Functional Supramolecular Polymeric Networks: The Marriage of Covalent Polymers and Macrocycle-Based Host–Guest Interactions

Abstract

Covalent polymers connected by non-covalent interactions constitute a fascinating set of materials known as supramolecular polymer networks (SPNs). A key feature of SPNs is that the underlying covalent polymers endow the resulting self-assembled materials with features, such as structural and mechanical integrity, good processability, recyclability, stimuli-responsiveness, self-healing, and shape memory, that are not recapitulated in the case of classic covalent polymer systems. The unique nature of SPNs derives from the controlled marriage of traditional covalent polymers and macrocycle-based host−guest interactions. As a consequence, supramolecular polymeric networks have played important roles in a number of diverse fields, including polymer science, supramolecular chemistry, materials science, biomedical materials, and information storage technology. In this Review, we summarize advances made in the area of functional SPNs, with a focus on original literature reports appearing in the past five years. The treatment is organized according to the key macrocycle-based host−guest interactions used to produce various SPNs. The role of the underlying polymer backbones is also discussed.

Construction of Supramolecular Polymers Based on Host‐Guest Recognition†

“…Moreover, supramolecular polymer materials can be combined with covalent polymer materials to achieve functions and uses that are difficult to have for covalent polymer materials. [ 55‐58 ] With these further investigations, both the scientific and social values of supramolecular polymer studies can be demonstrated.…”

Macrocycles-assisted polymeric self-assemblies fabricated by host–guest complexation and their applications

“…Hence, the prepared CEs functionalized polymeric gels were investigated for their self-healing properties and stimuli-responsiveness under different stimuli such as cation, anion, and pH-changes. 16 Han et al 51 constructed thermo-and ion-responsive supramolecular hydrogels by incorporating CEs into the poly(N-isopropylacrylamide) (PNIPAM) polymer. The swelling ratio (SR) of the copolymeric hydrogel was decreased in comparison to the pristine PNIPAM.…”

“…15 These stimuli-responsive MPs have been utilized for the development of functional materials, which show great potential in sensing, catalysis, hydrogels, and drug (gene) delivery applications. [16][17][18] The macrocycle-assisted host-guest strategy is unique, owing to its self-complementary interactions and directional properties. The host-guest interactions have played a crucial…”

Cyclobutene based macrocycles

“…The concepts of supramolecular chemistry provide a natural translation of molecule constructions to create functional materials. [1][2][3] Supramolecular assemblies containing extended p-conjugated macrocycles are particularly attractive for applications in organic electronics/devices, 4,5 examples of note include cyclic porphyrins, 6,7 annulenes, 8-10 phenylenes [11][12][13][14][15] and oligothiophenes. [16][17][18] The most common building blocks of p-extended macrocycles are phenylenes, ethynylenes, thiophenes and pyrroles.…”