Molecules that use non-covalent interactions to self-organize into supramolecular structures have the potential to generate functional materials with a broad range of applications. This review article focuses on the design and synthesis of molecules that use transition metal ions and long alkyl chains to direct the formation of ordered supramolecular phases. This unique combination of coordination bonds and alkyl interdigitation provide exceptional control over intermolecular interactions and can generate nanoscale molecular order as liquid crystalline states, Langmuir-Blodgett films on surfaces, highly ordered lyotropic phases such as metallo-micelles in water and reverse metallo-micelles in organic media. The synthetic strategy for alkane-rich ligands and the coordination- and lipid-directed self-assembly of these molecules are described.