Rigidification of Poly(p-phenylene)s through ortho-Phenyl Substitution

[Image: see text] A sterically π-congested ortho-phenylated poly(p-phenylene) (PPP) has been synthesized with unprecedentedly high molecular weights up to 29 kDa after fractionation, as confirmed by gel permeation chromatography coupled with a multiangle laser light scattering detector. The chain translation diffusion coefficient obtained from dynamic light scattering experiments displayed strong scaling (∼L(w)(–0.8)) to the chain contour length, indicating a rodlike shape with remarkably high rigidity of this novel PPP. These results provide an interesting insight into the relationship between the structure and the chain stiffness of PPP-based polymers and challenge the validity of the existing diffusion models in polymer physics.