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The selective adsorption of a corrosive gas, SO$_2$, into two microporouspillared paddle-wheel frameworks M(bdc)(ted)0.5 [M = Ni, Zn; bdc =1,4-benzenedicarboxylate; ted = triethylenediamine] is studied by volumetricadsorption measurements and a combination of in-situ infrared spectroscopy andab initio density functional theory (DFT) calculations. The uptake of SO$_2$ inM(bdc)(ted)0.5 at room temperature is quite significant, 9.97 mol/kg at 1.13bar. The major adsorbed SO$_2$ molecules contributing to the isothermmeasurements are characterized by stretching bands at 1326 and 1144 cm$^{-1}$.Theoretical calculations including van der Waals interactions (based on vdW-DF)suggest that two adsorption configurations are possible for these SO$_2$molecules. One geometry involves an SO$_2$ molecule bonded through its sulfuratom to the oxygen atom of the paddle-wheel building unit and its two oxygenatoms to the C-H groups of the organic linkers by formation of hydrogen bonds.Such a configuration results in a distortion of the benzene rings, which isconsistent with the experimentally observed shift of the ring deformation mode.In the other geometry, SO$_2$ establishes hydrogen bonding with -CH$_2$ groupof the ted linker through its two oxygen atoms simultaneously. ThevdW-DF-simulated frequency shifts of the SO$_2$ stretching bands in these twoconfigurations are similar and in good agreement with spectroscopicallymeasured values of physisorbed SO$_2$.In addition, the IR spectra reveal thepresence of another minor species, characterized by stretching modes at 1242and 1105 cm$^{-1}$ and causing significant perturbations of MOFs vibrationalmodes (CH$_x$ and carboxylate groups). This species is more strongly bound,requiring a higher temperature ($\sim$150 $^\circ$C) to remove it than for themain physisorbed species.

Mechanism of preferential adsorption of SO$_2$ into two microporous paddle wheel frameworks M(bdc)(ted)0.5