at the interface with ITO thus partially screening the bulk
from the built-in electric field. Under forward bias (b), the positive ions accumulate at the cathode, reducing the width of the electron injection barrier. (c) External quantum efficiency . The average of the maximum external quantum effciency of the devices tested (more than 10 devices per type) as a function of the PEO concentration for the unthreaded (dashed line) and threaded polymers (solid line). Error bars are the standard deviations.

A Conjugated Thiophene-Based Rotaxane: Synthesis, Spectroscopy and Modeling (p3933-3941)
Leszek Zalewski, Michael Wykes, Sergio Brovelli, Massimo Bonini, Thomas Breiner, Marcel Kastler, Florian Dotz, David Beljonne, Harry L. Anderson, Franco Cacialli and Paolo Samorì
Published Online: March 15 2010
DOI: 10.1002/chem200903353

A dithiophene rotaxane and its shape persistent corresponding dumbbell were synthetized and fully characterized. 2D NOESY experiments, supported by molecular dynamics calculations, revealed a very mobile macrocycle (alpha-CD). Steady-state and time-resolved photoluminescence experiments in solution were employed to elucidate the excited-state dynamics for both systems and to explore the effect of cyclodextrin encapsulation. The photoluminescence (PL) spectrum of alpha-CD was found to be blueshifted with respect to the dumbbell (2.81 and 2.78 eV respectively). Additionally, in contract to previous observations, neither PL spectra nor the decay kinetics of both threaded and unthreade systems showed changes upon increasing the concentration or changing the polarity of the solutions, thereby providing evidence for a lack of tendency toward aggregation of the unthreaded backbone

Electrochemical synthesis of PEDOT derivatives bearing imidazolium-ionic liquid moieties (p 3010-3021)
Markus Döbbelin, Cristina Pozo-Gonzalo, Rebeca Marcilla, Raúl Blanco, José L. Segura, Jose A. Pomposo, David Mecerreyes
Published Online: May 7 2009 10:55AM
DOI: 10.1002/pola.23384



Novel poly(3,4-ethylenedioxythiophene) (PEDOT) polymers bearing imidazolium-ionic liquid moieties were synthesized by electrochemical polymerization. The polymers could be dissolved in a range of polar organic solvents such as dimethylformamide, propylene carbonate, and dimethyl sulfoxide making them interesting candidates for wet processing methods. Interestingly, the hydrophobic character of electropolymerized films could be modified depending on the anion type. The hydrophobicity followed the trend PFb > (CF3SO2)2N- > BFa > pure PEDOT as determined by water contact angle measurements.

Influence of cyclodextrin size on fluorescence quenching in conjugated polyrotaxanes by methyl viologen in aqueous solution
Francine E. Oddy, Sergio Brovelli, Matthew T. Stone, Eric J. F. Klotz, Franco Cacialli and Harry L. Anderson

Poly(4,4alpha-diphenylenevinylene) rotaxanes and [2]rotaxanes with beta-, alpha-, gamma-cyclodextrin macrocycles were synthesised and their sensitivities to fluorescence quenching by methyl viologen in aqueous solution were determined, relative to uninsulated analogues. Stern–Volmer analysis revealed that the fluorescence quenching response of polyrotaxanes is strongly dependent on the diameter of the cyclodextrins. Polyrotaxanes, composed of the smaller diameter alpha- or gamma-cyclodextrins, are the least easily quenched, with Stern–Volmer constants about two orders of magnitude smaller than from the wider beta-cyclodextrin polyrotaxane and the uninsulated polymer. Time-resolved photoluminescence results demonstrate the crucial role of interchain aggregation on the sensitivity to fluorescence quenchers. The materials with the highest Stern–Volmer constants exhibit the most biexponential photoluminescence decay, which is indicative of aggregation, and the emission spectra of solutions containing methyl viologen resemble the early-time emission spectra (0–3 ns after excitation) of the unquenched samples. The results show that the threaded '-cyclodextrin is effective in preventing aggregation, and in hindering fluorescence quenching, even when only a small fraction of the conjugated polymer is encapsulated. This conclusion is relevant to the application of these materials in optoelectonic devices, such as light-emitting diodes, where it is essential to prevent luminescence quenching without hindering charge transport.

(J. Mater. Chem., 2009, 19, 2846 - 2852, DOI: 10.1039/b821950h)

Mechanism of Charge Transport along Zinc Porphyrin-Based Molecular Wires

Aleksey A. Kocherzhenko, Sameer Patwardhan, Ferdinand C. Grozema, Harry L. Anderson and Laurens D. A. Siebbeles.

In this study charge transport along zinc porphyrin-based molecular wires is simulated, considering both bandlike and hopping mechanisms. It is shown that bandlike transport simulations yield significantly overestimated hole mobility values. On the basis of kinetic and thermodynamic considerations, it is inferred that charge transport along zinc porphyrin-based molecular wires occurs by small polaron hopping. Hole mobility values on the order of 0.1 cm2 /(V s) are found from small polaron hopping simulations, which agree well with previously reported experimental results. It is suggested that the experimentally observed increase of the charge carrier mobility on formation of supramolecular ladderlike structures is determined by two factors. One of these is an increase of charge transfer integrals between monomer units due to molecular wire planarization. A more important factor is the reduction of the amount of energetic disorder along the molecular wire and in its environment. General guidelines for determining the mechanism of charge transport along molecular wires are discussed.

(JACS, 2009, ASAP.DOI: 10.1021/ja809174y)

Supramolecular Crystal Engineering at the Solid-Liquid Interface from First Principles: Toward Unraveling the Thermodynamics of 2D Self-Assembly (p NA)
Carlos-Andres Palma, Massimo Bonini, Thomas Breiner, Paolo Samorì

The formation of highly ordered 2D supramolecular architectures self-assembled at the solid-solution interfaces is subject to complex interactions between the analytes, the solvent, and the substrate. These forces have to be mastered in order to regard self-assembly as an effective bottom-up approach for functional-device engineering. At such interfaces, prediction of the thermodynamics governing the formation of spatially ordered 2D arrangements is far from being fully understood, even for the physisorption of a single molecular component on the basal plane of a flat surface. Two recent contributions on controlled polymorphism and nanopattern formation render it possible to gain semi-quantitative insight into the thermodynamics of physisorption at interfaces, paving the way towards 2D supramolecular crystal engineering. Although in these two works different systems have been chosen to tackle such a complex task, authors showed that the chemical design of molecular building blocks is not the only requirement to fulfill when trying to preprogram self-assembled patterns at the solid-liquid interface.

(Advanced Materials, Published Online: Feb 6 2009 7:17AM, DOI: 10.1002/adma.200802068)

Pre-programmed bicomponent porous networks at the solid–liquid interface: the low concentration regime
Carlos-Andres Palma, Massimo Bonini, Anna Llanes-Pallas, Thomas Breiner, Maurizio Prato, Davide Bonifazi and Paolo Samorì

The control over the formation of a bicomponent porous network was attained by self-assembly at the solid–liquid interface, exploiting triple H-bonds between melamine and bis-uracyl modules.
Chem. Commun., 2008, 5289 - 5291, DOI: 10.1039/b811534f


Tuning Intrachain versus Interchain Photophysics via Control of the Threading Ratio of Conjugated Polyrotaxanes
Sergio Brovelli, Gianluca Latini, Michael J. Frampton, Shane O. McDonnell, Francine E. Oddy, Oliver Fenwick, Harry L. Anderson and Franco Cacialli

Effective nanoscale control of intermolecular interactions in conjugated polymers is needed for the optimal development and exploitation of the latter in low-cost, large-area consumer electronics items, such as light-emitting and photovoltaic diodes, or transistors. Here we report our investigations on insulated molecular wires constituted by conjugated polymers threaded into cyclodextrin rings. Until now, there has been no detailed quantitative understanding of the role of progressive cyclodextrin encapsulation (quantifiable by the so-called “threading ratio”, TR, or number of cyclodextrins per repeat unit) in tailoring the photophysics of the conjugated polymeric wires. We combine spectroscopic, electrical and surface analysis techniques to elucidate how the TR of cyclodextrin-threaded molecular wires controls formation of interchain species and related physical properties (0 < TR = 2.3; the maximum theoretical TR for close-packed CDs is 2.8). Increasing TR enhances the solid-state photoluminescence (PL) and electroluminescence quantum efficiency. To unravel the effect of progressive encapsulation on the intrachain decay kinetics of the polymer backbone, we added an electron-accepting quenching agent, methyl viologen (MV), to the polymer solutions. MV predominantly quenches the aggregate PL, thus enabling measurement of the decay kinetics of the intrinsic exciton even for low-TR polyrotaxanes, for which the different contributions are otherwise difficult to disentangle.
(Nano Lett., 2008, 8 (12), pp 4546–4551)

Control of Rapid Formation of Interchain Excited States in Sugar-Threaded Supramolecular Wires 
Annamaria Petrozza, Sergio Brovelli, Jasper J. Michels, Harry L. Anderson, Richard H. Friend, Carlos Silva, Franco Cacialli

The time-resolved photoluminescence of cyclodextrin-threaded conjugated molecular wires and their unthreaded analogues is studied to probe suppression of intermolecular interactions by supramolecular encapsulation. The polyrotaxane dynamics are exponential and independent of concentration, different from those of unthreaded semiconductors, which display instead optical signatures of interchain species. This is fundamental insight into the photophysics of semiconducting polymers, and crucial for the development of organic electronics.
(Advanced Materials, 2008, 20, 17, 3218-3223)

Synthesis and Optoelectronic Properties of Nonpolar Polyrotaxane Insulated Molecular Wires with High Solubility in Organic Solvents 
Michael J. Frampton, Giuseppe Sforazzini, Sergio Brovelli, Gianluca Latini, Emily Townsend, Charlotte C. Williams, Ana Charas, Leszek Zalewski, Naeem S. Kaka, Mallena Sirish, Lisa J. Parrott, Joanne S. Wilson, Franco Cacialli, Harry L. Anderson

Alkylation, silylation, and esterification are used to inflate the insulation around a conjugated polymer backbone, making the polyrotaxane soluble in nonpolar solvents, increasing the photoluminescence efficiency in the solid state, and simplifying fluorescence decay behavior.
(Advanced Functional Materials, 2008, 18, 3367–3376)

Ground- and Excited-State Pinched Cone Equilibria in Calix[4]arenes Bearing Two Perylene Bisimide Dyes
Catharina Hippius, Ivo H. M. van Stokkum, Ennio Zangrando, René M. Williams, Michael Wykes, David Beljonne and Frank Würthner

We report on a series of bis-chromophoric compounds o2c, g2c, and r2c, afforded by linking two identical orange, green, or red perylene bisimide (PBI) units, respectively, through a calix[4]arene spacer unit.
(J. Phys. Chem. C 2008, 112, 14626–14638 )

Radical Cation Stabilization in a Cucurbituril Oligoaniline Rotaxane
Rienk Eelkema, Kiminori Maeda, Barbara Odell, and Harry L. Anderson
A cucurbituril-encapsulated oligoaniline rotaxane is synthesized in high yield by reductive amination in aqueous acid. Spectroscopic and electrochemical measurements show that encapsulation by cucurbit[7]uril increases the thermodynamic and kinetic stability of the radical cation of the threaded oligoaniline. This radical cation has a stoichiometry similar to that of the conducting emeraldine salt form of polyaniline, which implies that cucurbituril insulation of polyaniline might drastically alter the oxidation potential of the threaded conjugated polymer chain.
(J. Am. Chem. Soc. 2007, 129, 12384–12385)

Cyclodextrin-Threaded Conjugated Polyrotaxanes for Organic Electronics: The Influence of the Counter Cations 

Gianluca Latini, Lisa-Jodie Parrott, Sergio Brovelli, Michael J. Frampton, Harry L. Anderson, Franco Cacialli
The influence of counter cations on the optical properties of conjugated polyelectrolytes and of their cyclodextrin-threaded rotaxanes is studied. Exchange of Li+ with K+, Cs+, or Me4N+ results in higher electroluminescence efficiency for both rotaxanes and unthreaded polymers, narrowing (unthreaded analogues) and a slight red-shift of the absorption spectra (rotaxanes) and a blue-shift and PL efficiency enhancement of the luminescence.
(Advanced Functional Materials, 18, 16,2419-2427,2008)


Amylose-wrapped luminescent conjugated polymers

Michael J. Frampton, Timothy D. W. Claridge, Gianluca Latini, Sergio Brovelli, Franco Cacialli and Harry L. Anderson

Highly luminescent inclusion complexes consisting of poly(para-phenylene) ( PPP) or poly(4,4-diphenylene-vinylene) ( PDV) in the helical cavity of amylose have been synthesised, structurally characterised by nuclear Overhauser spectroscopy and used to fabricate electroluminescent light-emitting diodes.
(Chemical Communications, 24, 2797-2799, 2008 )

Nucleation-Governed Reversible Self-Assembly of an Organic Semiconductor at Surfaces: Long-Range Mass Transport Forming Giant Functional Fibers 

G. De Luca, A. Liscio, P. Maccagnani, F. Nolde, V. Palermo, K. Müllen, P. Samorì


Solvent-vapor annealing has been successfully employed to increase the degree of order in the self-organization of a perylene-bis(dicarboximide) derivative cast on different substrates from solution (see figure). Upon exposure to tetrahydrofuran vapors, the starting needle-like structures rearrange into millimeter-long fibers, which have a sub-micrometer cross section, with remarkable mass transport at the surface.
(Adv. Funct. Mater., 2007, 17, 3791-3798 & 3687)

Back to top