Two Novel Nanoporous Supramolecular Architectures Based on Copper(I) Coordination Polymers with Uniform (8, 3) and (8210) Nets: In Situ Formation of Tetrazolate Ligands

The hydro/solvothermal reactions of Cu(I)/Cu(II) salt, NaN3, and acetonitrile in water or methanol yield two noninterpenetrated supramolecular networks containing 1D hexagonal and square nanochannels, {[Cu(Mtta)]·0.17H2O}n (1) and its pseudopolymorph [Cu(Mtta)]n (2) (Mtta = 5-methyl tetrazolate), involving ligand in-situ formation by cycloaddition of nitriles and azides. The copper(I) centers in both complexes are all bridged by Mtta ligands, forming the different shapes of the cavity. 1 exhibits an unprecedented uniform (8, 3) topological metal network, whereas 2 is a 3-connected (8210) metal net.