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Transient absorption three-beam pump-push-probe experiments demonstrate that cyclodextrin-encapsulation of conjugated polymer chains prevents interchain effects, such as energy migration and charge hopping. In the unencapsulated polymer, transient population of high-lying singlet states leads to interchain ionization, generating long-lived charge-separated species. Supramolecular encapsulation prevents this process; with high-lying singlets undergoing on-chain ionization, followed by very rapid charge recombination. Threading is an efficient way to control charge recombination and to obtain a material suitable for photonic applications, where the push effect can be implemented for all-optical ultrafast switching. © 2009 The American Physical Society.

The operation of a supramolecular interaction between conjugated macromolecular polyelectrolytes and the ion-transporting polymer PEO at the single molecule level and in bulk solid films was investigated. The polyelectrolytic properties of insulated molecular wires (IMW) along with lithium carboxylate and sulfonate substituents were used for the formation of supramolecular complexes with polymers featuring ion-coordination properties. It was observed that the interaction increases the photoluminescence(PL) and electroluminescence(EL) efficiencies of light emitting polyelectrolytes. The results show that the external quantum efficiency increases by a factor of 200, reaching 0.40%.

An astonishing assortment of structures have been described as "insulated molecular wires" (IMWs), thus illustrating the diversity of approaches to molecular-scale insulation. These systems demonstrate the scope of encapsulation in the molecular engineering of optoelectronic materials and organic semiconductors. This Review surveys the synthesis and structural characterization of IMWs, and highlights emerging structure-property relationships to determine how insulation can enhance the behavior of a molecular wire. We focus mainly on three IMW architectures: polyrotaxanes, polymer-wrapped pi systems, and dendronized polymers, and compare the properties of these systems with those of conjugated polymers threaded through mesoporous frameworks and zeolites. Encapsulation of molecular wires can enhance properties as diverse as luminescence, electrical transport, and chemical stability, which points to applications in electroluminescent displays, sensors, and the photochemical generation of hydrogen.

Here, it is demonstrated that energy transfer in a blend of semiconducting polymers can be strongly reduced by non-covalent encapsulation of one constituent, ensured by threading of the conjugated strands into functionalized cyclodextrins. Such macrocycles control the minimum intermolecular distance of chromophores with similar alignment, at the nanoscale, and therefore the relevant energy transfer rates, thus enabling fabrication of white-light-emitting diodes (CIE coordinates: x = 0.282, y = 0.336). In particular, white electroluminescence in a binary blend of a blueemitting, organic-soluble rotaxane based on a polyfluorene derivative and the green-emitting poly(9,9-dioctylfluorene-alt-benzotrtiadiazote (F8BT) is achieved. Morphological and structural analyses by atomic force microscopy, fluorescence mapping, μ-Raman, and fluorescence lifetime microscopy are used to complement optical and electroluminescence characterization, and to enable a deeper insight into the properties of the novel blend. © 2010 WILEY-VCH Verlag GmbH and Co. KGaA.

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

We have investigated the effect of interchain interactions on the ultrafast depolarization of the photoluminescence from solid films of a conjugated polymer. Accurate control was exercised over the interchain separation by threading of the conjugated chains with insulating macrocycles or complexation with an inert host polymer. Our measurements indicate that excitation into the higher electronic states of a chain aggregate is followed by a fast (

Conjugated dendrimers provide an excellent molecular architecture for tuning material properties for organic light emitting diodes. Here we demonstrate a modular approach allowing highly efficient fluorescent and phosphorescent emissive chromophores to be used to make red, green and blue solution-processed light emitting diodes. The choice of a common dendritic architecture ensures good solubility and film forming properties irrespective of the choice of core unit. In addition, this architecture allows blending of dendrimers with different cores without phase separation. We show that blending provides a simple but powerful way of tuning the colour of dendrimer LEDs from deep blue to blue-green, and from green to red with little impact on the device properties.

We present gain and lasing results from a polyrotaxane consisting of a conjugated polymer (polyfluorene-alt-biphenylene) threaded through sugar macrocycles (Β -cyclodextrin). Encapsulation suppresses interchain charge separation, leading to lasing emission not observed in the unthreaded polymer, and enlargement of the stimulated emission in threaded polymer is observed. We demonstrate all-optical switching distributed feedback laser. © 2009 American Institute of Physics.

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.

A study is presented on how encapsulation of conjugated polymer chains affects the motion of photoexcitations and the formation of interchain aggregates in solid films. It is shown that threading of a poly(diphenylene vinylene) backbone inside insulating cyclodextrins (rotaxination) and/or complexation of the chains with poly(ethylene oxide) are effective means of preventing the diffusion of excitons to nonradiative defect sites. Ultrafast time-resolved photoluminescence data reveal that excitation transfer between encapsulated chains is still possible and, for the case of rotaxination, is likely to be facilitated through close packing of end groups belonging to adjacent chains. © 2006 American Institute of Physics.