Design, Synthesis, and Applications of Emerging Zeolitic Tetrazolate Frameworks.

The development of porous materials with extended cage-like architectures remains a central challenge in chemistry and materials science. Zeolitic tetrazolate frameworks (ZTFs) represent an emerging class of metal-organic frameworks (MOFs) constructed from tetrazolate linkers and transition metal ions. Their topological and porous architectures can be systematically tuned by employing diverse tetrazolate building units. Structurally, ZTFs share similarities with zeolitic imidazolate frameworks (ZIFs), yet the substitution of imidazoles with tetrazolates introduces uncoordinated nitrogen sites. These sites promote unique coordination modes and stronger framework-guest interactions, thereby imparting superior functional properties compared to their ZIF counterparts. Experimental studies demonstrate that ZTFs with uncoordinated nitrogen atoms exhibit remarkable performance in gas adsorption, separation, energy harvesting, and sensing. To the best of our knowledge, this perspective represents the first comprehensive account of ZTFs, encompassing synthetic strategies, structural diversity, coordination chemistry, and emerging applications. Furthermore, we discuss in detail the unique characteristics that distinguish ZTFs from other porous materials and highlight future opportunities for their advancement in materials chemistry.