Supramolecular inclusion of a pillared double-layered host by an anion-directed second-sphere coordination

In this paper, we have illustrated the utilisation of a second-sphere coordination approach to construct supramolecular inclusion solids with varieties of guest molecules. A flexible molecule N,N,N',N'-tetra-p-methylbenzyl-ethylenediamine (L1) bearing doubly protonated H-bond donors was designed, capable of forming N-H...Cl hydrogen bonds with a crystallographically unique chloride anion, to construct an anion-directed ligand. The pillared double-layered host framework was constructed by an anion-directed ligand and primary coordination sphere [CoCl4]2- through weak C-H...Cl hydrogen-bonding interactions. A variety of guest molecules, such as p-anisaldehyde, 1,4-dimethoxy-2,5-bis(methoxymethyl)benzene, can be included, leading to the formation of novel supramolecular inclusion solids: [L1]center dot 4[H]+center dot[CoCl4]2-center dot 2Cl-center dot 1.5[C8H8O2]center dot 0.25[CH3OH] (1) and [L1]center dot 4[H]+center dot[CoCl4]2-center dot 2Cl-center dot 1.5[C12H20O4]center dot 0.5[CH3OH] (2). [image omitted]We have presented herein the utilisation of a second-sphere coordination approach to construct supramolecular inclusion solids with a variety of guest molecules. A novel type of a pillared double-layered host framework was constructed by a second-sphere coordination between the anion-directed ligand (L1=N,N,N',N'-tetra-p-methylbenzyl-ethylenediamine) and [CoCl4]2- through weak C-H...Cl hydrogen-bonding interaction, and a variety of guest molecules, such as p-anisaldehyde, 1,4-dimethoxy-2,5-bis(methoxymethyl)benzene, can be included, leading to the formation of supramolecular inclusion solids: [L1]center dot 4[H]+center dot[CoCl4]2-center dot 2Cl-center dot 1.5[C8H8O2]center dot 0.25[CH3OH] (1) and [L1]center dot 4[H]+center dot[CoCl4]2-center dot 2Cl-center dot 1.5[C12H20O4]center dot 0.5[CH3OH] (2).