Thermo‐responsive topological metamorphosis in covalent‐and‐supramolecular polymer architectures

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.

New strategies that can simultaneously detect and remove highly toxic environmental pollutants such as heavy metal ions are still in urgent need. Herein, through supramolecular host-guest interactions, a fluorescent supramolecular polymer has been facilely constructed from a newly designed [2]biphenyl-extended pillar[6]arene equipped with two thymine sites as arms (H) and a tetraphenylethylene (TPE)-bridged bis(quaternary ammonium) guest (G) with aggregation-induced emission (AIE) property. Interestingly, supramolecular assembly-induced emission enhancement (SAIEE) could be switched on upon addition of Hg2+ into the above-mentioned supramolecular polymer system to generate spherical-like supramolecular nanoparticles, due to the restriction of intramolecular rotation (RIR)-related AIE feature of G. Significantly, this supramolecular polymer with integrated modalities has been successfully used for real-time detection and removal of toxic heavy metal Hg2+ ions from water with quick response, high selectivity, and rapid adsorption rates, which could be efficiently regenerated and recycled without any loss via a simple treatment with Na2S. The newly developed supramolecular polymer system combines the inherent rigid and spacious cavity of novel extended-pillarene host with the AIE characteristics of TPE-based guest, suggesting a great potential in the treatment of heavy metal pollution and environmental sustainability.

Supramolecular polymers exhibit well-controlled dynamics with fascinating capacity for remodeling, self-healing, and stimuli-responsiveness. Supramolecular kinetics of non-covalent bonds is a dominant control handle among the relevant factors to tailor dynamics of supramolecular polymers. This Review focuses on elucidating how supramolecular kinetics dictates the polymer dynamics in supramolecular polymer systems. The ways to tailor supramolecular kinetics are firstly examined as prerequisites for structure-activity study of supramolecular polymers. We next discuss the role of supramolecular kinetics in supramolecular polymers under different polymer architectures by the combination of both of theoretical and experimental studies. Finally, we conclude by discussing the existing challenges and opportunities in the current studies.

Recent studies have shown that enhanced oil recovery will be the focal point for approximately 50% of the global oil production in the upcoming two-three decades. According to the several ballpark studies conducted on EOR techniques, results show that for reservoirs with oil viscosities ranging from 10 to 150 m Pa.s., polymer flooding seems to be an ideal development strategy. However, when the oil viscosities exceed 150 m Pa.s., polymer injectivity and pumping efficiencies can turn out to be major inhibiting factors, thereby limiting the range of oil viscosities for which polymer flooding can be utilized. The core reason for this is that the values of viscosity for the injected water containing polymer, calculated for the beneficial mobility ratio, can lead to the inhibiting factor stated above. Previously conducted lab studies have shown that supramolecular systems are very resistant in high temperature - high salinity systems. To be able to achieve the easier injection, the injected supramolecular viscosity will be kept at lower values and then increased to the levels right before or upon contacting the oil in the reservoir. The core difference between conventional polymer systems and supramolecular polymer systems is that the latter disassemble and re-assemble as opposed to degradation when exposed to extreme shear stress and temperatures. It can therefore be said that supramolecular polymer systems are self-healing in nature. The phenomenon has been observed in cases where polymers with high molecular weight are forced through narrow flow channels. Though molecular division takes place, supramolecular systems have shown a tendency of reassembly later on. Therefore, adaptability of these systems to bounded or restricted environments can be established. This study will add the modeling and simulation components of supramolecular systems which can be effectively utilized in high temperature-high salinity conditions through adjustments to viscosities and interfacial properties of these assemblies. This will help compare the displacement efficiency of supramolecular systems which efficiently perform in a wide range of reservoirs such as thin zones, and reservoirs within permafrost conditions. This can significantly benefit the oil and gas companies worldwide in preparing a technically feasible, but also, a cost effective EOR development strategy, whenever polymer injection is of consideration.

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.

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.

Owing to the mastery exhibited by Nature in integrating both covalent and noncovalent interactions in a highly efficient manner, the quest to construct polymeric systems that rival not only the precision and fidelity but also the structure of natural systems has remained a daunting challenge. Supramolecular chemists have long endeavored to control the interplay between covalent and noncovalent bond formation, so as to examine and fully comprehend how function is predicated on self-assembly. The ability to reliably control polymer self-assembly is essential to generate "smart" materials and has the potential to tailor polymer properties (i.e., viscosity, electronic properties) through fine-tuning the noncovalent interactions that comprise the polymer architecture. In this context, supramolecular polymers have a distinct advantage over fully covalent systems in that they are dynamically modular, since noncovalent recognition motifs can be engineered to either impart a desired functionality within the overall architecture or provide a designed bias for the self-assembly process. In this Account, we describe engineering principles being developed and pursued by our group that exploit the orthogonal nature of noncovalent interactions, such as hydrogen bonding, metal coordination, and Coulombic interactions, to direct the self-assembly of functionalized macromolecules, resulting in the formation of supramolecular polymers. To begin, we describe our efforts to fabricate a modular poly(norbornene)-based scaffold via ring-opening metathesis polymerization (ROMP), wherein pendant molecular recognition elements based upon nucleobase-mimicking elements (e.g., thymine, diaminotriazine) or SCS-Pd(II) pincer were integrated within covalent monofunctional or symmetrically functionalized polymers. The simple polymer backbones exhibited reliable self-assembly with complementary polymers or small molecules. Within these systems, we applied successful protecting group strategies and template polymerizations to enhance the control afforded by ROMP. Main-chain-functionalized alternating block polymers based upon SCS-Pd(II) pincer-pyridine motifs were achieved through the combined exploitation of bimetallic initiators and supramolecularly functionalized terminators. Our initial design principles led to the successful fabrication of both main-chain- and side-chain-functionalized poly(norbornenes) via ROMP. Utilizing all of these techniques in concert led to engineering orthogonality while achieving complexity through the installation of multiple supramolecular motifs within the side chain, main chain, or both in our polymer systems. The exploitation and modification of design principles based upon functional ROMP initiators and terminators has resulted in the first synthesis of main-chain heterotelechelic polymers that self-assemble into A/B/C supramolecular triblock polymers composed of orthogonal cyanuric acid-Hamilton wedge and SCS-Pd(II) pincer-pyridine motifs. Furthermore, supramolecular A/B/A triblock copolymers were realized through the amalgamation of functionalized monomers, ROMP initiators, and terminators. To date, this ROMP-fabricated system represents the only known method to afford polymer main chains and side chains studded with orthogonal motifs. We end by discussing the impetus to attain functional materials via orthogonal self-assembly. Collectively, our studies suggest that combining covalent and noncovalent bonds in a well-defined and precise manner is an essential design element to achieve complex architectures. The results discussed in this Account illustrate the finesse associated with engineering orthogonal interactions within supramolecular systems and are considered essential steps toward developing complex biomimetic materials with high precision and fidelity.

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.

Development of self-healing and photostimulated luminescent supramolecular polymeric materials is important for artificial soft materials. A supramolecular polymeric hydrogel is reported based on the host-guest recognition between a β-cyclodextrin (β-CD) host polymer (poly-β-CD) and an α-bromonaphthalene (α-BrNp) polymer (poly-BrNp) without any additional gelator, which can self-heal within only about one minute under ambient atmosphere without any additive. This supramolecular polymer system can be excited to engender room-temperature phosphorescence (RTP) signals based on the fact that the inclusion of β-CD macrocycle with α-BrNp moiety is able to induce RTP emission (CD-RTP). The RTP signal can be adjusted reversibly by competitive complexation of β-CD with azobenzene moiety under specific irradiation by introducing another azobenzene guest polymer (poly-Azo).

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.

Reported herein is the supramolecular polymerization of a mixture of a feet-to-feet connected biscavitand and a homoditopic quinuclidinium guest that is regulated by cooperativity in the host–guest association. Diffusion-ordered NMR spectroscopy (DOSY) was used to evaluate the supramolecular polymerization in toluene, CHCl3, and tetrahydrofuran (THF). Upon concentrating the solutions of the biscavitand with the quinuclidinium guest in CHCl3 and THF, the diffusion coefficient (D) values were meaningfully decreased, indicating that the host–guest complexation facilitated supramolecular polymerization. In contrast, the slight change of the D value in toluene suggests that supramolecular polymerization was suppressed, although the binding constant (K) between the cavitand and quinuclidinium guest was reported to be 105 L mol−1 in toluene. The viscosity measurements showed both the critical polymerization concentration (CPC) and entangled concentration (Ce) upon concentrating the CHCl3 solution of the mixture. Neither the CPC nor Ce was seen in the toluene solution of the mixture. Accordingly, the strong negative cooperativity in the 1:2 host–guest complexation of the biscavitand discouraged the supramolecular polymerization in toluene. These findings are valuable in deepening the understanding of host–guest association-driven supramolecular polymerization behaviors regulated by a combination of cooperativity and K value in solution.

A novel supramolecular polymer system, in which the terminal pyrenyl groups of a polyamide intercalate into the chain-folds of a polyimide via electronically-complementary pi-pi stacking, shows both enhanced mechanical properties relative to those of its individual components and facile healing characteristics as a result of the thermoreversibility of non-covalent interactions.

By incorporating a photochromophore, an azobenzene group, into a low molecular weight heteroditopic AB-type monomer, photo-responsive linear or cross-linked supramolecular polymers were prepared. After UV irradiation, both the linear and cross-linked supramolecular polymers showed obvious decrease in viscosity. More importantly, gels formed from the cross-linked supramolecular polymer could realize reversible photo-induced sol–gel transitions via UV or visible light irradiation. The work presented here provided an effective strategy to introduce photo-responsive properties into supramolecular polymers with different topological structures and to prepare complex and highly ordered supramolecular structures.

A series of poly(lactide) (PLA)‐based supramolecular polymers based on linear PLLA‐b‐PCL‐b‐PLLA triblock copolymers (PLLA, poly(l‐lactide); PCL, poly(ε‐caprolactone)) or/and three‐arm star (PCL‐b‐PDLA)3 block copolymers (PDLA, poly(d‐lactide)) were synthesized. The effects of the structure and composition on crystal structure, crystallization behavior, spherulite morphology and mechanical properties of the synthesized supramolecular polymers were investigated. The results of DSC and polarized optical microscopy indicated that the supramolecular polymer exhibited poor crystallization ability with respect to PCL/PLA block copolymer, and the crystallinity of the supramolecular polymer with alternating PCL/PLA multiblock structure was stronger than that with similar crosslinked network structure. The presence of molten PCL blocks disturbed the orientation of lamellae, forming spherulites with feather‐like dendrites, and ring‐banded spherulites were observed as the molecular weight of the PLA blocks increased. The results of tensile tests demonstrated that supramolecular polymers with larger molecular weight of PLA blocks showed the pronounced ductile fracture. On this basis, stereocomplexed supramolecular polymers were also synthesized, and it was found that the stereocomplex crystals had a significant impact on the crystallization and mechanical properties of the supramolecular polymers. Therefore, in this work a novel technique for manufacturing toughened PLA‐based material and tuning its performances is proposed, which may promote the application of PLA‐based materials in more fields. © 2022 Society of Industrial Chemistry.

ConspectusSince its inception in the early 1990s, the field of supramolecular polymers (SPs) has grown into an interdisciplinary field of chemistry. It expanded from the self-assembly of molecular building blocks based on H-bonding into the realm of complex dynamic material, encompassing both supramolecular noncovalent and molecular covalent regimes. It has paved the path for a more diverse field of research into a new class of polymeric materials, coined dynamic polymers or dynamers. Dynamers are bringing a paradigm shift not only in material science research but also in a broad field of applications from self-healing materials to biocompatible polymeric materials. The present Account presents the evolution of supramolecular polymer chemistry from simple linear polymeric chains to complex dynamic polymers imparting novel functional properties, such as component exchange and self-healing. We explore how SPs led to materials of increasing complexity, starting from simple main-chain polymers to the formation of more complex columnar SPs and lateral SPs. The field has experienced three partially overlapping periods. The main goal was first the generation of polymeric entities from various molecular components connected through noncovalent interactions, especially complementary hydrogen bonding recognition patterns as well as stacked columnar SPs. Thereafter, attention was directed in parallel to the exploration of the properties of SPs and their applications as novel materials. In a third period, the dynamic properties of supramolecular polymers were explored, taking advantage of the lability of noncovalent interactions to perform component rearrangement and exchange. We illustrate how the field of SPs has emerged as a multidisciplinary field of chemistry, biology, and materials science with selected examples from the literature. The SPs, specifically dynamic owing to their inherent reversibility, also pave the path to easier sorting and recycling, as desired in the plastics industry.One of the biggest challenges that the plastics industry is facing today is the end-of-life fate of plastics. Plastics that cannot be recycled end up in landfills or are improperly disposed of in rivers and oceans, polluting and damaging the environmental balance irreversibly. Dynamic polymeric materials presenting inherent dynamicity could pave the way for addressing this long-standing challenge of nonrecyclability of plastics. Dynamers formed via noncovalent interactions or reversible covalent bonds can be broken into components that could be easily recycled and reused. Therefore, dynamers could play a pivotal role toward closing the loop for the plastics industry and provide a solution to an elusive circular economy with plastics being an integral part.