The Effect of Pendent Groups upon Flexibility in Coordination Networks with Square Lattice Topology

Gas or vapor-induced phase transformations in flexible coordination networks (CNs) offer the potential to exceed the performance of their rigid counterparts for separation and storage applications. However, whereas ligand modification has been used to alter the properties of such stimulus-responsive materials, they remain understudied compared with their rigid counterparts. Here, we report that a family of Zn²⁺ CNs with square lattice (sql) topology, differing only through the substituents attached to a linker, exhibit variable flexibility. Structural and CO₂ sorption studies on the sql networks, [Zn(5-Ria)(bphy)]_n, ia = isophthalic acid, bphy = 1,2-bis(pyridin-4-yl)hydrazine, R = −CH₃, −OCH₃, −C(CH₃)₃, -N═N-Ph, and -N═N-Ph(CH₃)₂, 2-6, respectively, revealed that the substituent moieties influenced both structural and gas sorption properties. Whereas 2-3 exhibited rigidity, 4, 5, and 6 exhibited reversible transformation from small pore to large pore phases. Overall, the insight into the profound effect of pendent moieties of linkers upon phase transformations in this family of layered CNs should be transferable to other CN classes.