Self‐Assembly of a Bilayer 2D Supramolecular Organic Framework in Water

Abstract Accurate control of the layer number of orderly stacked 2D polymers has been an unsettled challenge in self‐assembly. Herein we describe the fabrication of a bilayer 2D supramolecular organic framework from a monolayer 2D supramolecular organic framework in water by utilizing the cooperative coordination of a rod‐like bipyridine ligands to zinc porphyrin subunits of the monolayer network. The monolayer supramolecular framework is prepared from the co‐assembly of an octacationic zinc porphyrin monomer and cucurbit[8]uril (CB[8]) in water through CB[8]‐encapsulation‐promoted dimerization of 4‐phenylpyridiunium subunits that the zinc porphyrin monomer bear. The bilayer 2D supramolecular organic framework exhibits structural regularity in both solution and the solid state, which is characterized by synchrotron small‐angle X‐ray scattering and high‐resolution transmission electron microscopic techniques. Atomic force microscopic imaging confirms that the bilayer character of the 2D supramolecular organic framework can be realized selectively on the micrometer scale.