Impact of Synthetic Variables on the Structural Diversity of Tb-Carboxylate Frameworks: Gas Adsorption, Magnetism, and Organocatalysis Investigations.

In this work, three unique Tb-carboxylate frameworks with the formula {[Tb(OH)(HO)(abtc)]·2HO} (), {[Tb(abtc)(HO)(DMA)]·HO} () and {[Tb(abtc)(HO)]·HO} (), each displaying structural variations, have been successfully synthesized by the solvothermal reactions of Tb(NO)·6HO with the azo-containing ligand 3,3',5,5'-azobenzene tetracarboxylic acid (Habtc) under varying conditions. Detailed single-crystal X-ray diffraction (SC-XRD) analysis manifested a remarkable diversity in these structures, demonstrating various coordination patterns of Tb-metal nodes with the carboxylate groups of the organic linker, which contributed to the generation of intricate three-dimensional (3D) coordination networks with remarkable chemical resistance. Furthermore, frameworks and , characterized by porous networks containing two and three independent Tb-metal nodes, respectively, were both demonstrated to be efficient heterogeneous catalysts toward the cyanosilylation of imines under mild conditions with excellent reusability. In addition, direct current () magnetic susceptibility measurements conducted on frameworks , , and indicated that there were obvious antiferromagnetic interactions among the Tb-metal nodes, which suggests the involvement of intricate - and exchange channels, adding another fascinating dimension to their physical properties.