Pure hydrocarbons with shape and conjugation properties that can be switched by external stimuli is an intriguing prospect in the design of new responsive materials and single-molecule electronics. Here, we develop an oligomeric [8]annulene-based material that combines a remarkably efficient topological switching upon redox changes with structural simplicity, stability, and straightforward synthesis: 5,12-alkyne linked dibenzo[a,e]cyclooctatetraenes (dbCOTs). Upon reduction, the structures accommodate a reversible reorganization from a pseudo-conjugated tub-shape to a conjugated aromatic system. This switching in oligomeric structures gives rise to multiple defined states that are deconvoluted by electrochemical, NMR, and optical methods. The combination of stable electromechanical responsivity and ability to relay electrons stepwise through an extended (pseudo-conjugated) π-system in partially reduced structures validate alkyne linked dbCOTs as a practical platform for developing new responsive materials and switches based on [8]annulene cores.

The stability of nanoparticles and their supports are critical, but poorly understood, parameters for applications of such systems in liquid environments. Here we develop an approach to systematically investigate the stability of aerosol-generated nanoparticles after exposure to commonly used solvents using a combination of identical location-SEM and density/size analysis. We demonstrate that the choice of solvent needs to be carefully matched with both the particle and support materials. We show that thermal annealing significantly increases the adhesion of the particles and expands the scope of applications in aqueous media and for biological applications. The results clarify combinations of inorganic nanoparticles on oxide and semiconductor supports with solvents and environmental conditions that give sufficient stability. Combined, the presented methods should be of value in investigating the stability of nanoparticle systems after exposure to solvent and can be used for future developments of high-performing supported aerosol-generated nanoparticles for solvent-based applications.

Diareno[ a , e ]cyclooctatetraenes find widespread applications as building blocks, ligands, and responsive cores in topologically switchable materials. However, current synthetic methods to these structures suffer from low yields or operational disadvantages. Here, we describe a practical three-step approach to diareno[ a , e ]cyclooctatetraenes using an efficient copper(I) catalyzed double decarboxylation as the key step. The sequence relies on cheap and abundant reagents, is readily performed on scale, and is amenable also to unsymmetrical derivatives that expand the utility of this intriguing class of structures.

No abstract

Dehydrogenation reactions that produce molecular hydrogen are thermodynamically unfavourable. Desired is to couple them with a green driving force, such as oxidation with oxygen or electric current. This, in turn,...