Ordered Microporous Layered Lanthanide 1,3,5‐Benzenetriphosphonates Pillared with Cationic Organic Molecules

Novel isomorphous pillared‐layer‐type crystalline lanthanide 1,3,5‐benzenetriphosphonates were prepared with bpy and dbo as organic pillars (LnBP‐bpy and LnBP‐dbo; Ln: Ce, Pr, and Nd). Ab initio crystal structure solution using synchrotron X‐ray powder diffraction data revealed that the organic pillars do not exist as neutral coordinating ligands but as cationic molecules. Especially the LnBP‐dbo phases have ordered interlayer space filled with water molecules between the dbo pillars, and the interlayer water is successfully removed by heating under vacuum with slightly distorted but basically retained pillared layer structures. Microporosity of the materials is confirmed by adsorption of nitrogen, carbon dioxide, and hydrogen gases. Such microporous layered metal phosphonates pillared with cationic molecules should be unprecedented and should offer new strategies to design ordered microporous materials.