Triply phenanthryl‐ and tetrahelicenyl‐substituted triazine‐hexaalkyl esters with short alkyl chains show glass transitions conveniently above room temperature within the hexagonal columnar liquid crystalline state, resulting in a solid columnar order at room temperature. As the hexagonal columnar mesophase is easily aligned with the director perpendicular to a solid substrate, such glassy columnar liquid matrices are aimed at for the orientation of guest emitters, to obtain anisotropic emission. A condition for face‐on alignment on substrates are attainable melting and clearing temperatures, which is achieved with the moderately nonplanar tetrahelicenyl derivatives in spite of their short alkyl periphery. An unusual phase transition between two columnar mesophases of same hexagonal symmetry, but very different long‐distance regularity of the column lattice, is found in one phenanthryl homolog.

Most organic room‐temperature phosphorescence (RTP) emitters do not show their RTP in solution. Here, we incorporated sulfur‐containing thiophene bridges between the donor and acceptor moieties in D3A‐type tristriazolotriazines (TTTs). The thiophene inclusion increased the spin‐orbit coupling associated with the radiative T1→S0 pathway, allowing RTP to be observed in solution for all compounds, likely assisted by protection of the emissive TTT‐thiophene core from the environment by the bulky peripheral donors.

Columnar liquid crystals with very small molecular masses that form anisotropic glasses well above room temperature are obtained by mixed dissymmetric substitution of sym‐triazine with ester‐bearing phenyl and phenanthryl or tetrahelicenyl moieties. The combination of low molecular symmetry with configurational flexibility and short polar ester moieties stabilizes the mesophase over large temperature ranges and induces pronounced calorimetric glass transitions within the anisotropic fluid despite the smallness of the molecules. In contrast to more symmetrical homologs, no ester tails longer than ethyl are necessary to induce the liquid crystalline state, allowing for the near‐absence of any insulating and weight‐increasing alkyl periphery. Films drop‐cast from solution show in all cases emission spectra that do not show significant change of fluorescence emission upon annealing, indicating that the columnar hexagonal mesoscopic order is obtained directly upon deposition from solution and is resistant to crystallization upon annealing.