A more sustainable and easier applicable synthesis of aliphatic isocyanides in DMC is introduced using non-hazardous p-toluenesulfonyl chloride as dehydration reagent.

The concept of sequence-definition in the sense of polymer chemistry is introduced to conjugated, rod-like oligo(phenylene ethynylene)s via an iterative synthesis procedure. Specifically, monodisperse sequence-defined trimers and pentamers were prepared via iterative Sonogashira cross-coupling and deprotection. The reaction procedure was extended to tetra- and pentamers for the first time yielding a monodisperse pentamer with 18% and a sequence-defined pentamer with 3.2% overall yield. Furthermore, three novel trimers with a 9H-fluorene building block at predefined positions within the phenylene ethynylene chain were synthesised in 23–52% overall yields. Hence, it was confirmed that a functionality of interest can be incorporated selectively at a pre-defined position of these monodisperse oligomers. All respective intermediate structures were fully characterised by proton and carbon NMR, mass spectrometry, size-exclusion chromatography, and IR spectroscopy. Additionally, thermal and optical transitions are reported for the different oligomers.

An efficient isocyanide‐based synthesis of S‐thiocarbamates was discovered and thoroughly investigated. The new reaction protocol is a one‐pot procedure and allows the direct conversion of N‐formamides into thiocarbamates by initial dehydration with p‐toluene sulfonyl chloride to the respective isocyanide and subsequent addition of a sulfoxide component. Contrary to recent literature, which also uses isocyanides as starting material, but with other sulfur reagents than sulfoxides, in this protocol, no isolation and purification of the isocyanide component is necessary, thus significantly decreasing the environmental impact and increasing the efficiency of the synthesis. The new protocol was applied to synthesize a library of sixteen thiocarbamates, applying four N‐formamides and four commercially available sulfoxides. Furthermore, experiments were conducted to investigate the reaction mechanism. Finally, four norbornene‐based thiocarbamate monomers were prepared and applied in controlled ring‐opening metathesis polymerization (ROMP) reactions. The polymers were characterized by size‐exclusion chromatography (SEC) and their properties were investigated utilizing differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA).

Linear uniform oligomers synthesized via a two‐step iterative cycle are postmodified with uniform octaethylene glycol monomethyl ether and finally coupled via azide‐alkyne cycloaddition to yield uniform star‐shaped block macromolecules with a mass ranging from 10 to 14 kDa. Each of the molecules is carefully characterized by NMR, electrospray ionization mass spectrometry (ESI‐MS), and size exclusion chromatography (SEC) to underline their purity as well as their uniformity. The obtained star‐shaped macromolecules are investigated in their ability to encapsulate dye molecules by carrying out qualitative solid–liquid phase transfer experiments.