Modulation of the Sorption Characteristics for an H‐bonded porous Architecture by Varying the Chemical Functionalization of the Channel Walls

Five isostructural microporous supramolecular architectures prepared by H‐bonded assembly between the hexa‐anionic complex [Zr(2)(Ox)(7)](6−) (Ox=oxalate, (C(2)O(4))(2−)) and tripodal cations (H(3)‐TripCH(2)‐R)(3+) with R=H, CH(3), OH and OBn (Bn=CH(2)Ph) are reported. The possibility to obtain the same structure using a mixture of tripodal cations with different R group (R=OH and R=CH(3)) has also been successfully explored, providing a unique example of three‐component H‐bonded porous framework. The resulting SPA‐1(R) materials feature 1D pores decorated by R groups, with apparent pore diameters ranging from 3.0 to 8.5 Å. Influence of R groups on the sorption properties of these materials is evidenced through CO(2) and H(2)O vapor sorption/desorption experiments, as well as with I(2) capture/release experiments in liquid media. This study is one of the first to demonstrate the possibility of tuning the porosity and exerting precise control over the chemical functionalization of the pores in a given H‐bonded structure, without modifying the topology of the reference structure, and thus finely adjusting the sorption characteristics of the material.