Porosity switching in the crystalline solid state is a unique phenomenon observed only in a limited number of materials. The switching behavior of two metal-organic frameworks as well as their respective solid solutions of composition [Zn₂(BME-bdc)_x(DB-bdc)_2-xdabco]_n (x = 2; 1.5; 1.0; 0.5; 0) is studied in situ during the adsorption of CO₂ and Xe using X-ray diffraction and NMR techniques. The diffraction data, measured during the adsorption suggest a direct one-step phase transition (switching) from the narrow pore phase to the large pore phase beyond the transition pressure. An intermediate phase was found only in one compound within a narrow pressure range around the phase transition pressure region. In situ high-pressure ¹³C NMR spectroscopy of adsorbed CO₂ also allowed following the gating behavior of the studied materials by monitoring the signal of adsorbed CO₂. The ¹³C NMR spectra exhibit a pronounced broadening indicating a certain degree of order for the adsorbed molecules inside the pores. This ordering effect and the resulting line broadening depend on the linker functionalization as could be confirmed by corresponding molecular dynamics (MD) simulations.