In-Situ X-ray Diffraction Studies of Host−Guest Properties in Nanoporous Zinc-Triazolate-Based Framework Materials

Two nanoporous metal−organic framework materials incorporating the exotridentate bridging ligand 3-amino-1,2,4-triazolate (AmTAZ) have been synthesized through variation of secondary bridging anions: [Zn3(AmTAZ)3S](NO3)·(H2O) (1·(H2O)) and Zn7(AmTAZ)8(CO3)2(OH)2·2(EtOH) (2·2(EtOH); EtOH = ethanol). 1·(H2O) crystallizes in the cubic space group I23 and is constructed from triangular Zn3S units that are bridged through AmTAZ ligands into a cationic three-dimensional (3D) network with nitrate and water molecules residing in the cavities. 2·2(EtOH) crystallizes in the monoclinic space group C2/c and shows a complex 3D network constructed from seven crystallographically unique zinc centers bridged by AmTAZ, carbonate, and hydroxide anions. The porous nature of both materials has been explored by thermogravimetric analysis, nitrogen sorption, and in situ synchrotron-based powder X-ray diffraction.