Using Postsynthetic X-Type Ligand Exchange to Enhance CO₂ Adsorption in Metal-Organic Frameworks with Kuratowski-Type...

Postsynthetic modification methods have emerged as indispensable tools for tuning the properties and reactivity of metal-organic frameworks (MOFs). In particular, postsynthetic X-type ligand exchange (PXLE) at metal building units has gained increasing attention as a means of immobilizing guest species, modulating the reactivity of framework metal ions, and introducing new functional groups. The reaction of a Zn-OH functionalized analogue of CFA-1 (1-OH, Zn(ZnOH)₄(bibta)₃, where bibta^2- = 5,5'-bibenzotriazolate) with organic substrates containing mildly acidic E-H groups (E = C, O, N) results in the formation of Zn-E species and water as a byproduct. This Brønsted acid-base PXLE reaction is compatible with substrates with pK_a(DMSO) values as high as 30 and offers a rapid and convenient means of introducing new functional groups at Kuratwoski-type metal nodes. Gas adsorption and diffuse reflectance infrared Fourier transform spectroscopy experiments reveal that the anilide-exchanged MOFs 1-NHPh and 1-NHPh exhibit enhanced low-pressure CO₂ adsorption compared to 1-OH as a result of a Zn-NHPh + CO₂ ⇌ Zn-O₂CNHPh chemisorption mechanism. The MFU-4l analogue 2-NHPh ([Zn₅(OH)_2.1(NHPh)_1.9(btdd)₃], where btdd^2- = bis(1,2,3-triazolo)dibenzodioxin), shows a similar improvement in CO₂ adsorption in comparison to the parent MOF containing only Zn-OH groups.