Selective Gas Adsorption and Unique Structural Topology of a Highly Stable Guest‐Free Zeolite‐Type MOF Material with N‐rich Chiral Open Channels

A new multifunctional di‐topic tetrazolate‐based ligand, 2,3‐di‐1 H ‐tetrazol‐5‐ylpyrazine (H 2 dtp) has been designed and synthesized. The solvothermal reaction of this ligand with ZnCl 2 gave a robust guest‐free three‐dimensional zeolite‐like chiral metal‐organic framework (MOF) complex, [Zn(dtp)], which crystallized in chiral space group P 6 1 and possessed chiral open channels with nitrogen‐rich walls and the diameter of approximately 4.1 Å. This framework presents a unique uniform etd (8,3) topology, is the first example of its type in MOFs, and exhibits high thermal stability with the decomposition temperature above 380 °C and permanent porosity. It is interesting that this material is able to selectively adsorb O 2 and CO 2 over N 2 gas, being a rare example in MOFs. In addition, C 2 H 2 and MeOH adsorption results show that although the framework channel holds nitrogen‐rich walls that may provide H‐bonding sites, no N⋅⋅⋅H H‐bond effect between the guest molecules and microporous surface was observed.