Modulation of Water Vapor Sorption by Pore Engineering in Isostructural Square Lattice Topology Coordination Networks

High Resolution Image Download MS PowerPoint Slide We report a crystal-engineering study conducted upon a platform of three mixed-linker square lattice ( sql ) coordination networks of general formula [Zn(Ria)(bphy)] [bphy = 1,2-bis(pyridin-4-yl)hydrazine, H 2 Ria = 5-position-substituted isophthalic acid, and R = –Br, –NO 2, and –OH; compounds 1 – 3 ]. Analysis of single-crystal X-ray diffraction data of 1 – 2 and the simulated crystal structure of 3 revealed that 1 – 3 are isomorphous and sustained by bilayers of sql networks linked by hydrogen bonds. Although similar pore shapes and sizes exist in 1 – 3, distinct isotherm shapes (linear and S shape) and uptakes (2.4, 11.6, and 13.3 wt %, respectively) were observed. Ab initio calculations indicated that the distinct water sorption properties can be attributed to the R groups, which offer a range of hydrophilicity. Calculations indicated that the significantly lower experimental uptake in compound 1 can be attributed to a constricted channel. The calculated water-binding sites provide insights into how adsorbed water molecules bond to the pore walls, with the strongest interactions, water–hydroxyl hydrogen bonding, observed for 3 . Overall, this study reveals how pore engineering can result in large variations in water sorption properties in an isomorphous family of rigid porous coordination networks.