Supramolecular polymerization behavior of a ditopic self-folding biscavitand

Dynamic enzymatic synthesis of γ-cyclodextrin using a photoremovable hydrazone template

Inspired by the vast array of assemblies present in nature, supramolecular chemistry has attracted significant attention on account of its diverse supra-structures, which include micelles, vesicles, and fibers, in addition to its extensive applications in luminescent materials, sensors, bioimaging, and drug delivery over the past decades. Supramolecular polymers, which represent a combination of supramolecular chemistry and polymer science, are constructed by non-covalent interactions, such as host-guest interactions, hydrogen bonding, hydrophobic or hydrophilic interactions, metal-ligand interactions, π-π stacking, and electrostatic interactions. To date, numerous host-guest recognition systems have been reported, including crown ethers, cyclodextrins, calixarenes, cucurbituril, pillararenes, and other macrocyclic hosts. Among them, crown ethers, as the first generation of macrocyclic hosts, provide a promising and facile alternative route to supramolecular polymers. In addition, the incorporation of fluorophores into supramolecular polymers could endow them with multiple properties and functions, thereby presenting potential advantages in the context of smart materials. Thus, this review focuses on the fabrication strategies, interesting properties, and potential applications of fluorescent supramolecular polymers based on crown ethers. Typical examples are presented and discussed in terms of three different types of building blocks, namely covalently bonded low-molecular-weight compounds, polymers modified by hosts or guests, and supramolecular coordination complexes.

Pagoda[5]arene (P5), which is composed of five 2,6-dimethoxylanthracene (2,6-DMA) subunits bridged by methylene groups at 1,5 positions, was conveniently synthesized in 43% by trifluoroacetic acid ...

Bisporphyrin cleft molecule 1 Zn possessing a guest moiety assembled to form supramolecular polymers through host–guest interactions. Bispyridine cross‐linkers created interchain connections among the supramolecular polymers to form networked polymers in solution. Solution viscometry confirmed that the cross‐linked supramolecular polymers were highly entangled. Frequency‐dependent linear viscoelastic spectroscopy revealed that the supramolecular polymers generated well‐entangled solutions with associating and networking polymers, whereas the solid‐like aggregates moved individually without breaking and reforming structures below the transition temperature of 9.6 °C. Morphological transition of the supramolecular polymers was evidenced by AFM images; the non‐cross‐linked polymer resulted in wide‐spread thin networks, while the cross‐linked networks produced thicker worm‐like nanostructures. The supramolecular networks gelled in 1,1,2,2‐tetrachloroethane, and an elastic free‐standing film was fabricated with a Young’s modulus of 1 GPa.

Assessment of techniques for DOSY NMR data processing

Supramolecular polymers, in which monomers are assembled via intermolecular interactions, have been extensively studied. The fusion of supramolecular polymers with conventional polymers has attracted the attention of many researchers. In this review article, the recent progress in the construction of supramolecular star polymers, including regular star polymers and miktoarm star polymers, is discussed. The initial sections briefly provide an overview of the conventional classification and synthesis methods for star polymers. Coordination-driven self-assembly was investigated for the supramolecular synthesis of star polymers. Star polymers with multiple polymer chains radiating from metal-organic polyhedra (MOPs) have also been described. Particular focus has been placed on the synthesis of star polymers featuring supramolecular cores formed through hydrogen-bonding-directed self-assembly. After describing the synthesis of star polymers based on host-guest complexes, the construction of miktoarm star polymers based on the molecular recognition of coordination capsules is detailed.

Supramolecular polymers are widely utilized and applied in self-assembly or self-healing materials, which can be repaired when damaged. Normally, the healing process is classified into two types, including extrinsic and intrinsic self-healable materials. Therefore, the aim of this work is to review the intrinsic self-healing strategy based on supramolecular interaction or non-covalent interaction and molecular recognition to obtain the improvement of mechanical properties. In this review, we introduce the main background of non-covalent interaction, which consists of the metal–ligand coordination, hydrogen bonding, π–π interaction, electrostatic interaction, dipole–dipole interaction, and host–guest interactions, respectively. From the perspective of mechanical properties, these interactions act as transient crosslinking points to both prevent and repair the broken polymer chains. For material utilization in terms of self-healing products, this knowledge can be applied and developed to increase the lifetime of the products, causing rapid healing and reducing accidents and maintenance costs. Therefore, the self-healing materials using supramolecular polymers or non-covalent interaction provides a novel strategy to enhance the mechanical properties of materials causing the extended cycling lifetime of products before replacement with a new one.

This communication describes a new method of fabricating supramolecular polymers through supramolecular polymerization of supramonomers.

ABC-type miktoarm star terpolymers accessed by H-bonding driven supramolecular self-assembly

A water-soluble supramolecular polymer with a high degree of polymerization and viscosity has been constructed based on the strong host-guest interaction between p-sulfonatocalix[4]arenes (SC4As) and viologen. A homoditopic doubly ethyl-bridged bis(p-sulfonatocalix[4]arene) (d-SC4A) was prepared and its binding behavior towards methyl viologen compared with the singly ethyl-bridged bis(p-sulfonatocalix[4]arene) (s-SC4A) by NMR spectroscopy and isothermal titration calorimetry. By employing a viologen dimer (bisMV(4+)) as the homoditopic guest, two linear AA/BB-type supramolecular polymers, d-SC4A⊃bisMV(4+) and s-SC4A⊃bisMV(4+), were successfully constructed. Compared with s-SC4A⊃bisMV(4+), d-SC4A⊃bisMV(4+) shows much higher solubility and viscosity, and has also been characterized by viscosity, diffusion-ordered NMR spectroscopy, dynamic light scattering, and atomic force microscopy measurements. Furthermore, the polymer is responsive to electrostimulus as viologen is electroactive, which was studied by cyclic voltammetry. This study represents a proof-of-principle as the polymer can potentially be applied as a self-healing and degradable polymeric material.

Topological metamorphosis represents a powerful approach to modulate the properties of polymers. However, it still remains a major challenge to achieve the tunability of bulk mechanical properties via topological transformation in supramolecular polymer systems. Herein, we couple the covalent polymer and supramolecular polymer in a single system—referred to as covalent‐and‐supramolecular polymer (CSP)—to realize a thermo‐responsive macromolecular metamorphosis. The CSP is able to topologically switch from grafted polymer to cross‐linked network by taking advantage of synergistic dynamic covalent interactions and host–guest interactions. Benefiting from the topologically structural transformation, brittleness intrinsically evolves into toughness in our CSP architectures with minimum change of their molecular compositions from furan–maleimide to anthracene–maleimide linkers. Our work demonstrates that supramolecular polymers are a promising platform to design smart materials not only due to their inherent stimuli‐responsive properties but also because of their abilities in determining bulk mechanical properties of polymers with alterable topological structures.

Influence of self-assembly of amphiphilic imidazolium ionic liquids on their host–guest complexes with cucurbit[n]urils

Cooperative supramolecular polymerization of π-conjugated compounds into one-dimensional nanostructures has received tremendous attentions in recent years. It is commonly achieved by incorporating amide linkages into the monomeric structures, which provide hydrogen bonds for intermolecular non-covalent complexation. Herein, the effect of amide linkages is elaborately studied, by comparing supramolecular polymerization behaviors of two structurally similar monomers with the same platinum(II) acetylide cores. As compared to the N-phenyl benzamide linkages, N-[(1S)-1-phenylethyl] benzamide linkages give rise to effective chirality transfer behaviors due to the closer distances between the chiral units and the platinum(II) acetylide core. They also provide stronger intermolecular hydrogen bonding strength, which consequently brings higher thermo-stability and enhanced gelation capability for the resulting supramolecular polymers. Supramolecular polymerization is further strengthened by varying the monomers from monotopic to ditopic structures. Hence, with the judicious modulation of structural parameters, the current study opens up new avenues for the rational design of supramolecular polymeric systems.

Analytical ultracentrifugation (AUC) is the leading technique for determining the molar mass, state of association in solution, and association constants of biological macromolecules. Even though it is little used for supramolecular polymers, this technique has already been shown to represent one of the best options in the characterization of these systems. The use of supramolecular assemblies in the field of nanotechnology requires the arrangement of such systems on surfaces, from solution. Therefore, the control and investigation of solution properties is of major importance. In this contribution we highlight the applicability and advantages of using AUC by presenting a summary of the results of the past few years on the characterization of various types of synthetic polymers and supramolecular polymer systems.

Orthogonal self-assembly represents a useful methodology to construct supramolecular polymers with AA- and AB-type monomers, as commonly used for covalently linked polymers. So far, the design of such monomers has relied heavily on three-dimensional macrocycles, and the use of two-dimensional shape-persistent macrocycles for this purpose remains rather rare. Here, we demonstrate a dimerization motif based on a hydrogen-bonded macrocycle that can be effectively applied to form orthogonal supramolecular polymers. The macrocycle-mediated connectivity was confirmed by single-crystal X-ray diffraction, which revealed a unique 2:2 binding motif between host and guest, bridged by two cationic pyridinium end groups through π-stacking interactions and other cooperative intermolecular forces. Zinc ion-induced coordination with the macrocycle and a terpyridinium derivative enabled orthogonal polymerization, as revealed by 1H NMR, DLS, and TEM techniques. In addition, viscosity measurements showed a transition from oligomers to polymers at the critical polymerization concentration of 17 μM. These polymers were highly concentration-dependent. Establishing this new dimerization motif with shape-persistent H-bonded macrocycles widens the scope of noncovalent building blocks for supramolecular polymers and augurs well for the future development of functional materials.