Tetrazole-based porous metal-organic frameworks for selective CO adsorption and isomerization studies.

Tetrazole-based molecules have numerous bridging coordination modes which afford great synthetic possibilities for the preparation of porous metal-tetrazolate architectures for many applications, such as carbon capture. We reported here three tetrazole-based MOFs: 1, {[Cu(ttz)Cl(HO)]·11Cl} (Httz = N,N,N-tris(4-(1H-tetrazol-5-yl)phenyl)-1,3,5-triazine-2,4,6-triamine), contains highly positively charged Cu clusters and the largest mesopores (32 Å) among the reported MOFs based on a tri-topic tetrazole ligand. 2 and 3 are two MOF isomers built by using Cu and 2-(1H-tetrazol-5-yl)pyrimidine. 3 contains nonporous layers, while 2 contains 1D channels and showed high selectivity for adsorbing CO, which should be attributed to the high density of free nucleophilic tetrazole N atoms on the pore surfaces. We found that the isomerization between 2 and 3 was caused by the diverse coordination modes of tetrazole-based ligands and can be controlled in synthesis processes.