Sequential ROMP of electron rich and electron deficient paracyclophanediene monomers gives donor–acceptor di-, tri- and even tetrablock phenylenevinylene coploymers.

The highly strained ortho-diethylhexyloxy [2.2]paracyclophane-1,9-diene (M1) can be synthesized by ring contraction of a dithia[3.3]paracyclophane using a benzyne-induced Stevens rearrangement. This paracyclophanediene undergoes ring-opening metathesis polymerization to give well-defined 2,3-dialkoxyphenylenevinylene polymers with an alternating cis/trans alkene stereochemistry and controllable molecular weight. Fully conjugated block copolymers with electron-rich and electron-deficient phenylene vinylene polymer segments can be prepared by sequential monomer additions. These polymers can be readily isomerized to the all-trans stereochemistry polymer. The optical and electrochemical properties of these polymers were investigated by theory and experiment.

A modular approach to underexplored, unsymmetrical [1]benzothieno[3,2-b]benzothiophene (BTBT) scaffolds delivers a library of BTBT materials from readily available coupling partners by combining a transition-metal free Pummerer CH-CH-type cross-coupling and a...

Ortho-diethylhexyloxyphenylene benzothiadiazole paracyclophane-1,9-diene as a mixture of diastereomers was synthesized by a sequential benzyne Stevens rearrangement, oxidation and pyrolysis of a dithia[3.3]paracyclophane. Reaction of these highly strained cyclophanedienes with the...

Understanding the stability of conjugated polymers towards mechanical stimuli is critical for optimizing the processing and use of these materials in a range of electronic and optoelectronic devices, such as...