A porous Ni(II)-MOF, which was constructed from a new bent fluorene-bridged ligand and NiCl2 under solvothermal conditions, can reversibly uptake organic solvent molecules and iodine species in a single-crystal-to-single-crystal (SC–SC) fashion. Furthermore, the obtained I2⊂Ni(II)-MOF can be a highly active heterogeneous catalyst to promote solvent-free silylcyanation of aromatic aldehydes under mild conditions.
