Self-Assembly of Discrete and Polymeric Metal-Organic Frameworks via a Semirigid Glycoluril-Based Molecular Clip

Glycoluril-based molecular clip L bearing two N,N′-chelating sites and a rigid cavity has been prepared. With L, one metallomacrocycle and three metal-organic frameworks, [Cu(L)(OAc)₂(H₂O)·2H₂O]_n (1), [Co(L)₂(NO₃)₂(H₂O)₂·4H₂O]_n (2), [Zn(L)₂(NO₃)₂(H₂O)₂·7H₂O]_n (3), and [Cu(L)(I)·DMF]_n (4) were crystallized, which display three different structure types. In 1, two ligands are arranged in a face-to-face conformation to coordinate two Cu(II) ions from opposite directions through axial positions, generating a pesudo-rectangular metallomacrocycle. Polymer 2 is an 1D double ribbons. Interestingly, each double ribbons is connected by hydrogen bond with the result that the channels are formed and run parallel to the ab diagonal, and the water chains with the symbol C4 are located within the channels. Polymer 3 exhibits the same topological morphology as polymer 2. However, each double ribbons in 3 is connected by a different type of hydrogen bond with the result that the channels are formed along the b axis. Polymer 4 is a two-dimensional (2D) tubular sheet constructed by an unprecedented [CuI]_∞ column and clip ligand L. The type of the [CuI]_∞ column can be described as a zigzag chain and has been rarely reported. The DMF solvent molecules are located within the channels.