By auxiliary N-donor ligand-directed assembled, two entangled Co^II-coordination nets have been constructed from 3,3′,5,5′-azobenzenetetracarboxylic acid (H₄abtc), which present a rare 2D→3D polythreading motif constructed from 2-fold (6,3) polymeric layers with thickness being 10.2 Å and a 3-fold interpenetrating pillar-layered framework based on linear trinuclear Co^II-SBUs. In addition, two Co^II-complexes both show an antiferromagnetic coupling by long organic spacers and H₂O bridges, respectively.

A novel armed-polyrotaxane, comprising two interpenetrating chains of rings with arms, is self-assembled from the flexible ligands 3,3′,4,4′-diphenylsulfonetetracarboxylic acid, as an annular linker motif, and 1,2-di(4-pyridyl)ethylene, as linking rods, which further assembles into a 2D ladder network through hydrogen bonding interactions.