We report the incorporation of graphene-oxide quantum dots (GOQDs) into films, diluted solutions, and light-emitting diodes (LEDs) as part of a water-soluble derivative of poly(p-phenylene vinylene), or PDV.Li, to investigate their impact on the light-emission properties of this model conjugated polymer. Despite the well-known ability of graphene and graphene oxide to quench the photoluminescence of nearby emitters, we find that the addition of GOQDs to diluted solutions of PDV.Li does not significantly affect the photoluminescence (PL) dynamics of PDV.Li, bringing about only a modest quenching of the PL. However, loading the polymer with GOQDs led to a substantial decrease in the turn-on voltage of LEDs based on GOQD–PDV.Li composites. This effect can be attributed to either the improved morphology of the host polymer, resulting in an increase in the charge mobility, or the enhanced injection through GOQDs near the electrodes.

We have prepared a new borazine derivative that bears mesityl substituents at the boron centers and displays exceptional chemical stability. Detailed crystallographic and solid-state fluorescence characterizations revealed the existence of several polymorphs, each of which showed different emission profiles. In particular, a bathochromic shift is observed when going from the lower- to the higher-density crystal. Computational investigations of the conformational dynamics of borazine 1 in both the gas phase and in the solid state using molecular dynamics (MD) simulations showed that the conformation of the peripheral aryl groups significantly varies when going from an isolated molecule (in which the rings are able to flip over the 90° barrier at RT) to the crystals (in which the rotation is locked by packing effects), thus generating specific nonsymmetric intermolecular interactions in the different polymorphs. To investigate the optoelectronic properties of these materials by fabrication and characterization of light-emitting diodes (LEDs) and light-emitting electrochemical cells (LECs), borazine 1 was incorporated as the active material in the emissive layer. The current and radiance versus voltage characteristics, as well as the electroluminescence spectra reported here for the first time are encouraging prospects for the engineering of future borazine-based devices.

White electroluminescence and fine-tuning of the emission color from binary blends of a blue-emitting polymer and a green/yellow-emitting threaded molecular wire consisting of a conjugated polymer supramolecularly encapsulated by functionalized cyclodextrins are demonstrated. Encapsulation controls the minimum intermolecular distance on the nanoscale, resulting in suppressed energy-transfer between the blend constituents and reduced formation of interchain charge-transfer complexes. The use of a green-emitting polyrotaxane significantly improves the electrical properties with respect to blends of a blue electroluminescent polyrotaxane and leads to a significant reduction in the turn-on voltage required for achieving white electroluminescence (V_ON = 3 V), with only 20% by weight of the encapsulated material.

In the search for new ways to combine the appealing simplicity of solution processing methods and the need for a high performance of the active layer of organic (opto)electronic devices, the possibilities given by the joint use of well-established casting techniques and post-treatment procedures are explored, as well as new and unconventional deposition protocols to tailor self-assembled architectures with a high degree of order at different length scales, from the subnanometer up to the macroscopic scale. In fact, even the same organic molecule can give rise to different molecular architectures which, in turn, may offer the possibility to exploit a large variety of new functionalities of the deposited materials, paving the way towards the fabrication multifunctional organic-based devices.

In the search for new ways to combine the appealing simplicity of solution processing methods and the need for a high performance of the active layer of organic (opto)electronic devices, the possibilities given by the joint use of well-established casting techniques and post-treatment procedures are explored, as well as new and unconventional deposition protocols to tailor self-assembled architectures with a high degree of order at different length scales, from the subnanometer up to the macroscopic scale. In fact, even the same organic molecule can give rise to different molecular architectures which, in turn, may offer the possibility to exploit a large variety of new functionalities of the deposited materials, paving the way towards the fabrication multifunctional organic-based devices.

A comparative study of the self-assembly at a variety of surfaces of a dithiophene rotaxane 1⊂β-CD and its corresponding dumbbell, 1, by means of atomic force microscopy (AFM) imaging and scanning tunneling microscopy (STM) imaging on the micrometer and nanometer scale, respectively. The dumbbell is found to have a greater propensity to form ordered supramolecular assemblies, as a result of π–π interactions between dithiophenes belonging to adjacent molecules, which are hindered in the rotaxane. The fine molecular structure determined by STM was compared to that obtained by molecular modelling. The optical properties of both rotaxane and dumbbell in the solid state were investigated by steady-state and time-resolved photoluminescence (PL) experiments on spin-cast films and diluted solutions. The comparison between the optical features of the threaded and unthreaded systems reveals an effective role of encapsulation in reducing aggregation and exciton migration for the rotaxanes with respect to the dumbbells, thus leading to higher PL quantum efficiency and preserved single-molecule photophysics for longer times after excitation in the threaded oligomers.

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.

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.

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 blue-emitting, organic-soluble rotaxane based on a polyfluorene derivative and the green-emitting poly(9,9-dioctylfluorene-alt-benzothiadiazole (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.

A dithiophene rotaxane 1⊂β-CD and its shape-persistent corresponding dumbbell 1 were synthesized and fully characterized. 2D NOESY experiments, supported by molecular dynamics calculations, revealed a very mobile macrocycle (β-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 1⊂β-CD was found to be blueshifted with respect to the dumbbell 1 (2.81 and 2.78 eV, respectively). Additionally, in contrast to previous observations, neither PL spectra nor the decay kinetics of both threaded and unthreaded 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.

Hydrophilic polyanionic conjugated polyrotaxanes are readily synthesized in water by Suzuki coupling, but their high polarity and ionic nature limit the potential applications of these materials. Here, we demonstrate three methods for transforming these polar polyelectrolytes into nonpolar lipophilic insulated molecular wires. A water-soluble polyfluorene-alt-biphenylene β-cyclodextrin (CD) polyrotaxane was converted into nonpolar derivatives by methylation of the carboxylic acid groups with diazomethane and conversion of the hydroxyl groups of the CDs to benzyl ethers, trihexylsilyl ethers, benzoyl esters, and butanoate esters to yield polyrotaxanes that are soluble in organic solvents such as chloroform and cyclohexane. Elemental analysis, NMR spectroscopy, and gel permeation chromatography (GPC) data support the proposed structures of the organic-soluble polyrotaxanes. The extents of reaction of the polyrotaxane CD hydroxyl groups were 55% for trihexylsilyl chloride/imidazole; 81% for benzyl chloride/sodium hydride; 72% for benzoyl chloride/pyridine/4-dimethylaminopyridine; and 98% butanoic anhydride/pyridine/4-dimethylaminopyridine. Alkylation, silylation, and esterification increase the bulk of the encapsulating sheath, preventing interstrand aggregation, increasing the photoluminescence efficiency in the solid state and simplifying the time-resolved fluorescence decay. The organic-soluble polyrotaxanes were processed into polymer light-emitting diodes (PLEDs) from solution in nonpolar organic solvents, thereby excluding ionic impurities from the active layer.