Poly(Arylene Alkylene)s with Tetrazole Pendants for Alkaline Ion-Solvating Polymer Electrolytes.

Alkaline ion-solvating membranes derived from a tetrazole functionalized poly(arylene alkylene) are prepared, characterized and evaluated as electrode separators in alkaline water electrolysis. The base polymer, poly[[1,1'-biphenyl]-4,4'-diyl(1,1,1-trifluoropropan-2-yl)], is synthesized by superacid catalyzed polyhydroxyalkylation and subsequently functionalized with tetrazole pendants. After equilibration in aqueous KOH, the relatively acidic tetrazole pendants are deprotonated to form the corresponding potassium tetrazolides.

Electrode Separators for the Next-Generation Alkaline Water Electrolyzers.

Multi-gigawatt-scale hydrogen production by water electrolysis is central in the green transition when it comes to storage of energy and forming the basis for sustainable fuels and materials. Alkaline water electrolysis plays a key role in this context, as the scale of implementation is not limited by the availability of scarce and expensive raw materials. Even though it is a mature technology, the new technological context of the renewable energy system demands more from the systems in terms of higher energy efficiency, enhanced rate capability, as well as dynamic, part-load, and differential pressure operation capability.

Carbonyl-to-Alkyne Electron Donation Effects in up to 10-nm-Long, Unimolecular Oligo(-phenylene ethynylenes).

We synthesized some of the longest unimolecular oligo(-phenylene ethynylenes) (OPEs), which are fully substituted with electron-withdrawing ester groups. An iterative convergent/divergent (a.k.

Size-selective Catalytic Polymer Acylation with a Molecular Tetrahedron.

Selective catalysis at the molecular level represents a cornerstone of chemical synthesis. However, it still remains an open question how to elevate tunable catalysis to larger length scales to functionalize whole polymer chains in a selective manner. We now report a hydrazone-linked tetrahedron with wide openings, which acts as a catalyst to size-selectively functionalize polydisperse polymer mixtures.

Selective Monofunctionalization Enabled by Reaction-History-Dependent Communication in Catalytic Rotaxanes.

Selective monofunctionalization of substrates with distant, yet equally reactive functional groups is difficult to achieve, as it requires the second functional group to selectively modulate its reactivity once the first functional group has reacted. We now show that mechanically interlocked catalytic rings can effectively regulate the reactivity of stoppering groups in rotaxanes over a distance of about 2 nm. Our mechanism of communication is enabled by a unique interlocked design, which effectively removes the catalytic rings from the substrates by fast dethreading as soon as the first reaction has taken place.

Enantioselective Electrophilic Aromatic Nitration: A Chiral Auxiliary Approach.

Enantioselective electrophilic aromatic nitration methodology is needed to advance chirality-assisted synthesis (CAS). Reported here is an enantioselective aromatic nitration strategy operating with chiral diester auxiliaries, and it provides an enantioselective synthesis of a C -symmetric tribenzotriquinacene (TBTQ). These axially-chiral structures are much sought-after building blocks for CAS, but they were not accessible prior to this work in enantioenriched form without resolution of enantiomers.

Crystal-Packing-Driven Enrichment of Atropoisomers.

Crystal-packing forces can have a significant impact on the relative stabilities of different molecules and their conformations. The magnitude of such effects is, however, not yet well understood. Herein we show, that crystal packing can completely overrule the relative stabilities of different stereoisomers in solution.