We present the synthesis and characterization of novel homo-and copolymers containing mono-and dialkylated 3, 4-propylenedioxythiophenes with the purpose of creating new π- conjugated polymers to be exploited in the field of polymer electronics and photonics. We show that the large seven-membered dioxepine ring attached to the thiophene moiety causes unfavorable steric interactions, especially in the homopolymers; it thus prevents ...