TY - JOUR
T1 - Modulation of Water Vapor Sorption by Pore Engineering in Isostructural Square Lattice Topology Coordination Networks
AU - Li, Xia
AU - Bezrukov, Andrey A.
AU - Graham, Wells
AU - Sensharma, Debobroto
AU - Kong, Xiang Jing
AU - Thonhauser, Timo
AU - Zaworotko, Michael J.
N1 - Publisher Copyright:
© 2024 The Authors. Published by American Chemical Society.
PY - 2024/7/3
Y1 - 2024/7/3
N2 - 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, H2Ria = 5-position-substituted isophthalic acid, and R = -Br, -NO2, 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.
AB - 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, H2Ria = 5-position-substituted isophthalic acid, and R = -Br, -NO2, 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.
KW - crystal engineering
KW - hydrolytically stable
KW - metal−organic materials
KW - pore chemistry
KW - water sorbents
UR - http://www.scopus.com/inward/record.url?scp=85196647188&partnerID=8YFLogxK
U2 - 10.1021/acsami.4c06412
DO - 10.1021/acsami.4c06412
M3 - Article
C2 - 38902851
AN - SCOPUS:85196647188
SN - 1944-8244
VL - 16
SP - 34402
EP - 34408
JO - ACS Applied Materials and Interfaces
JF - ACS Applied Materials and Interfaces
IS - 26
ER -