Over the past several years, columnar liquid crystals have been the focus of extensive investigations, driven in large part by of their potential use as organic semiconductors. Although the molecules that form these phases are typically monomeric aromatic compounds, columnar phases can also arise from the self-assembly of dimers comprised of two aromatic discs covalently linked by a flexible spacer. These "discotic dimers" are especially attractive because they exhibit a strong tendency to form anisotropic glasses that maintain liquid crystalline ordering at room temperature. Because molecular shape is one of the principal factors governing the formation of liquid crystal phases, rigid molecules are often preferred starting points in the design of new materials. In contrast, it is much harder to predict the shape, and hence the mode of self-assembly, of flexible molecules such as discotic dimers. For this reason, molecules capable of adopting multiple conformations tend to make less reliable building blocks. Elucidating the factors that govern the conformational dynamics of discotic dimers therefore is essential if these molecules are to be systematically exploited as new materials. In the course of investigating the effects of conformational dynamics on the self-assembly of discotic dimers, we have discovered a new class of molecules that adopt tightly folded intramolecular pi-stacked structures both in solution and in the liquid crystal phase. The LC phases of these compounds exist over broad temperature ranges, exhibit uniform alignment and supercool into ordered glasses. Significantly, their strong tendency to adopt a specific folded conformation makes this class of molecules a dependable structural motif that self-assembles in a predictable manner. Moreover, because the linking group can subtly alter the overall shape of these dimers, it is possible to rationally fine-tune their electronic properties and self-assembly. We will report on our latest efforts to understand the structural features that govern the folding of these compounds in solution and in the liquid crystal phase.