Non‐Covalent Interactions Enable Hierarchical Self‐Assembly in TeTrazine‐Bearing Systems: From Soft Matter to Mesogens

ABSTRACT Tetrazines are heterocyclic aromatic molecules with notable properties, such as elevated electron affinity, yet their supramolecular self‐assembly properties are scarcely investigated. In this work, a novel family of compounds featuring a central tetrazine core is presented, where structure‐property relations are established upon introducing linear or branched chiral side chains. Different non‐covalent interactions enable self‐assembly in the system, where H bonding emerges as the main driving force responsible for the aggregation process, leading to the formation of supramolecular gel networks that are characterized by rheology. Additionally, in the solid state, the presence of liquid crystals is explored, highlighting the formation of columnar mesophases, reported here for the first time in tetrazine‐bearing species. This study provides fundamental structure—self‐assembly properties in the liquid and solid state, highlighting the relevance of non‐covalent interactions.