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 selfassembly.H erein we describe the fabrication of ab ilayer 2D supramolecular organic framework from am onolayer 2D supramolecular organic framework in water by utilizing the cooperative coordination of ar od-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.T he 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.A tomic force microscopic imaging confirms that the bilayer character of the 2D supramolecular organic framework can be realized selectively on the micrometer scale.

Through-Space Conjugated Supramolecular Polymer Radicals from Spatial Organization of Cucurbit[8]uril: An Efficient Approach for Electron Transfer and Smart Photochromism Materials

“…A cucurbit[8]­uril (Q[8] or CB[8]) host is a larger homologue of the Q­[ n ]­s family, which not only can accommodate and stabilize V •+ radicals in the confined cavity ,− but also distinguishes itself by encapsulating V 2+ derivative guests as the electron-accepting moiety and an electron-donating guest to form a host-enhanced charge-transfer complex in its rigid space. − In addition, Q[8] as the host can also simultaneously include two homo guests, such as arylpyridinium or naphthalene, which can be dimerized inside the cavity to form highly stable Q[8]-enhanced π–π complexes under the macrocyclic confinement effect. ,− Evidently, these results indicate that the confined space of the Q[8] cavity has the excellent advantages of strengthening the weak intermolecular interactions and controlling the orientation of the two encapsulated guests. However, to the best of our knowledge, V •+ radicals that are directly triggered by the Q[8]-confined space via intermolecular PET have not yet been studied …”

Two‐Dimensional Covalent and Supramolecular Polymers: From Monolayer to Bilayer and the Thicker

“…Nonetheless, this system represents a formal bilayer with high regularity. In 2021, Yu and co‐workers demonstrated that coordination could be used to guide two 2DSP‐11/CB[8] monolayers to form bilayer structures [13] . In order to achieve this structure, ditopic ligand M15 was prepared to coordinate the zinc porphyrins of the monolayer (Scheme 3).…”

“…In 2021, Yu and co-workers demonstrated that coordination could be used to guide two 2DSP-11/CB [8] monolayers to form bilayer structures. [13] In order to achieve this structure, ditopic ligand M15 was prepared to coordinate the zinc porphyrins of the monolayer (Scheme 3). At a M15/porphyrin ratio of 0.5, the penta-coordination geometry of Zn 2 + enabled selective formation of the corresponding bilayer 2DSP-M11/CB [8] (Figure 1), as was confirmed by AFM investigations.…”

“…[11] Very recently, Yu and co-workers showed that zinc porphyrin M11 and CB [8] (1 : 2) co-assembled to afford 2D supramolecular polymer 2DSP-11/CB [8] (Scheme 3). [13] Different from covalent 2DPs, the building blocks of 2DSPs are cationic. Their electrostatic repulsion can suppress the stacking of the monolayers and endow the monolayers with good water-solubility.…”

“…This Concept review will firstly summarize the approaches for the construction of monolayered 2D covalent and supramolecular architectures. We then highlight two recent strategies for the synthesis of bilayer 2DP and 2DSP [4d,13] . Following these highlights, we will discuss potential approaches to realizing 2D materials with more than two layers.…”