Star-shaped oligobenzoates with naphthalene chromophores assemble in columnar mesophases. In the low-temperature phases, mesogens self-organize helically along the columns, leading to columnar liquid crystal phases with 3D order (see image). The formation of these structures is driven by optimization of space-filling and nanosegregation. Naphthalene chromophores are segregated in the center of the columns and operate as hopping sites for charges.