Improving the Stability and Visualizing the Structural Transformation of the Stimuli-Responsive Metal-Organic Frameworks (MOFs).

New metal-organic frameworks (MOFs) based on flexible tetra-carboxylate ligands and Cu(II) are designed to gain stimuli-responsive materials. Unstable MOFs can be more stable with unabated flexibility by replacing coordinated solvent molecules with auxiliary N-based ligands. Two of them are intensively studied by in situ single-crystal X-ray diffraction (SCXRD) analysis and the unit cell parameters during transformations have been observed in detail. They undergo exceptional structural transformations which can be divided into two processes: the thermal-responsive phase transition and the solvent-responsive phase transition. The thermal-responsive phase transition takes place in a narrow temperature interval reversibly. However, the solvent-responsive phase transition is a gradual and irreversible process. The stimuli-responsive mechanism has also been explored by comparing the parameters of the crystal structures under different temperatures. Fascinatingly, their exceptional structural transformations correlate with the flexibility of the ligand fragments and the [Cu2(RCOO)4] clusters.