The self-assembly of a series of dehydro[24]-annulene derivatives into columnar stacks has been examined for its latent ability to form pi-conjugated carbon-rich nanotubular structures through topochemical polymerizations. We have studied the parameters affecting self-assembly, including the nature of the substituent and crystallization conditions, using 10 different dehydro[24]annulene derivatives. In particular, hydrogen-bonding interactions through carbamate groups were found to be especially useful at directing the formation of nanotubular supramolecular assemblies. We have also evaluated the electronic coupling between neighboring dehydroannulene molecules within these supramolecular assemblies. Density functional calculations on the stacked supramolecular nanotube assemblies show that transfer integrals vary considerably between the three columnar assemblies, ranging from moderate to high (59-98 meV for the highest occupied molecular orbitals, 63-97 meV for the lowest unoccupied molecular orbitals), depending on the local molecular topology. In addition, the dehydro[24]annulene derivatives afforded distinct architectures in the crystal, including nanochannel arrays, sheets with solvent-filled pores, and lamellae. This work is an essential step toward a controlled formation of covalently linked carbon-rich nanostructures generated from molecular precursors with a latent diacetylene reactivity.