As a new conformational motif of vinyl polymers having side-chain π-electronic groups, we have introduced a ‘π-stacked structure’ in which side-chain chromophores are regularly stacked on top of each other and main-chain C-C bonds have a nearly all-trans, zigzag conformation. π-Stacked polymers can be prepared by vinyl polymerization of dibenzofulvene (DBF) and its derivatives. On the basis of the controlled structure, poly(DBF) and its derivatives exhibit unique photophysical and electronic properties as vinyl polymers. Introduction of chirality to π-stacked polymers was also achieved.
