Formation of Bundle Assemblies of Stereoregular Polymers in Thermal Solid-State Polymerization of 7,7,8,8-Tetrakis(aryloxycarbonyl)-p-quinodimethanes

7,7,8,8-Tetrakis(aryloxycarbonyl)-p-quinodimethanes with bulky aryloxy groups such as benzyloxy (1a), pentafluorobenzyloxy (1b), and both benzyloxy and pentafluorobenzyloxy (1c) were synthesized. We investigated effects of these bulky groups on thermal solid-state polymerization reactivities on the basis of crystal structures of 1a–1c. Thermal polymerizations gave 1,6-trans-type stereoregular polymers in quantitative yields in 1 day at 110 °C for 1a, 1 day at 150 °C for 1b, and 6 days at 110 °C for 1c. Their initial crystal shapes were retained in appearance during polymerization to yield solid bundle assemblies of their polymeric chains. X-ray single-crystal structure analysis indicates that their crystals adopt molecular arrangements suitable for one-dimensional polymerization with the 1,6-trans-type addition along one crystallographic axis. Such arrangements led to expansion polymerization of 1b and contraction one of 1c. The resulting stereoregular polymers form less ordered bundle assemblies than tho...