Nanochannel {InZn}-Organic Framework with a High Catalytic Performance on CO2 Chemical Fixation and Deacetalization-Knoevenagel Condensation

The rare combination of In-III 5p and Zn-II 3d in the presence of a structureoriented TDP6- ligand led to a robust hybrid material of {(Me2NH2)[InZn(TDP)(OH2)]center dot 4DMF center dot 4H(2)O}(n) (NUC-42) with the interlaced hierarchical nanochannels (hexagonal and cylindrical) shaped by six rows of undocumented [InZn(CO2)(6)(OH2)] clusters, which represented the first 5p-3d nanochannel-based heterometallic metal-organic framework. With respect to the multifarious symbiotic Lewis acid-base and Bronsted acid sites in the high porous framework, the catalytic performance of activated NUC-42a upon CO2 cycloaddition with styrene oxide was evaluated under solvent-free conditions with 1 atm of CO2 pressure, which exhibited that the reaction could be well completed at ambient temperature within 48 h or at 60 degrees C within 4 h with high yield and selectivity. Moreover, because of the acidic function of metal sites and a central free pyridine in the TDP6- ligand, deacetalization-Knoevenagel condensation of acetals and malononitrile could be efficiently facilitated by an activated sample of NUC-42a under lukewarm conditions.

Automated summary

A robust hybrid material of {(Me2NH2)[InZn(TDP)(OH2)]center dot 4DMF center dot 4H(2)O}(n) (NUC-42) was developed, featuring interlaced hierarchical nanochannels shaped by six rows of undocumented [InZn(CO2)(6)(OH2)] clusters, representing the first 5p-3d nanochannel-based heterometallic metal-organic framework. The catalytic performance of activated NUC-42a was evaluated for CO2 cycloaddition with styrene oxide and deacetalization-Knoevenagel condensation reactions, showing high efficiency under mild conditions.