Regioregular, alkyl-substituted poly(heteroaromatics) tend to crystallize in π-stacked structures as opposed to the herringbone pattern characteristic of non-substituted, planar aromatic molecules, e.g. sexithiophene. π-Stacking, favored by the crystallization of the sidechains, induces planarity in the conjugated backbone. The increased planarity causes a large (50-100 nm) shift in λmax (abs.) compared to the solution phase in which the backbone is twisted out of coplanarity, π-Stacking is a form of ground state aggregation that causes “fine structure” on the absorption peak. Excitation into the aggregate states rapidly leads to the formation of excimers as shown by the excitation spectra. In -stacked polymers, photoluminescence is almost entirely from the excimer states.