Macrocyclic poly( p -phenylenevinylene)s by ring expansion metathesis polymerisation and their characterisation by single-molecule spectroscopy.

Ring expansion metathesis polymerisation (REMP) has proven to be a viable approach to prepare high purity cyclic polymers. Macrocyclic polymers with a fully conjugated defect free backbone are of particular interest as these polymers have no end groups that can act as charge traps. In this work soluble macrocyclic poly( p -phenylenevinylene)s ( c PPV s) have been prepared directly via the REMP of substituted paracyclophanedienes. Single-molecule spectroscopy of the two topological forms of PPV i.e. , linear ( l PPV ) and cyclic ( c PPV ) revealed that l PPV exists in an extended conformation whereas the c PPV adopts a restricted ring-like conformation. Despite such large differences in the chain conformation, the spectral properties of the two compounds are unexpectedly very similar, and are dominated by torsional deformations in relatively short conjugated segments.