Conjugated oligomers and polymers containing planar structural constraints are synthetically challenging targets displaying a variety of unusual properties. We develop novel routes for the efficient production of new members of this materials class, such as fused oligothiophenes, and study their behavior in the solid state as it relates to important device applications such as organic thin film transistors (OTFTs). These structure types also find application in the construction of porous solids for applications ranging from gas storage to catalysis.