An Ultramicroporous Physisorbent Sustained by a Trifecta of Directional Supramolecular Interactions

2D and 3D porous coordination networks (PCNs) as exemplified by metal-organic frameworks, MOFs, have garnered interest for their potential utility as sorbents for molecular separations and storage. The inherent modularity of PCNs has enabled the development of crystal engineering strategies for systematic fine-tuning of pore size and chemistry in families of related PCNs. The same cannot be said about one-dimensional (1D) coordination polymers, CPs, which are understudied with respect to porosity. Here, we report that permanent porosity is exhibited by the previously reported family of linear (L) 1D porous CPs, PCPs, of formula [M(bipy)(NO₃)₂(H₂O)₂]n (L-chn-1-M-NO3: M = Co, Ni; bipy = 4,4'-bipyridine). Their pore structure comprises 1D channels sustained by three types of directional interaction: coordination bonds; hydrogen bonds; offset π-π interactions. Heating L-chn-1-M-NO3 in vacuo or above 383 K resulted in removal of the aqua ligands and concomitant transformation to nonporous anhydrate phases ZZ-chn-1-Co-NO3 (ZZ = zigzag) and HT-Ni. Exposure of these anhydrate phases to ambient humidity resulted in regeneration of L-chn-1-M-NO3. That L-chn-1-M-NO3 exhibits permanent porosity was supported by CO₂ and water sorption measurements, which afforded reversible type I and stepped (S-shaped) isotherm profiles, respectively, making this work the first demonstration of reversible water sorption in a 1D PCP. The water sorption properties are pertinent to atmospheric water harvesting: onset of uptake at ca. 12% relative humidity; activation required only mild heat or vacuum; relatively fast adsorption/desorption kinetics; performance retained over >100 adsorption/desorption cycles. We project water harvesting productivity of L-chn-1-M-NO3 of 3.3 L kg^-1 d^-1, on par with some leading MOF desiccants. DFT and Monte Carlo simulations provide insights into the structure of water molecules in the channels, provide their influence on the host framework, and provide a plausible argument for the experimental water vapor isotherms. This work demonstrates that easily scalable 1D PCPs, a potentially vast class of materials, can exhibit porous structures sustained by three types of directional supramolecular synthons and offer desirable water sorption properties.