Recent advances in TPT-based crystalline hybrid materials: from structural design to functional applications

2,4,6-Tri(4-pyridyl)-1,3,5-triazine (TPT), featuring a rigid C 3 -symmetric π-conjugated skeleton, an electron-deficient triazine core, and three pyridyl coordination sites, has emerged as a powerful building block for the construction of crystalline hybrid materials. The unique combination of coordination capability, electronic characteristics, and supramolecular recognition ability enables TPT to integrate metal ions, inorganic clusters, auxiliary ligands, and molecular guests into diverse architectures, including metal–organic cages (MOCs), metal–organic frameworks (MOFs), and cocrystalline assemblies. This review provides a comprehensive overview of the structural engineering and functional applications of TPT-based crystalline materials, with emphasis on the relationship between strategies, structural features, and emergent properties. The intrinsic structural characteristics and assembly principles of TPT are first introduced, followed by a discussion of how metal coordination, auxiliary-ligand regulation, and supramolecular interactions govern the formation of diverse crystalline architectures. Representative MOCs, MOFs, and cocrystalline systems are then summarized, highlighting their structural diversity and functional evolution. Particular attention is devoted to their applications in stimuli-responsive behaviors, luminescence and sensing, gas adsorption and separation, catalysis, and crystalline sponge-based molecular recognition, with a focus on how precise structural regulation enables tailored performance. Finally, current challenges and future perspectives toward the rational design, multifunctional integration, and mechanism-driven development of TPT-based crystalline materials are discussed. This review aims to provide fundamental insights into the structural versatility of TPT and inspire the development of advanced crystalline platforms with programmable functions.