Don't forget poly(disulfide)s. There is a rich literature pointing out the advantages of the dynamic nature of single disulfide bridges to explore self-sorting, biomolecular engineering, biomembrane analysis, and so on. Disulfide bonds between polymer chains are essential for protein folding, materials properties and the stabilization of various supramolecular architectures. However, poly(disulfide)s with disulfide bonds in the main chain are rarely used today to create interesting structures or functions. To attract attention and outline scope and limitations of poly(disulfide)s to build modern supramolecular systems, the rather eclectic recent literature on the topic is summarized. The review is moving from fascinating basic studies including photoinduced metathesis, polycatenanes and polyrotaxanes to applications in biosupramolecular systems such as micelles, membranes, tubes, gels, carriers, pores, sensors, catalysts and photosystems

The patterning of functional materials represents a crucial step for the implementation of organic semiconducting materials into functional devices. Classical patterning techniques such as photolithography or shadow masking exhibit certain limitations in terms of choice of materials, processing techniques and feasibility for large area fabrication. The use of self-assembled monolayers (SAMs) as a patterning tool offers a wide variety of opportunities, from the region-selective deposition of active components to guiding the crystallization direction. Here, we discuss general techniques and mechanisms for SAM-based patterning and show that all necessary components for organic electronic devices, i.e., conducting materials, dielectrics, organic semiconductors, and further functional layers can be patterned with the use of self-assembled monolayers. The advantages and limitations, and potential further applications of patterning approaches based on self-assembled monolayers are critically discussed.

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.

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.

Conjugated polymers (CPs) are promising materials for fluorescence imaging application. However, a significant problem in this field is the unexplained abnormally low fluorescence brightness (or number of fluorescence photons detected per one excitation photon) exhibited by most of CP single chains in solid polymer hosts. Here it is shown that this detrimental effect can be fully avoided for short chains of polyfluorene-bis-vinylphenylene (PFBV) embedded in a host polymer matrix of PMMA, if the conjugated backbone is insulated by cyclodextrin rings to form a polyrotaxane (PFBV-Rtx). Fluorescence kinetics and quantum yields are measured for the polymers in liquid solutions, pristine films, and solid PMMA blends. The fluorescence brightness of PFBV-Rtx single chains dispersed in a solid PMMA is very close to that expected for a chain with 100% fluorescence quantum yield, while the unprotected PFBV chains of the same length possess 4 times lower brightness. Despite this, the fluorescence decay kinetics are the same for both polymers, suggesting the presence of static or ultrafast fluorescence quenching in the unprotected polymer. About 80% of an unprotected PFBV chain is estimated to be completely quenched. The hypothesis is that the cyclodextrin rings prevent the quenching by working as 'bumpers' reducing the mechanical forces applied by the host polymer to the conjugated backbone and help retaining its conformational freedom. While providing a recipe for making CP fluorescence bright at the single-molecule level, these results identify a lack of fundamental understanding in the community of the influence of the environment on excited states in conjugated materials.