2D and 3D metal-organic frameworks constructed with a mechanically rigidified [3]rotaxane ligand.

ABSTRACT

A mechanically interlocked [3]rotaxane was newly designed, synthesized, and employed as a ligand for constructing metal-organic frameworks (MOFs). The nano-confinement by macrocycles forces the soft bis-isophthalate axle into a pseudo-rigid conformation and coordinates to zinc(II) ions, affording a two- or three-dimensional MOF under controlled conditions. The 2D MOF exhibits a neutral framework with a periodic puckering sheet structure, while an anionic framework with a pts topology was observed for the 3D MOF. The phase purity of both bulk materials was confirmed by powder X-ray diffraction. Thermogravimetric analysis reveals that both materials are stable up to 250 °C. The success of applying mechanical bonds to rigidify flexible ligands provides new insights for the design of metal-organic frameworks.