Precise Macroscopic Supramolecular Assembly by Combining Spontaneous Locomotion Driven by the Marangoni Effect and Molecular Recognition

Macroscopic supramolecular assembly bridges fundamental research on molecular recognition and the potential applications as bulk supramolecular materials. However, challenges remain to realize stable precise assembly, which is significant for further functions. To handle this issue, the Marangoni effect is applied to achieve spontaneous locomotion of macroscopic building blocks to reach interactive distance, thus contributing to formation of ordered structures. By increasing the density of the building blocks, the driving force for assembly transforms from a hydrophobic–hydrophobic interaction to hydrophilic–hydrophilic interaction, which is favorable for introducing hydrophilic coatings with supramolecular interactive groups on matched surfaces, consequently realizing the fabrication of stable precise macroscopic supramolecular assemblies.     

Reversible Assembly of a Supramolecular Cage Linked by Boron–Nitrogen Dative Bonds

Boron–nitrogen dative bonds provide a suitable motif for reversible, yet strong and directed interactions, leading to the highly efficient self‐assembly of small organic building blocks into supramolecular cage structures. A bipyramidal [2+3] assembly, as the first example of a supramolecular cage mediated by B?N dative bonds that exists as a discrete species in solution, is quantitatively obtained from a tribenzotriquinacene‐based trisboronate ester and 1,4‐diazabicyclo[2.2.2]octane. Thermodynamic equilibria of cage formation are investigated by isothermal titration calorimetry and fully reversible cage opening can be observed at elevated temperatures.     

Precise Macroscopic Supramolecular Assemblies: Strategies and Applications

Macroscopic supramolecular assembly (MSA) is a new concept in supramolecular science with a focus on interfacial assembly of macroscopic building blocks, which has largely extended the applicable materials of supramolecular assembly and provided new solutions to fabricating tissue scaffolds, soft devices, etc. The precision of the assembled structures is of great interest; unlike molecular assemblies, MSA precision is highly dependent on the matching degree of assembled surfaces because of the large interactive area and group number, which result in remarkably increased kinetic possibilities and metastable assemblies. This Concept introduces the principle, history, and development of MSA, elaborates the low-precision challenge in MSA, summarizes the strategies for precise MSA based on the different thermodynamic stability of precise/imprecise structures and control over assembly kinetics, and finally demonstrates the applications of precise MSA structures in advanced manufacture such as tissue scaffolds.     

Elasticity‐Dependent Fast Underwater Adhesion Demonstrated by Macroscopic Supramolecular Assembly

Macroscopic supramolecular assembly (MSA) is a recent development in supramolecular chemistry to associate visible building blocks through non‐covalent interactions in a multivalent manner. Although various substrates (e.g. hydrogels, rigid materials) have been used, a general design rule of building blocks in MSA systems and interpretation of the assembly mechanism are lacking and are required. Herein we design three model systems with varied elastic modulus and correlated the MSA probability with the elasticity. Based on the effects of substrate deformability on multivalency, we have proposed an elastic‐modulus‐dependent rule that building blocks below a critical modulus of 2.5 MPa can achieve MSA for the used host/guest system. Moreover, this MSA rule applies well to the design of materials for fast underwater adhesion: Soft substrates (0.5 MPa) can achieve underwater adhesion within 10 s with one order of magnitude higher strength than that of rigid substrates (2.5 MPa).     

Macroscopic Supramolecular Assembly and Its Applications

Macroscopic supramolecular assembly (MSA) has been a recent progress in supramolecular chemistry.MSA mainly focuses on studies of the building blocks with a size beyond ten micrometers and the non-covalent interactions between these interactive building blocks to form ordered structures.MSA is essential to realize the concept of"self-assembly at all scales" by bridging most supramolecular researches at molecular level and at macroscopic scale.This review summaries the development of MSA,the basic design principle and related strategies to achieve MSA and potential applications.Correspondingly,we try to elucidate the correlations and differences between "macroscopic assembly" and MSA based on intermolecular interactions;the design principle and the underlying assembly mechanism of MSA are proposed to understand the reported MSA behaviors;to demonstrate further applications of MSA,we introduce some methods to improve the ordered degree of the assembled structures from the point of precise assembly and thus envision some possible fields for the use of MSA.     

Squeezing,Then Stacking: From Breathing Pores to Three‐Dimensional Ionic Self‐Assembly under Electrochemical Control

We demonstrate the spontaneous and reversible transition between the two‐ and three‐dimensional self‐assembly of a supramolecular system at the solid–liquid interface under electrochemical conditions, using in situ scanning tunneling microscopy. By tuning the interfacial potential, we can selectively organize our target molecules in an open porous pattern, fill these pores to form an auto‐host–guest structure, or stack the building blocks in a stratified bilayer. Using a simple electrostatic model, we rationalize which charge density is required to enable bilayer formation, and conversely, which molecular size/charge ratio is necessary in the design of new building blocks. Our results may lead to a new class of electrochemically controlled dynamic host–guest systems, artificial receptors, and smart materials.     

Hierarchical Self‐Assembly of Supramolecular Hydrophobic Metallacycles into Ordered Nanostructures

We describe herein the hierarchical self‐assembly of discrete supramolecular metallacycles into ordered fibers or spherical particles through multiple noncovalent interactions. A new series of well‐defined metallacycles decorated with long alkyl chains were obtained through metal–ligand interactions, which were capable of aggregating into ordered fibroid or spherical nanostructures on the surface, mostly driven by hydrophobic interactions. In‐depth studies indicated that the morphology diversity was originated from the structural information encoded in the metallacycles, including the number of alkyl chains and their spatial orientation. Interestingly, the morphology of the metallacycle aggregates could be tuned by changing the solvent polarity. These findings are of special significance since they provide a simple yet highly controllable approach to prepare ordered and tunable nanostructures from small building blocks by means of hierarchical self‐assembly.     

Hydrogen‐Bonding Induced Alternate Stacking of Donor (D) and Acceptor (A) Chromophores and their Supramolecular Switching to Segregated States

This paper reports comprehensive studies on the mixed assembly of bis‐(trialkoxybenzamide)‐functionalized dialkoxynaphthalene (DAN) donors and naphthalene‐diimide (NDI) acceptors due the cooperative effects of hydrogen bonding, charge‐transfer (CT) interactions, and solvophobic effects. A series of DAN as well as NDI building blocks have been examined (wherein the relative distance between the two amide groups in a particular chromophore is the variable structural parameter) to understand the structure‐dependent variation in mode of supramolecular assembly and morphology (organogel, reverse vesicle, etc.) of the self‐assembled material. Interestingly, it was observed that when the amide functionalities are introduced to enhance the self‐assembly propensity, the mode of co‐assembly among the DAN and NDI chromophores no longer remained trivial and was dictated by a relatively stronger hydrogen‐bonding interaction instead of a weak CT interaction. Consequently, in a highly non‐polar solvent like methylcyclohexane (MCH), although kinetically controlled CT‐gelation was initially noticed, within a few hours the system sacrificed the CT‐interaction and switched over to the more stable self‐sorted gel to maximize the gain in enthalpy from the hydrogen‐bonding interaction. In contrast, in a relatively less non‐polar solvent such as tetrachloroethylene (TCE), in which the strength of hydrogen bonding is inherently weak, the contribution of the CT interaction also had to be accounted for along with hydrogen bonding leading to a stable CT‐state in the gel or solution phase. The stability and morphology of the CT complex and rate of supramolecular switching (from CT to segregated state) were found to be greatly influenced by subtle structural variation of the building blocks, solvent polarity, and the DAN/NDI ratio. For example, in a given D–A pair, by introducing just one methylene unit in the spacer segment of either of the building blocks a complete change in the mode of co‐assembly (CT state or segregated state) and the morphology (1D fiber to 2D reverse vesicle) was observed. The role of solvent polarity, structural variation, and D/A ratio on the nature of co‐assembly, morphology, and the unprecedented supramolecular‐switching phenomenon have been studied by detail spectroscopic and microscopic experiments in a gel as well as in the solution state and are well supported by DFT calculations.     

Self-Assembled Dipeptide Aerogels with Tunable Wettability

Constructing supramolecular materials with tunable properties and functions is a great challenge due to the complex competition between multiple assembly pathways. Herein, we report that dipeptides can self-assemble into aerogels with entirely different surface wettability through precisely controlling the assembly pathways. Charged groups or aromatic residues are selectively exposed on the surface of their nanoscale building blocks which results either in a superhydrophilic or highly hydrophobic surface. With this special property, single component dipeptide aerogels can play diverse roles in medical care applications. This study suggests great promise in the synthesis of supramolecular materials with different targeted functions from the same molecular unit.     

Remote Chiral Communication in Coadsorber‐Induced Enantioselective 2D Supramolecular Assembly at a Liquid/Solid Interface

Remote chiral communication in 2D supramolecular assembly at a liquid/solid interface was investigated at the molecular level. The stereochemical information in a chiral coadsorber was transmitted over a flexible spacer with a length of up to five methylene groups to a 2D supramolecular assembly of achiral building blocks with the cooperation of specific hydrogen bonding between the chiral coadsorber and achiral building blocks and the confinement effect during 2D crystallization. When the position of the stereogenic center was changed with respect to the stereocontrolling moiety, an odd–even effect was found. A stereogenic center closer to the stereocontrolling moiety transmitted the stereochemical information to the 2D supramolecular assembly more reliably. This result is beneficial not only for mechanistic understanding of chiral communication in 2D supramolecular assembly on surfaces but also for the rational design of homochiral supramolecular assemblies on surfaces.     

Stimuli-responsive supramolecular polymeric materials

Supramolecular materials, dynamic materials by nature, are defined as materials whose components are bridged via reversible connections and undergo spontaneous and continuous assembly/disassembly processes under specific conditions. On account of the dynamic and reversible nature of noncovalent interactions, supramolecular polymers have the ability to adapt to their environment and possess a wide range of intriguing properties, such as degradability, shape-memory, and self-healing, making them unique candidates for supramolecular materials. In this critical review, we address recent developments in supramolecular polymeric materials, which can respond to appropriate external stimuli at the fundamental level due to the existence of noncovalent interactions of the building blocks.     

Photocontrol Over Self‐Assembled Nanostructures of π–π Stacked Dyes Supported by the Parallel Conformer of Diarylethene

Diarylethenes (DAEs) have rarely been used in the design of photoresponsive supramolecular assemblies with a well‐defined morphology transition owing to rather small structural changes upon photoisomerization. A supramolecular design based on the parallel conformation of DAEs enables the construction of photoresponsive dye assemblies that undergo remarkable nanomorphology transitions. The cooperative stacking of perylene bisimide (PBI) dyes was used to stabilize the parallel conformer of DAE through complementary hydrogen bonds. Atomic force microscopy, UV/Vis spectroscopy, and molecular modeling revealed that our DAE and PBI building blocks coassembled in nonpolar solvent to form well‐defined helical nanofibers featuring J‐type dimers of PBI dyes. Upon irradiating the coassembly solution with UV and visible light in turn, a reversible morphology change between nanofibers and nanoparticles was observed. This system involves the generation of a new self‐assembly pathway by means of photocontrol.     

Self‐Assembled Dipeptide Aerogels with Tunable Wettability

Constructing supramolecular materials with tunable properties and functions is a great challenge due to the complex competition between multiple assembly pathways. Herein, we report that dipeptides can self‐assemble into aerogels with entirely different surface wettability through precisely controlling the assembly pathways. Charged groups or aromatic residues are selectively exposed on the surface of their nanoscale building blocks which results either in a superhydrophilic or highly hydrophobic surface. With this special property, single component dipeptide aerogels can play diverse roles in medical care applications. This study suggests great promise in the synthesis of supramolecular materials with different targeted functions from the same molecular unit.     

A Periodic System of Supramolecular Elements

Chemistry “beyond the molecule” is based on weak, noncovalent, and reversible interactions. As a consequence of these bonds being weak, structural organization by folding and self‐assembly can only be fully exploited with larger molecules that can provide multiple binding sites. Such “supramolecules” can now be synthesized and their folding into desired conformations predicted. A new level of chemistry can now be realized through the creation of non‐natural entities composed of molecular building blocks with defined secondary structures. Herein we define these building blocks as “supramolecular elements”. We anticipate that further research on such large molecules will reveal construction principles dictated by recurring motifs that govern structure formation through folding and self‐assembly. These principles are comparable to the organization of atoms in the Periodic Table of Chemical Elements and may lead to the establishment of a Periodic System of Supramolecular Elements.     

Main-chain supramolecular block copolymers

Block copolymers are key building blocks for a variety of applications ranging from electronic devices to drug delivery. The material properties of block copolymers can be tuned and potentially improved by introducing noncovalent interactions in place of covalent linkages between polymeric blocks resulting in the formation of supramolecular block copolymers. Such materials combine the microphase separation behavior inherent to block copolymers with the responsiveness of supramolecular materials thereby affording dynamic and reversible materials. This tutorial review covers recent advances in main-chain supramolecular block copolymers and describes the design principles, synthetic approaches, advantages, and potential applications.     

In Situ Controlled Construction of a Hierarchical Supramolecular Chiral Liquid‐Crystalline Polymer Assembly

Hierarchical supramolecular chiral liquid‐crystalline (LC) polymer assemblies are challenging to construct in situ in a controlled manner. Now, polymerization‐induced chiral self‐assembly (PICSA) is reported. Hierarchical supramolecular chiral azobenzene‐containing block copolymer (Azo‐BCP) assemblies were constructed with π–π stacking interactions occurring in the layered structure of Azo smectic phases. The evolution of chirality from terminal alkyl chain to Azo mesogen building blocks and further induction of supramolecular chirality in LC BCP assemblies during PICSA is achieved. Morphologies such as spheres, worms, helical fibers, lamellae, and vesicles were observed. The morphological transition had a crucial effect on the chiral expression of Azo‐BCP assemblies. The supramolecular chirality of Azo‐BCP assemblies destroyed by 365 nm UV irradiation can be recovered by heating–cooling treatment; this dynamic reversible achiral–chiral switching can be repeated at least five times.     

Dual‐Mode Controlled Self‐Assembly of TiO2 Nanoparticles Through a Cucurbit[8]uril‐Enhanced Radical Cation Dimerization Interaction

The realization of controllable multicomponent self‐assembly through reversible supramolecular interactions is a challenging goal, and is an important strategy for the fabrication of switchable nanomaterials. Herein we show that the self‐assembly of TiO₂ nanoparticles (NP) functionalized with methyl viologen can be controlled both by light irradiation and chemical reduction through cucurbit[8]uril‐enhanced radical cation dimerization interactions. Moreover, the controlled assembly and disassembly of this system are accompanied by switchable photocatalytic activity of the TiO₂ NPs, which shows potential application as a novel smart and recyclable photocatalyst.     

Small‐Peptide‐Based Organogel Kit: Towards the Development of Multicomponent Self‐Sorting Organogels

The results presented here highlight the extremely useful nature of ultra‐short peptides as building blocks in the development of smart multicomponent supramolecular devices. A facile bottom‐up strategy for the synthesis of a small library of stimuli‐responsive smart organogelators has been proposed based on the predictive self‐assembly of ultra‐short peptides. More importantly, the narcissistic self‐sorting of the gelators has been evaluated as a simple method for the efficient co‐assembly of a donor–acceptor dual‐component gel, allowing the investigation of possible future applications of similar systems in the development of a supramolecular photo‐conversion device. Interestingly, it was observed that the self‐organization of the components can lead to highly ordered systems in which discrimination between compatible and non‐compatible building blocks directs the effective organization of the chromophores and gives rise to the formation of an excited‐state complex with exciplex‐like emission. The current report may prove important in the development of organogel‐based multicomponent smart devices.     

Discrete Stimuli‐Responsive Multirotaxanes with Supramolecular Cores Constructed through a Modular Approach

The synthesis of discrete multirotaxanes with well‐defined structures remains a great challenge. Herein, we present the successful construction of diverse discrete multirotaxanes with well‐defined supramolecular metallacycles as cores by a modular approach. Moreover, these novel multirotaxanes featured a stimuli‐responsive property that enabled the introduction and removal of the bromide anion by taking advantage of dynamic nature of the supramolecular metallacycle scaffold. Through the combination of rotaxane‐containing prefunctionalized building blocks with the corresponding different organoplatinum(II) acceptor building blocks (60, 120, or 180°), diverse discrete multirotaxanes with well‐defined metallacycles (rhomboid or hexagon) as cores as well as certain numbers of rotaxane units were successfully obtained quantitatively by means of coordination‐driven self‐assembly. Furthermore, owing to the existence of a dynamic metallacycle as the supramolecular cores, the resultant multirotaxanes showed anion‐induced disassembly and reassembly properties, which allowed for the reversible transformation between multirotaxanes and the corresponding individual rotaxane‐containing building blocks. Therefore, this research not only enriches the family of discrete multirotaxanes, but also provides a novel strategy for the construction of “smart” stimuli‐responsive multirotaxane systems.     

Biocatalytic Self‐Assembly of Supramolecular Charge‐Transfer Nanostructures Based on n‐Type Semiconductor‐Appended Peptides

The reversible in situ formation of a self‐assembly building block (naphthalenediimide (NDI)–dipeptide conjugate) by enzymatic condensation of NDI‐functionalized tyrosine ( NDI‐Y ) and phenylalanine‐amide ( F‐NH₂ ) to form NDI‐YF‐NH₂ is described. This coupled biocatalytic condensation/assembly approach is thermodynamically driven and gives rise to nanostructures with optimized supramolecular interactions as evidenced by substantial aggregation induced emission upon assembly. Furthermore, in the presence of di‐hydroxy/alkoxy naphthalene donors, efficient charge‐transfer complexes are produced. The dynamic formation of NDI‐YF‐NH₂ and electronic and H‐bonding interactions are analyzed and characterized by different methods. Microscopy (TEM and AFM) and rheology are used to characterize the formed nanostructures. Dynamic nanostructures, whose formation and function are driven by free‐energy minimization, are inherently self‐healing and provide opportunities for the development of aqueous adaptive nanotechnology.