A highly robust cluster-based indium(iii)–organic framework with efficient catalytic activity in cycloaddition of CO2 and Knoevenagel condensation

Abstract

The efficient catalytic performance displayed by MOFs is decided by an appropriate charge/radius ratio of defect metal sites, large enough solvent-accessible channels and Lewis base sites capable of polarizing substrate molecules. Herein, the solvothermal self-assembly led to a highly robust nanochannel-based framework of {[In₄(CPDD)₂(μ₃-OH)₂(DMF)(H₂O)₂]·2DMF·5H₂O}_n (NUC-66) with a 56.8% void volume, which is a combination of a tetranuclear cluster [In₄(μ₃-OH)₂(COO)₁₀(DMF)(H₂O)₂] (abbreviated as {In₄}) and a conjugated tetracyclic pentacarboxylic acid ligand of 4,4′-(4-(4-carboxyphenyl)pyridine-2,6-diyl)diisophthalic acid (H₅CPDD). To the best of our knowledge, NUC-66 is a rarely reported {In₄}-based 3D framework with embedded hierarchical triangular-microporous (2.9 Å) and hexagonal-nanoporous (12.0 Å) channels, which are shaped by six rows of {In₄} clusters. After solvent exchange and vacuum drying, the surface of nanochannels in desolvated NUC-66a is modified by unsaturated In³⁺ ions, N_pyridine atoms and μ₃-OH groups, all of which display polarization ability towards polar molecules due to their Lewis acidity or basicity. The catalytic experiments performed showed that NUC-66a had high catalytic activity in the cycloaddition reactions of epoxides with CO₂ under mild conditions, which should be ascribed to its structural advantages including nanoscale channels, rich bifunctional active sites, large surface areas and chemical stability. Moreover, NUC-66a, as a heterogeneous catalyst, could greatly accelerate the Knoevenagel condensation reactions of aldehydes and malononitrile. Hence, this work confirms that the development of rigid nanoporous cluster-based MOFs built on metal ions with a high charge and large radius ratio will be more likely to realize practical applications, such as catalysis, adsorption and separation of gas, etc.