Two Zn^II Metal‐Organic Frameworks with Coordinatively Unsaturated Metal Sites: Structures, Adsorption, and Catalysis

Assembly of Zn(NO₃)₂ with the tripodal ligand H₃TCPB (1,3,5‐tri(4‐carboxyphenoxy)benzene) affords two porous isoreticular metal‐organic frameworks, [Zn₃(TCPB)₂⋅2DEF]⋅ 3DEF (1) and [Zn₃(TCPB)₂⋅2H₂O]⋅ 2H₂O⋅4DMF (2). Single‐crystal X‐ray diffraction analyses reveal that 1 crystallizes in the monoclinic space group P2₁/c and possesses a 2D network containing 1D microporous opening channels with an effective size of 3.0×2.9 Ų, whereas 2 crystallizes in the trigonal space group ${P\bar 3}$ c1 and also possesses a 2D network containing 1D channels, with an effective aperture of 4.0×4.0 Ų. TOPOS analysis reveals that both 1 and 2 have a (3,6)‐connected network topology with the Schläfli symbol of (4³⋅6¹²) (4³)₂. According to the variable‐temperature powder X‐ray diffraction patterns, the solid phase of 1 can be converted into that of 2 during a temperature‐induced dynamic structural transformation, thus indicating that the framework of 2 represents the most thermally stable polymorph. Desolvated 2 exhibits highly selective adsorption behaviors toward H₂/N₂, CO₂/N₂, and CO₂/CH₄; furthermore, it displays size‐selective catalytic activity towards carbonyl cyanosilylation and Henry (nitroaldol) reactions.