Nanocage-Based In^III{Tb^III}₂-Organic Framework Featuring Lotus-Shaped Channels for Highly Efficient CO₂ Fixation and...

The exquisite combination of independent 3p [In(CO₂)₄] units and 4f [Tb₂(CO₂)₈] clusters in the presence of the designed hexatopic 2,4,6-tri(2,4-dicarboxyphenyl)pyridine ligand engenders one peculiar nanocaged In(III){Tb(III)}₂-organic framework: ({(Me₂NH₂)[InTb₂(HTDP)₂]·3DMF·3H₂O}_n, designated as NUC-5), which features dual types of lotus-shaped channels along the [100] and [110] axes with related node windows of 5.3 × 6.8 and 12.1 × 9.2 Ų, respectively. To the best of our knowledge, except several coexisted 3p-4f In/Ln clusters of {In₃Ln}- and {In₃Ln₂}-based metal-organic frameworks (MOFs), NUC-5 is one novel type of In/Ln heterometallic framework. In addition, its topology was an unprecedented 3D TAYZIC net with a Schläfli symbol of {4.⁴6²}{4.⁵6⁵}₂{4.⁶6.⁸8}. Moreover, activated NUC-5 is proved to be one efficient adsorbent for CO₂ and one recycled cycloaddition catalyst for the transformation of epoxides into related carbonates with high yields under mild conditions. Furthermore, the excellent reversible sorption performance for I₂ in the volatilization phase or in cyclohexane solution with a maximum adsorption capacity of 609.1 mg/g (3.75 iodine molecules per unit cell) makes NUC-5 a promising adsorbent for radioactive products of ¹²⁹I and ¹³¹I in the field of nuclear industry. This study provides one synthetic strategy that the original nature of MOFs could be enhanced by introducing some specific function-prompted inorganic subunits with the aid of predesigned supporting ligands.