Dinickel-Catalyzed N═N Bond Rotation.

Azoarenes function as molecular switches that can be triggered by external stimuli, such as heat, light, and electrochemical potential. Here, we show that a dinickel catalyst can induce cis/trans isomerization in azoarenes through a N═N bond rotation mechanism. Catalytic intermediates containing azoarenes bound in both the cis and trans forms are characterized. Solid-state structures reveal the importance of π-back-bonding interactions from the dinickel active site in lowering the N═N bond order and accelerating bond rotation. The scope of the catalytic isomerization includes high-performance acyclic, cyclic, and polymeric azoarene switches.

Catalytic Synthesis of Conjugated Azopolymers from Aromatic Diazides.

Conjugated polymers containing main chain azoarene repeat units are synthesized by a dinickel catalyzed N=N coupling reaction of aromatic diazides. The polymerization exhibits broad substrate scope and is compatible with heterocycles commonly featured in high performance organic materials, including carbazole, thiophene, propylenedioxythiophene (ProDOT), diketopyrrolopyrrole (DPP), and isoindigo. Copolymerizations can be carried out using monomer mixtures, and monoazide chain stoppers can be used to install well-defined end groups. Azopolymers possess unique properties owing to the functionality of the azo linkages. For example, protonation at nitrogen results in LUMO lowering and red-shifted absorption bands. Additionally, N=N bonds possess low-lying π* levels, allowing azopolymers to be reversibly reduced under mild conditions.