The interactions between building units govern both the structural integrity and processability of porous materials. This study introduces a new class of porous framework materials constructed through precisely modulated ion–dipole interactions, which overcome the challenges posed by the strong solvation effects and non-directionality of alkali metal ions. We employ an assembly strategy employing anionic silicate R[SiO4]− clusters as structural units, where their high charge density and optimal Lewis basicity enable efficient cation binding, even in competitive solvent environments. Single crystal X-ray diffraction (SCXRD) reveals well-defined silicate cage-based framework architectures, while comprehensive characterization demonstrates the simultaneous retention of molecular-scale host-guest recognition in solution and framework-level gas adsorption properties in the solid state. One of the silicate cage-based framework, MeSi-K, exhibits exceptional separation potential for C2H2/C2H4 with an IAST selectivity reaching as high as 7.2, benefiting from electrostatic interactions and π-complexation between C2H2 and the alkali metal ions. The crystallinity porous solid, exhibiting selective gas separation performance, can be easily regenerated through solvent removal. This work establishes a new paradigm for utilizing ion–dipole interactions to construct porous materials, opening exciting possibilities for developing multifunctional materials with tailored properties.
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