Nanocage-Based In^III{Tb^III}₂-Organic Framework Featuring Lotus-Shaped Channels for Highly Efficient CO₂ Fixation and I₂ Capture

Abstract

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 Å2, 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.

Lanthanide Coordination Polymers through Design for Exceptional Catalytic Performances in CO2 Cycloaddition Reactions

“…To assess the maneuvering performance, yields of the reactions using 0.50 and 0.031 mol % of the catalysts were additionally determined using mesitylene as the internal standard (entry 6 and 19), disclosing the satisfying values of >80% for Ib and >74% for IIb (Figures S11–S14). Compared with the other CPs/MOFs used in the reactions conducted under ambient CO 2 pressure and solvent-free condition (Table S7), ,− the TONs and TOFs reported here are worth noting as they are among the top-tier. In general, a long reaction time was required if complete conversion and high TONs were to be achieved, which on the other hand would aggravate the corresponding TOFs.…”

A Facile Strategy for Constructing a Carbon‐Particle‐Modified Metal–Organic Framework for Enhancing the Efficiency of CO2 Electroreduction into Formate

“…[Me 2 NH 2 ] + as the counterions were generated from the decomposition of DMF under high temperature conditions,w hich was also demonstrated in the reported literature. [28] Tr eating In III as node,a nd BCP 4À ligand as linker,t he framework can be simplified as a(4,4)-connected und-type topology via TOPOS (Figure 1c). There are two types of 1D open channels with ad iameter of 12 and 16 along c direction in V11 (Figure 1d).…”

Indium–Organic Framework with soc Topology as a Versatile Catalyst for Highly Efficient One-Pot Strecker Synthesis of α-aminonitriles

“…Since then, several indium and non-indium based catalysts were developed for this reaction. However, only a few SBUs such as monomeric [In­(CO 2 ) n ] h , trimeric [In 3 O­(CO 2 ) n (OH 2 ) n ], and chain-like [In­(O or OH)] n have been employed and new InOFs with novel structures and fine-designed functionalization are highly desirable. ,− …”