Ab Initio Study of Hydrostable Metal–Organic Frameworks for Postsynthetic Modification and Tuning toward Practical Applications

[Image: see text] Metal–organic frameworks (MOFs), a subclass of nanoporous coordination polymers, have emerged as one of the most promising next-generation materials. The postsynthetic modification method, a strategy that provides tunability and control of these materials, plays an important role in enhancing its properties and functionalities. However, knowing adjustments which leads to a desired structure–function a priori remains a challenge. In this comprehensive study, the intermolecular interactions between 21 industrially important gases and a hydrostable STAM-17-OEt MOF were investigated using density functional theory. Substitutions on its 5-ethoxy isophthalate linker included two classes of chemical groups, electron-donating (−NH(2), −OH, and −CH(3)) and electron-withdrawing (−CN, −COOH, and −F), as well as the effect of mono-, di-, and tri-substitutions. This resulted in 651 unique MOF–gas complexes. The adsorption energies at the ground state and room temperature, bond lengths, adsorption geometry, natural bond orbital analysis of the electric structure, HOMO–LUMO interactions, and the predicted zwitterionic properties are presented and discussed. This study provides a viable strategy for the functionalization, which leads to the strongest affinity for each gas, an insight into the role of different chemical groups in adsorbing various gas molecules, and identifies synthetic routes for moderating the gas adsorption capacity and reducing water adsorption. Recommendations for various applications are discussed. A custom Python script to assess and visualize the hypothetical separation of two equal gas mixtures of interest is provided. The methodology presented here provides new opportunities to expand the chemical space and physical properties of STAM-17-OEt and advances the development of other hydrostable MOFs.