A Strong‐Acid‐Resistant [Th6] Cluster‐Based Framework for Effectively and Size‐Selectively Catalyzing Reductive Amination of Aldehydes with N,N‐Dimethylformamide

Utilization of N,N-dimethylformamide (DMF) as an amine source and reductant for synthesizing tertiary amines is a promising way to replace the substrates formaldehyde and dimethylamine, and it is desirable to seek porous acid-resistant catalysts for heterogeneous catalysis of this reaction. Herein, a robust metal-organic framework (MOF) {[Th6 O4 (OH)4 (H2 O)6 (BCP)3 ]⋅10 DMF}n (1) containing stacked nanocages with a diameter of 1.55 nm was constructed. Compound 1 can maintain its single-crystal structure even kept in air at 400 °C for 3 h, and in DMF or water at 200 °C for 7 days. Density functional theory (DFT) calculations suggested that the high interaction energy between the [Th6 O4 (OH)4 (H2 O)6 ]12+ clusters and ligands was responsible for the excellent stability of 1. Catalytic investigations revealed that 1 can effectively and size-selectively catalyze the reductive amination of aldehydes with DMF, and it can be reused at least five times without obvious loss in catalytic activity.