Water Sorption Evolution Enabled by Reticular Construction of Zirconium Metal–Organic Frameworks Based on a Unique [2.2]Paracyclophane Scaffold

Water vapor sorption by metal-organic frameworks (MOFs) has gathered significant interest because of its prominent potential in many applications such as moisture harvesting, dehumidification, heat pump regulation, and hydrolysis catalysis. However, the reticular design and exploration of robust and high-performing Zr-MOFs for such purposes remains a sought-after endeavor. In this work, we present the deployment of reticular chemistry to target a series of robust Zr-MOFs based on a unique [2.2]paracyclophane (PCP) scaffold. The ease of functionalization of PCP enables the desired synthesis of three carboxylate linkers, one ditopic and two tetratopic, which further assemble into a total of five Zr-MOFs with distinct topological structures, i.e., a new 2D net (NU-700), fcu (NU-405), flu (NU-1800), she (NU-602), scu (NU-913). Notably, the water vapor sorption performances of all the Zr-MOFs are highly dependent on their framework topology and pore metric, in which NU-602 and NU-913 with uniform 1D channels exhibit S-shaped water sorption isotherms with a steep pore-filling step and high uptake capacities of 0.72 g g^-1 at 70% relative humidity (RH) and 0.88 g g^-1 at 60% RH, respectively. Moreover, NU-913 displays exceptionally high working capacity of 0.72 g g^-1 in the range of 40-60% RH. Additionally, we demonstrate that the hydrolytic stability and water adsorption-desorption recyclability of NU-913 can be remarkably improved by capping the Zr₆ nodes with the more hydrophobic agent, trifluoroacetic acid, making it a potential candidate for water sorption-based applications.