Porous and Nonporous Coordination Polymers Induced by Pseudohalide Ions for Luminescence and Gas Sorption

The three-dimensional (3D) coordination polymers [Cd(tpmd)(NCX)₂] [X = O (1), S (2), and BH₃ (3); tpmd = N,N,N',N'-tetrakis(pyridin-4-yl)methanediamine] have been determined to display their network structures through coordinated anionic ligands. Polymers 1 and 2 show nonporous structures, whereas polymer 3 shows a porous coordination framework. On the basis of the Cd(II) network structures, the 3D coordination polymer [Zn(tpmd)(NCBH₃)₂]·nMeOH (4) was self-assembled. In the cases of polymers 1 and 2, pseudohalide ions acted to form nonporous network structures; however, in polymers 3 and 4, NCBH₃^- helps to construct porous network structures. Polymers 1-4 show strong ultraviolet luminescence emissions, depending on the pseudohalide ions present, compared to the tpmd ligands. Interestingly, coordination polymers 3 and 4 that possess NCBH₃^- ions exhibit high porosities and gas sorption properties. The polymers appeared to absorb N₂, H₂, CO₂, and CH₄. In the case of polymer 4, the structure is almost identical with that of polymer 3, except for the Cd(II) ion. However, polymer 4 has a larger void volume and higher gas absorption ability for N₂ gas than polymer 3. For the sorption of gases, polymers 3 and 4 showed similar behaviors.