Search

Investigating the self‐sorting behaviour of assemblies with subtle structural differences is a captivating yet challenging endeavour. Herein, we elucidate the unusual self‐sorting behaviour of metallacages with subtle structural differences in batch reactors and microdroplets. Narcissistic self‐sorting of metallacages has been observed for two ligands with identical sizes, shapes, and symmetries, with only minor differences in the substituted groups. In particular, the self‐sorting process in microdroplets occurs within 1 min at room temperature, in stark contrast to batch reactors, which require equilibration for 30 min. To reveal the mechanism of self‐sorting and the role of microdroplets, we conducted a series of experiments and theoretical calculations, including competitive self‐assembly, cage‐to‐cage transformation, control experiments involving model metallacages with larger cavities, noncovalent interaction analysis, and root mean square deviation (RMSD) analysis. This research demonstrates an unusual case of self‐sorting of very similar assemblies and provides a new strategy for facilitating the self‐sorting efficiency of supramolecular systems. [ABSTRACT FROM AUTHOR]

Pd(II)‐based low‐symmetry coordination cages possessing anisotropic cavities are of great interest. The common strategies employed to achieve such cages utilize either more than one type of symmetrical ligands (e.g., Laa, Lbb etc.) or only one type of unsymmetrical ligand (e.g., Lab). To significantly enhance the anisotropy, we have designed two unsymmetrical bidentate ligands i.e., Lab and Lcd, aiming at a low‐symmetry Pd2Lab2Lcd2‐type cage. It was accomplished by high‐fidelity integrative self‐sorting of two different low‐symmetry cages having Pd2Lab4 and Pd4Lcd8‐type architectures (homoleptic complexes of the designed ligands). Structural constraints and geometry complementarity in the ligand design drive the non‐statistical exclusive self‐assembly of the Pd2Lab2Lcd2‐type cage. By taking advantage of the complemental geometries between ligands, a low‐symmetry Pd2Lab2Lcc2‐type cage was also obtained. Heteromeric completive self‐sorting of three homoleptic assemblies (Pd2Lab4, Pd4Lcc8 and Pd4Lcd8‐type cages) into an exclusive mixture of Pd2Lab2Lcd2 and Pd2Lab2Lcc2‐type mixed ligated assemblies was demonstrated through cage‐to‐cage transformations. [ABSTRACT FROM AUTHOR]

Multiple dynamic libraries of compounds are generated when more than one reversible reaction comes into play. Commonly, two or more orthogonal reversible reactions are used, leading to non‐communicating dynamic libraries which share no building blocks. Only a few examples of communicating libraries have been reported, and in all those cases, building blocks are reversibly exchanged from one library to the other, constituting an antiparallel dynamic covalent system. Herein we report that communication between two different dynamic libraries through an irreversible process is also possible. Indeed, alkyl amines cancel the dynamic regime on the nucleophilic substitution of tetrazines, generating kinetically inert compounds. Interestingly, such amine can be part of another dynamic library, an imine‐amine exchange. Thus, both libraries are interconnected with each other by an irreversible process which leads to kinetically inert structures that contain parts from both libraries, causing a collapse of the complexity. Additionally, a latent irreversible intercommunication could be developed. In such a way, a stable molecular system with specific host–guest and fluorescence properties, could be irreversibly transformed when the right stimulus was applied, triggering the cancellation of the original supramolecular and luminescent properties and the emergence of new ones. [ABSTRACT FROM AUTHOR]

Recently, π–π stacked antiaromatic π‐systems have received considerable attention because they can exhibit stacked‐ring aromaticity due to substantial intermolecular orbital interactions. Here, we report three antiaromatic norcorrole dimers that self‐assemble to form supramolecular architectures through chiral self‐sorting. A 2,2'‐linked norcorrole dimer with 3,5‐di‐tert‐butylphenyl groups forms a π‐stacked dimer both in solid and solution states via homochiral self‐sorting. Its association constant in solution is (3.6±1.7)×105 M−1 at 20 °C. In the solid state, 3,3'‐linked norcorrole dimers with 3,5‐di‐tert‐butylphenyl and phenyl groups afford macrocyclic and helical supramolecular assemblies via heterochiral and homochiral self‐sorting, respectively. Notably, the subtle modification in the substituent resulted in a complete change in the structure of the aggregates and the chiral self‐sorting mode. The present findings demonstrate that structural manipulation in antiaromatic monomer units leads to the formation of various supramolecular assemblies on the basis of the attractive interactions between antiaromatic π‐systems. [ABSTRACT FROM AUTHOR]

Incorporating chiral elements in host–guest systems currently attracts much attention because of the major impact such structures may have in a wide range of applications, from pharmaceuticals to materials science and beyond. Moreover, the development of multi‐responsive and ‐functional systems is highly desirable since they offer numerous benefits. In this context, we describe herein the construction of a metal‐driven self‐assembled cage that associates a chiral truxene‐based ligand and a bis‐ruthenium complex. The maximum separation between both facing chiral units in the assembly is fixed by the intermetallic distance within the lateral bis‐ruthenium complex (8.4 Å). The resulting chiral cavity was shown to encapsulate polyaromatic guest molecules, but also to afford a chiral triply interlocked [2]catenane structure. The formation of the latter occurs at high concentration, while its disassembly could be achieved by the addition of a planar achiral molecule. Interestingly the planar achiral molecule exhibits induced circular dichroism signature when trapped within the chiral cavity, thus demonstrating the ability of the cage to induce supramolecular chirogenesis. [ABSTRACT FROM AUTHOR]

The present work investigates the size based self-sorting behavior of particles near the contact line (CL) region of an evaporating sessile aqueous droplet containing bidispersed (1 and 3 μm) colloidal particles. Experiments were performed on hydrophilic glass and hydrophobic (Poly)dimethylsiloxane (PDMS) substrates maintained at different temperatures (Ts = 23°C, 50°C, and 80°C). The role of substrate wettability and substrate temperature in the modulation of final deposition specifically, the self-sorting characteristics was examined. Various experimental techniques namely, high-speed visualization, 3D optical profilometry, fluorescence microscopy, and scanning electron microscopy were implemented to analyze the droplet evaporation and the morphology of the final deposition. As per the findings, in the case of hydrophilic substrate self-sorting existed at all temperatures. However, an appreciable improvement in the sorting quality was observed only at elevated temperatures. Particularly, for the case of Ts = 80°C in which the final deposition demonstrated better sorting of 1 and 3 μm particles. Since, most of the region in the CL's vicinity had a substantial reduction in the intermixing of 1 and 3 μm particles, thus effectively favouring the suppression of mixed region. In the case of nonheated (Ts = 23°C) hydrophobic substrate it was observed that a continuous depinning of the CL, in conjunction, with a weak radial flow led to complete intermixing of the bidispersed particles thus, lacking any self-sorting behavior. However, for the heated hydrophobic substrate cases, a substantial delay in the depinning of the CL existed. This, in turn, combined with the outward-driven capillary flow and recirculatory thermal-Marangoni flow resulted in the manifestation of self-sorting phenomenon. This study is expected to offer novel fundamental insights into the underlying mechanisms that can be effectively leveraged, to gain better control of the governing parameters for the realization of desired sorting characteristics. [ABSTRACT FROM AUTHOR]

Co-assembly of inorganic nanoparticles (NPs) and nanostructured polymer matrix represents an intricate interplay of enthalpic or entropic forces. Particle size largely affects the phase behavior of the nanocomposite. Theoretical studies indicate that new morphologies would emerge when the particles become comparable to the soft matrix's size, but this has rarely been supported experimentally. By designing a multicomponent blend composed of NPs, block copolymer-based supramolecules, and small molecules, a 3-D ordered lattice beyond the native BCP's morphology was recently reported when the particle is larger than the microdomain of BCP. The blend can accommodate various formulation variables. In this paper, when the particle size equals the microdomain size, a symmetry-broken phase appears in a narrow range of particle sizes and compositions, which we named the "train track" structure. In this phase, the NPs aligned into a 3-D hexagonal lattice and packed asymmetrically along the c axis, making the projection of the ac and the bc plane resemble train tracks. Computational studies show that the broken symmetry reduces the polymer chain deformation and stabilizes the metastable hexagonally perforated lamellar morphology. Given the mobility of the multicomponent blend, the system shows a self-sorting behavior: segregating into two macroscopic phases with different nanostructures based on only a few nanometers NP size differences. Smaller NPs form "train track" morphology, while larger NPs form a "simple hexagon" structure, where the NPs take a symmetric hexagonal arrangement. Detailed structural evolution and simulation studies confirm the systematic-wide cooperativity across different components, indicating the strong self-regulation of the multicomponent system.

A unique microstructure‐driven self‐sorting of chemically indistinguishable side chains in alkyl siloxanes is reported for the first time. The difference in cooperativity among the side alkyl chains caused by the variation in backbone microstructure is the key to drive this self‐sorting. The study also reveals that while alkyl chains of random and fully blocked siloxane discriminate each other, the alkyl chains of partially blocked siloxane can form crystals with both polymers resulting in reinforcement of the mechanical property of the blends. [ABSTRACT FROM AUTHOR]

Self‐sorting is commonly observed in complex reaction systems, which has been utilized to guide the formation of single major by‐design molecules. However, most studies have been focused on non‐covalent systems, and using self‐sorting to achieve covalently bonded architectures is still relatively less explored. Herein, we first demonstrated the dynamic nature of spiroborate linkage and systematically studied the self‐sorting behavior observed in the transformation between spiroborate‐linked well‐defined polymeric and molecular architectures, which is enabled by spiroborate bond exchange. The scrambling between a macrocycle and a 1D helical covalent polymer led to the formation of a molecular cage, whose structures are all unambiguously elucidated by single‐crystal X‐ray diffraction. The results indicate that the molecular cage is the thermodynamically favored product in this multi‐component reaction system. This work represents the first example of a 1D polymeric architecture transforming into a shape‐persistent molecular cage, driven by dynamic covalent self‐sorting. This study will further guide the design of spiroborate‐based materials and open the possibilities for the development of novel complex yet responsive dynamic covalent molecular or polymeric systems. [ABSTRACT FROM AUTHOR]

The biointerface engineering of living cells by creating an abiotic shell has important implications for endowing cells with exogenous properties with improved cellular behavior, which then boosts the development of the emerging field of living cell hybrid materials. Herein, we develop a way to perform active nanoencapsulation of single cell, which then endows the encapsulated cells with motion ability that they do not inherently possess. The emerging motion characteristics of the encapsulated cells could be self-regulated in terms of both the motion velocity and orbits by different proliferation modes. Accordingly, by taking advantage of the emergence of differentiated moving abilities, we achieve the self-sorting between mother cells and daughter cells in a proliferated Saccharomyces cerevisiae cell community. Therefore, it is anticipated that our highlighted study could not only serve as a new technique in the field of single-cell biology analysis and sorting such as in studying the aging process in Saccharomyces cerevisiae, but also open up opportunities to manipulate cell functionality by creating biohybrid materials to fill the gap between biological systems and engineering abiotic materials. [ABSTRACT FROM AUTHOR]

Coordination chemistry is a powerful method to synthesize supramolecular cages with distinct features that suit specific applications. This work demonstrates the synthesis of discrete, homochiral FeII2L3 cages via chirality‐driven self‐assembly. Specifically, the installation of chirality – at both the vertices and ligand backbones – allows the formation of discrete, homochiral FeII2L3 cages of different sizes via stereochemical control of the iron(II) centers. We observed that larger cages require multiple chiral centra (chiral ligands and vertices). In contrast, the formation of smaller cages is stereoselective with solely chiral ligands. The latter cages can also be formed from two chiral subcomponents, but only when they have matching chirality. Single‐crystal X‐ray diffraction of these smaller FeII2L3 cages revealed several non‐covalent interactions as a driving force for narcissistic chiral self‐sorting. This expected behavior was confirmed utilizing the shorter ligands in racemic form, yielding discrete, homochiral FeII2L3 cages formed in enantiomeric pairs. [ABSTRACT FROM AUTHOR]

Aromatic oligoamide sequences programmed to fold into stable helical conformations were designed to display a linear array of hydrogen‐bond donors and acceptors at their surface. Sequences were prepared by solid‐phase synthesis. Solution 1H NMR spectroscopic studies and solid‐state crystallographic structures demonstrated the formation of stable hydrogen‐bond‐mediated dimeric helix bundles that could be either heterochiral (with a P and an M helix) or homochiral (with two P or two M helices). Formation of the hetero‐ or homochiral dimers could be driven quantitatively using different chlorinated solvents—exemplifying a remarkable case of either social or narcissistic chiral self‐sorting or upon imposing absolute handedness to the helices to forbid PM species. [ABSTRACT FROM AUTHOR]

Abstract The design of crosslinking domains is a vital factor to create functional hydrogels with controlled physical, mechanical, and adhesive properties. This paper demonstrates versatile synthetic systems of micelle‐crosslinked hydrogels with highly stretchable, self‐healing, and selectively adhesive properties. For this, methacrylate‐bearing random copolymer micelles are designed as physical and covalent crosslink domains via the self‐assembly of amphiphilic random copolymers carrying hydrophilic poly(ethylene glycol) (PEG), hydrophobic butyl or dodecyl groups, and methacrylate‐terminal PEG in water. The size, aggregation number, and pendant methacrylate number of the micelles are controlled by the composition and degree of polymerization. Hydrogels are efficiently obtained from the free radical polymerization of hydrophilic monomers such as PEG acrylate and acrylamide in the presence of the micelle crosslinkers in water. Owing to the dynamic yet selective chain exchange properties of the micelle domains, the hydrogels are highly stretchable up to over 1000% and show self‐healing and selectively adhesive properties. The self‐healing of hydrogels is promoted upon heating due to the fast chain exchange of the micelle domains, whereas hydrogels consisting of micelles with different alkyl groups are never adhesive because of their self‐sorting properties.

Mixing low molecular weight gelators (LMWGs) can be used to combine favorable properties of the individual components within a multifunctional gel. Such multicomponent systems are complex enough in themselves but the method of combining components is not commonly considered something to influence self‐assembly. Herein, two multicomponent systems comprising of a naphthalene‐based dipeptide hydrogelator and one of two modified naphthalene diimides (NDIs), one of which forms gels, and the other does not, are investigated. These systems are probed, examining the structures formed and their gel properties (when preparing a solution from either a mixed powder of both components or by mixing pre‐formed solutions of each component) using rheology, small angle neutron scattering (SANS), and absorbance spectroscopy. It is found that by altering the method of preparation, it is can either induce self‐sorting or co‐assembly within the fibers formed that underpin the gel network. [ABSTRACT FROM AUTHOR]

Designing artificial systems to mimic chiral superstructures and exploring how achiral molecules precisely modulate their chirality is crucial to understand the origin of homochirality in nature. Herein, the tunability nature of supramolecular chirality is subtly applied to fabricate robust chiral covalent polymers with controlled macroscopic helicity. When using conventional supramolecular transcription methods to prepare chiral poly(m‐phenylenediamine), simply introducing various small amounts of achiral diaminopyridines (DAPs) to copolymerize with m‐phenylenediamine (MPD) enables the resulting chiral copolymers with adjustable helical configurations and chiroptical activities in an enantiopure template system. The strong hydrogen bonds between DAPs and the template molecules ((S)/(R)‐PhgC16) proved to be the driving force for guiding the chiral polymerization mode of MPD. Impressively, the exquisite self‐sorting phenomenon is observed by tuning the stoichiometric ratio of DAP and (R)‐PhgC16, where the as‐prepared copolymers with opposite helicity can exist simultaneously to form a double network structure and their chiroptical activity can be well regulated. In addition, based on such a copolymerization strategy, a conceptual library of helical functional copolymers is built with editable polymer types including conducting polymers and designable amine‐aldehyde condensation‐based polymers. This copolymerization‐mediated synthetic strategy may facilitate the development of chiral polymers with controlled morphologies and dynamic compositions. [ABSTRACT FROM AUTHOR]

The concept of "reaction network" represents a system that is constructed from reactions between different organic units basing on logical transformation relationships. This network is refined through multiple parallel cascade reaction sequences, showcasing attributes such as "self-direction, self-sorting, convergence and normalization". The ability of synthesizing tissues within molecular systems is a key aspect that could serve as a valuable tool for the rational design of new reactions. In this paper, we summarized our research work on self-organized reaction network in the past two decades from three aspects: self-sorting convergent integration reaction network, self-labor convergent integration reaction network and complex integration reaction network. [Display omitted] [ABSTRACT FROM AUTHOR]

[Display omitted] • This study is the first example to use metal nanocluster (NCs) to construct a self-sorting assembly system. • A self-sorting assembly system of water-soluble silver NCs (Ag 9 -NCs) and hydrophobic peptides (D, D) through solvent regulation strategy were successfully constructed. • The introduction of higher concentrations of (D, D) caused the Ag 9 -NCs assembly to aggregate more closely, resulting in different morphologies from single Ag 9 -NCs. • The presence of (D, D) gel matrix induces the AIE effect of Ag 9 -NCs, which changes the system from weak orange fluorescence to bright white fluorescence. Self-sorting plays a crucial role in living systems, such as in the specific folding of proteins and the selective assembly of DNA. Inspired by these natural processes, scientists have begun to construct artificial systems containing multiple components, allowing for better analysis of complex natural systems. In this work, the self-sorting assembly of a water-soluble silver nanocluster ((NH 4) 9 [Ag 9 (mba) 9 ], H 2 mba = 2-mercaptobenzoic acid, Ag 9 -NCs) and hydrophobic peptide (Palmitoyl-DiAsparitcacid, D, D) was achieved through a solvent regulation strategy to construct a complex supramolecular system. Under the synergistic effect of hydrophobic interactions and hydrogen bonding, Ag 9 -NCs and (D, D) can form gels with effective phase separation in a very short time, exhibiting interesting self-sorting properties. Additionally, the (D,D) gel matrix boosts the crystallinity of the Ag9-NCs assembly and improves the organization of Ag 9 -NCs aggregates. This triggers the aggregation-induced emission (AIE) effect in Ag 9 -NCs, resulting in increased luminescence of the system. This study is the first to use metal NCs to create a self-sorting assembly system. It enhances our understanding of assembly mechanism of metal NCs, offers various solutions for their assembly and performance regulation, and marks significant progress towards mimicking multi-component self-sorting systems found in nature. [ABSTRACT FROM AUTHOR]

Dynamic covalent polymers of different topology have been synthesized from an aromatic dialdehyde and α,ω‐dinitroalkanes via the nitroaldol reaction. All dinitroalkanes yielded dynamers with the dialdehyde, where the length of the dinitroalkane chain played a vital role in determining the structure of the final products. For longer dinitroalkanes, linear dynamers were produced, where the degree of polymerization reached a plateau at higher feed concentrations. In the reactions involving 1,4‐dinitrobutane and 1,5‐dinitropentane, specific macrocycles were formed through depolymerization of the linear chains, further driven by precipitation. At lower temperature, the same systemic self‐sorting effect was also observed for the 1,6‐dinitrohexane‐based dynamers. Moreover, the dynamers showed a clear adaptive behavior, displaying depolymerization and rearrangement of the dynamer chains in response to alternative building blocks as external stimuli. [ABSTRACT FROM AUTHOR]

Pd(II)-based low-symmetry coordination cages possessing anisotropic cavities are of great interest. The common strategies employed to achieve such cages utilize either more than one type of symmetrical ligands (e.g., L aa , L bb etc.) or only one type of unsymmetrical ligand (e.g., L ab ). To significantly enhance the anisotropy, we have designed two unsymmetrical bidentate ligands i.e., L ab and L cd , aiming at a low-symmetry Pd 2 L ab 2 -type cage. It was accomplished by high-fidelity integrative self-sorting of two different low-symmetry cages having Pd cd 2 -type cage. It was accomplished by high-fidelity integrative self-sorting of two different low-symmetry cages having Pd 2 L ab 4 and Pd 4 L cd 8 -type architectures (homoleptic complexes of the designed ligands). Structural constraints and geometry complementarity in the ligand design drive the non-statistical exclusive self-assembly of the Pd 2 L ab -type cage was also obtained. Heteromeric completive self-sorting of three homoleptic assemblies (Pd 2 L cd 2 -type cage. By taking advantage of the complemental geometries between ligands, a low-symmetry Pd 2 L ab 2 L cc 2 -type cage was also obtained. Heteromeric completive self-sorting of three homoleptic assemblies (Pd 2 L ab 4 , Pd 4 L cc 8 and Pd 4 L cd 8 -type cages) into an exclusive mixture of Pd 2 L ab 2 L cd 2 and Pd 2 L ab 2 L cc 2 -type mixed ligated assemblies was demonstrated through cage-to-cage transformations., (© 2024 Wiley-VCH GmbH.)

Conductive flexible hydrogels have attracted immense attentions recently due to their wide applications in wearable sensors. However, the poor mechanical properties of most conductive polymer limit their utilizations. Herein, a double network hydrogel is fabricated via a self-sorting process with cationic polyacrylamide as the first flexible network and the lantern[3 3 ]arene-based hydrogen organic framework nanofibers as the second rigid network. This hydrogel is endowed with good conductivity (0.25 S m -1 ) and mechanical properties, such as large Young's modulus (31.9 MPa), fracture elongation (487%) and toughness (6.97 MJ m -3 ). The stretchability of this hydrogel is greatly improved after the kirigami cutting, which makes it can be used as flexible strain sensor for monitoring human motions, such as bending of fingers, wrist and elbows. This study not only provides a valuable strategy for the construction of double network hydrogels by lanternarene, but also expands the application of the macrocycle hydrogels to flexible electronics., (© 2024 Wiley‐VCH GmbH.)

Despite the high prevalence and functional significance of nonregular assemblies in biology, little attention has been given to realize them in artificial systems. Here, the discovery of general principles underlying the formation of nonregular objects is described by chemical self‐assembly. The cell‐shaped assemblies (CSAs) are characterized by a main body comprising a nonregular vesicle and dendritically shaped spiky projections. The major mechanisms of CSA morphogenesis are: first, polycrystalline structures consisting of grains and grain boundaries induce the formation of nonregular objects by promoting nonuniform supramolecular crystal growth. Second, the fibrous nanostructures in 2D networks and in 1D bundles firmly support the main body and the spiky projections, respectively. This study also shows that there exist certain connections among entirely disparate entities, that is, organic supramolecular assemblies, inorganic materials, and cells regarding their fundamental principles of building block organizations. The principle behind the CSA formation can be applied to control the dynamic and mechanical properties of self‐assembled materials. [ABSTRACT FROM AUTHOR]

Supramolecular gels formed by the combination of different organic molecules are of significant interest in the search of new functional materials. When two different molecules are mixed to form gels, the self‐assembled fibres can be a result of self‐sorting or co‐assembly. A key challenge is to control the network type. Here, we demonstrate that control over the network type can be achieved either by varying the hydrophobicity of a component or by employing a pH‐switch method. [ABSTRACT FROM AUTHOR]

Coordination driven self-assembly of achiral components, i.e., hexa-alkylated truxene ligands (L) with bis-metallic complexes (M2), afforded three chiral face-rotating stereoisomer polyhedra (M6L2). By tuning the length of the alkyl chains as well as the distance between both ligands facing each other in the self-assemblies (M6L2), one can control the diastereomeric distribution between the expected homo- and hetero-chiral structures. [ABSTRACT FROM AUTHOR]

Molecular recognition is a form of information transfer, seen in the base pairing in DNA which is derived from the identity (acceptor or donor) and number of hydrogen bond sites within each base. Here we report bis‐ligand palladium(II) complexes that exhibit similar complementarity. Pd(II) has square planar four‐coordinate geometry, giving control over ligand orientation and denticity. Pairings were developed using ligand denticity (3 : 1 or 2 : 2), and hydrogen bond capability (AA:DD or AD:DA) or lack thereof. Five pairings were investigated, with two sets of four being found fully orthogonal. The two 3 : 1 pairings exhibited limited ligand exchange. The extent of this exchange varied dependant on solvent from 2 : 1 (desired to undesired) to 6 : 1. A reliable and varied set of ligand pairs have therefore been developed for bis‐ligand coordination sphere engineering in pursuit of sorting for complex molecular architectures and molecular‐level information storage and transfer events. [ABSTRACT FROM AUTHOR]

Abstract Gels prepared from low-molecular-weight gelators (LMWGs) represent versatile soft materials. Self-assembly of LMWGs forms nanofibers and above critical gelation concentrations, the entanglement of which leads to self-supporting gels. Owing to the dynamic properties of the self-assembly process, stimuli-responsive LMWGs have prospered in the last decade. In addition, incorporating multiple LMWGs into one system brings the opportunity to achieve sophisticated designs and functions. This review covers recent advances in the field of supramolecular gels, from stimuli-responsive gelators to multicomponent systems that are self-sorting and/or co-assembling.

Three distinct four-component supramolecular nanorotors were prepared, using, for the first time, bipyridine instead of phenanthroline stations in the stator. Following our established self-sorting protocol to multicomponent nanodevices, the nanorotors were self-assembled by mixing the stator, rotators with various pyridine head groups, copper(I) ions and 1,4-diazabicyclo[2.2.2]octane (DABCO). Whereas the exchange of a phenanthroline vs. a bipyridine station did not entail significant changes in the rotational exchange frequency, the para-substituents at the pyridine head group of the rotator had drastic consequences on the speed: 4-OMe (k298 = 35 kHz), 4-H (k298 = 77 kHz) and 4-NO2 (k298 = 843 kHz). The exchange frequency (log k) showed an excellent linear correlation with both the Hammett substituent constants and log K of the copper(I)–ligand interaction, proving that rotator–copper(I) bond cleavage is the key determining factor in the rate-determining step.

Self‐assembled coordination cages and metal–organic frameworks have relied extensively on symmetric ligands in their formation. Here we have prepared a relatively simple system employing an unsymmetric ligand that results in two distinct self‐assembled structures, a [Fe2L3]4+ helicate and a [Fe4L6]8+ cage composed of 10 interconverting diastereomers and their enantiomers. We show that the steric profile of the ligand controls the complexity, thermodynamics and kinetics of interconversion of the system. [ABSTRACT FROM AUTHOR]

Over years self-sorting has developed into a powerful tool in supramolecular chemistry, for instance, to promote the error-free formation of intricate multicomponent assemblies. However, in order to use the enormous potential of self-sorting for sophisticated information processing more recent developments have focused on the reversible reconfiguration of multicomponent systems driven by multiple self-sorting protocols. The present mini review will provide an overview over the latest advancements in this field with a focus on reversibly switchable functions in discrete supramolecular systems.

Exploiting the orthogonal molecular interactions of natural (phospholipids) and synthetic (mono‐allyloxylated cucurbit[7]uril) amphiphiles to form their own vesicles, the formation of two different types of compartments in a self‐sorted manner mimicking cellular compartments is demonstrated. Even after simultaneous extrusion of both vesicles through small pore membranes, which transformed them into smaller vesicles, both vesicles were not fused but still appeared as independent compartments in sucrose solution. The simultaneous use of natural and synthetic amphiphiles, forming independent compartments, holds great potential for in‐depth investigation of self‐sorted multi‐compartments and their structures as prototype cells. [ABSTRACT FROM AUTHOR]

Nature creates exquisite molecular assemblies, required for the molecular-level functions of life, via self-assembly. Understanding and harnessing these complex processes presents an immense opportunity for the design and fabrication of advanced functional materials. However, the significant industrial potential of self-assembly to fabricate highly functional materials is hampered by a lack of knowledge of critical reaction intermediates, mechanisms, and kinetics. As we move beyond the covalent synthetic regime, into the domain of non-covalent interactions occupied by self-assembly, harnessing and embracing complexity is a must, and non-targeted analyses of dynamic systems are becoming increasingly important. Coordination driven self-assembly is an important subtype of self-assembly that presents several wicked analytical challenges. These challenges are “wicked” due the very complexity desired confounding the analysis of products, intermediates, and pathways, therefore limiting reaction optimisation, tuning, and ultimately, utility. Ion Mobility-Mass Spectrometry solves many of the most challenging analytical problems in separating and analysing the structure of both simple and complex species formed via coordination driven self-assembly. Thus, due to the emerging importance of ion mobility mass spectrometry as an analytical technique tackling complex systems, this review highlights exciting recent applications. These include equilibrium monitoring, structural and dynamic analysis of previously analytically inaccessible complex interlinked structures and the process of self-sorting. The vast and largely untapped potential of ion mobility mass spectrometry to coordination driven self-assembly is yet to be fully realised. Therefore, we also propose where current analytical approaches can be built upon to allow for greater insight into the complexity and structural dynamics involved in self-assembly.

Nature segregates fundamental tasks such as information storage/transmission and catalysis between two different compound classes (e.g. polynucleotides for replication and folded polyamides for catalysis). This division of labor is likely a product of evolution, raising the question of how simpler systems in which replicators and folded macromolecules co‐exist may emerge in the transition from chemistry to biology. In synthetic systems, achieving co‐existence of replicators and foldamers in a single molecular network remains an unsolved problem. Previous work on dynamic molecular networks has given rise to either self‐replicating fibers or well‐defined foldamer structures (or completely un‐sorted complex systems). We report a system in which two cross‐reactive dithiol (nucleobase‐ and peptide‐based) building blocks self‐sort into a replicator fiber and foldamer that both emerge spontaneously and co‐exist. The self‐sorting behavior remains prevalent across different building block ratios as two phases of emergence occur: replicator growth followed by foldamer formation. This is attributed to the autocatalytic formation of the replicator fiber, followed by enrichment of the system in the remaining building block, which is subsequently incorporated into a foldamer. [ABSTRACT FROM AUTHOR]

Supramolecular nanopatterns of arylene–alkynylene squares with side chains of different lengths are investigated by scanning tunneling microscopy at the solid/liquid interface of highly oriented pyrolytic graphite and 1,2,4-trichlorobenzene. Self-sorting leads to the intermolecular interdigitation of alkoxy side chains of identical length. Voids inside and between the squares are occupied by intercalated solvent molecules, which numbers depend on the sizes and shapes of the nanopores. In addition, planar and non-planar coronoid polycyclic aromatic hydrocarbons (i.e., butyloxy-substituted kekulene and octulene derivatives) are found to be able to intercalate into the intramolecular nanopores.

The quantitative double self-sorting between the three-component rectangle [Cu4(1)2(2)2]4+ and the four-component sandwich complex [Cu2(1)(2)(4)]2+ is triggered by inclusion and release of DABCO (4). The fully reversible and clean switching between two multicomponent supramolecular architectures can be monitored by fluorescence changes at the zinc porphyrin sites. The structural changes are accompanied by a huge spatial contraction/expansion of the zinc porphyrin–zinc porphyrin distances that change from 31.2/38.8 Å to 6.6 Å and back. The supramolecular interconversion was used for the highly selective detection of DABCO in a mixture of other similar compounds.

Coordination driven self-assembly of achiral components, i.e., hexa-alkylated truxene ligands (L) with bis-metallic complexes (M2), afforded three chiral face-rotating stereoisomer polyhedra (M6L2). By tuning the length of the alkyl chains as well as the distance between both ligands facing each other in the self-assemblies (M6L2), one can control the diastereomeric distribution between the expected homo- and hetero-chiral structures.

Chiral self‐sorting is intricately connected to the complicated chiral processes observed in nature and no artificial systems of comparably complexity have been generated by chemists. However, only a few examples of purely organic molecules have been reported so far, where the self‐sorting process could be controlled. Herein, we describe the chiral self‐sorting of large cubic [8+12] salicylimine cage compounds based on a chiral TBTQ precursor. Out of 23 possible cage isomers only the enantiopure and a meso cage were observed to be formed, which have been unambiguously characterized by single crystal X‐ray diffraction. Furthermore, by careful choice of solvent the formation of meso cage could be controlled. With internal diameters of din=3.3–3.5 nm these cages are among the largest organic cage compounds characterized and show very high specific surface areas up to approx. 1500 m2 g−1 after desolvation. [ABSTRACT FROM AUTHOR]

Self‐sorting plays a crucial role in living systems such as the selective assembly of DNA and specific folding of proteins. However, the self‐sorting of artificial helical polymers such as biomacromolecules has rarely been achieved. In this work, single‐handed helical poly(phenyl isocyanide)s bearing pyrene (Py) and naphthalene (Np) probes were prepared, which exhibited interesting self‐sorting properties driven by both helicity and molecular weight (Mn) in solution, solid state, gel, and on the gel surface as well. The polymers with the same helix sense and similar Mn can self‐sort and assemble into well‐defined two‐dimensional smectic architectures and form stable gels in organic solvents. In contrast, mixed polymers with opposite handedness or different Mn were repulsive to each other and did not aggregate. Moreover, the gels of helical polymers with the same handedness and similar Mn can recognize themselves and adhere together to form a gel. [ABSTRACT FROM AUTHOR]

The emerging field of molecular cybernetics has the potential to widely broaden our perception of chemistry. Chemistry will develop beyond its current focus that is mainly concerned with single transformations, pure compounds, and/or defined mixtures. On this way, chemistry will become autonomous, networked and smart through communicating molecules each of which serves a control engineering purpose, like the set of wheels in the machinery of life. The present personal account describes our latest developments in this field. [ABSTRACT FROM AUTHOR]

The bottom-up construction of Frank–Kasper (FK) phases in soft matter requires intricating tuning to balance entropic and enthalpic interactions. In contrast, sophisticated rules have been established in Metallurgy to dictate the packing structures of metal alloys. Inspired by alloy metallurgy, we develop a new self-sorting approach to construct nanostructures in condensed soft matters. This approach utilizes blends of nano-sized giant molecules to construct supramolecular motifs (“mesoatoms”) with controlled size heterogeneity, which is the key in rational design of diverse FK nanostructures. Especially, the scarcely observed thermodynamically stable Laves C14 and C15 phases are widely found. This approach sheds light on next-generation material engineering which allows nanostructure construction in a more predictable and straightforward way

The title nonplanar electron acceptor (1) fused with a selenadiazole ring selectively forms a crystalline charge‐transfer complex (CT crystal) with 2,6‐dimethylnaphthalene (2,6‐DMN). On the other hand, the sulfur analogue (2) has less recognition ability and forms CT crystals with both 2,6‐ and 2,7‐DMN. X‐ray analyses of 1, 2, and their CT crystals revealed that the Se⋅⋅⋅N chalcogen bond (ChB) in 1 is strong enough to determine the crystal packing with the formation of a cavity suitable for 2,6‐DMN. On the contrary, ChB through S⋅⋅⋅N contact in 2 competes with other weak interactions such as a C−H⋅⋅⋅N hydrogen bond. The stronger ChB involving Se is the key for 1 to separate 2,6‐DMN (>97 wt %) from a complex isomer mixture containing ca. 10 wt % each of 2,6‐ and 2,7‐DMN by a simple, efficient and straightforward mixing‐filtration‐heating process. [ABSTRACT FROM AUTHOR]

Background: The construction of gels from low molecular weight gelators (LMWG) has been extensively studied in the fields of bio-nanotechnology and other fields. However, the understanding gaps still prevent the prediction of LMWG from the full design of those gel systems. Gels with multicomponent become even more complicated because of the multiple interference effects coexist in the composite gel systems., Aim of Review: This review emphasizes systems view on the understanding of multicomponent low molecular weight gels (MLMWGs), and summarizes recent progress on the construction of desired networks of MLMWGs, including self-sorting and co-assembly, as well as the challenges and approaches to understanding MLMWGs, with the hope that the opportunities from natural products and peptides can speed up the understanding process and close the gaps between the design and prediction of structures., Key Scientific Concepts of Review: This review is focused on three key concepts. Firstly, understanding the complicated multicomponent gels systems requires a systems perspective on MLMWGs. Secondly, several protocols can be applied to control self-sorting and co-assembly behaviors in those multicomponent gels system, including the certain complementary structures, chirality inducing and dynamic control. Thirdly, the discussion is anchored in challenges and strategies of understanding MLMWGs, and some examples are provided for the understanding of multicomponent gels constructed from small natural products and subtle designed short peptides., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Production and hosting by Elsevier B.V.)

New results are presented on the multicomponent supramolecular synthesis of pseudo[1]rotaxanes, achieved by designing pairs of structurally matching N‐monoalkyl‐4,4'‐bipyridinium/2,7‐diazapyrenium‐based ligands having complementary π‐donor/acceptor features, and intended to self‐assemble into the targeted supramolecules by following integrative self‐sorting processes. In all the studied cases, it was found that the envisioned species, characterized by NMR spectroscopy and MS spectrometry, arise as the main products of the self‐assembly in aqueous media by using palladium(II)/platinum(II) metal centers as the guiding force. Crucially, we have also found that by improving the π‐donor/acceptor properties of the matching pairs of ligands (L4 and L5), the integrative self‐sorting processes prevail even in the absence of metallic ions to afford the heterodimeric species with an association constant being 756±43 M−1. [ABSTRACT FROM AUTHOR]

The article shows key physical properties of the grain mass: looseness, self-sorting and thermal-moisture conduction. Classical information was supplemented by practical and scientific observations of the author. The pile of millet and flax has such looseness that, if a person steps on its surface, he/she can plunge into it and be killed. The risk of death is connected with super-cooling and possible penetration of grains into respiratory ways. The situation can deteriorate, in case extra efforts and movements are made to get free, which could cause a quick sinking in grain. It is strictly forbidden to stay on the surface of grain pile during unloading by drift. The grain mass during transportation gets exfoliated in two triangle layers, which are different in quality. Self-sorting in a newly-formed grain pile during loading-unloading also has its peculiarities. The peripheral part of the pile, as a rule consists of light admixture and thin grain, while the central part – of high-quality grain. The author shows possible negative effects of thermalmoisture conduction. Knowledge of these characteristics can help work successfully with grain and avoid damage of grain due to its growing mouldy and self-heating.

The dynamics of hydrogen bonding do not only play an important role in many biochemical processes but also in Nature's multicomponent machines. Here, a three‐component nanorotor is presented where both the self‐assembly and rotational dynamics are guided by hydrogen bonding. In the rate‐limiting step of the rotational exchange, two phenolic O‐H–N,N(phenanthroline) hydrogen bonds are cleaved, a process that was followed by variable‐temperature 1H NMR spectroscopy. Activation data (ΔG≠298=46.7 kJ mol−1 at 298 K, ΔH≠=55.3 kJ mol−1, and ΔS≠=28.8 J mol−1 K−1) were determined, furnishing a rotational exchange frequency of k298=40.0 kHz. Fully reversible disassembly/assembly of the nanorotor was achieved by addition of 5.0 equivalents of trifluoroacetic acid (TFA)/1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) over three cycles. [ABSTRACT FROM AUTHOR]

Many interesting target guest molecules have low symmetry, yet most methods for synthesising hosts result in highly symmetrical capsules. Methods of generating lower symmetry pores are thus required to maximise the binding affinity in host–guest complexes. Herein, we use mixtures of tetraaldehyde building blocks with cyclohexanediamine to access low‐symmetry imine cages. Whether a low‐energy cage is isolated can be correctly predicted from the thermodynamic preference observed in computational models. The stability of the observed structures depends on the geometrical match of the aldehyde building blocks. One bent aldehyde stands out as unable to assemble into high‐symmetry cages‐and the same aldehyde generates low‐symmetry socially self‐sorted cages when combined with a linear aldehyde. We exploit this finding to synthesise a family of low‐symmetry cages containing heteroatoms, illustrating that pores of varying geometries and surface chemistries may be reliably accessed through computational prediction and self‐sorting. [ABSTRACT FROM AUTHOR]

The assembly of complex molecules, such as organic cages, can be achieved through supramolecular and dynamic covalent strategies. Their use in a range of applications has been demonstrated, including gas uptake, molecular separations, and in catalysis. However, the targeted design and synthesis of new species for particular applications is challenging, particularly as the systems become more complex. High‐throughput computation‐only and experiment‐only approaches have been developed to streamline the discovery process, although are still not widely implemented. Additionally, combined hybrid workflows can dramatically accelerate the discovery process and lead to the serendipitous discovery and rationalisation of new supramolecular assemblies that would not have been designed based on intuition alone. This Minireview focuses on the advances in high‐throughput approaches that have been developed and applied in the discovery of supramolecular organic cages. [ABSTRACT FROM AUTHOR]

The simple preparation of the multicomponent devices [Cu4(A)2]4+ and [Cu2(A)(B)]2+, both rotors with fluxional axles undergoing domino rotation, highlights the potential of self‐sorting. The concept of domino rotation requires the interconversion of axle and rotator, allowing the spatiotemporal decoupling of two degenerate exchange processes in [Cu4(A)2]4+ occurring at 142 kHz. Addition of two equiv of B to rotor [Cu4(A)2]4+ afforded the heteromeric two‐axle rotor [Cu2(A)(B)]2+ with two distinct exchange processes (64.0 kHz and 0.55 Hz). The motion requiring a pyridine→zinc porphyrin bond cleavage is 1.2×105 times faster than that operating via a terpyridine→[Cu(phenAr2)]+ rupture. Finally, both rotors are catalysts due to their copper(I) content. The fast domino rotor (142 kHz) was shown to suppress product inhibition in the catalysis of the azide–alkyne Huisgen cyclo-addition. [ABSTRACT FROM AUTHOR]

Three imine‐based metal complexes, having no overlap in terms of their compositions, have been simultaneously generated from the self‐sorting of a constitutional dynamic library (CDL) containing three amines, three aldehydes, and three metal salts. The hierarchical ordering of the stability of the three metal complexes assembled and the leveraging of the antagonistic and agonistic relationships existing between the constituents within the constitutional dynamic network corresponding to the CDL were pivotal in achieving the sorting. Examination of the process by NMR spectroscopy showed that the self‐sorting of the FeII and ZnII complexes depended on an interplay between the thermodynamic driving forces and a kinetic trap involved in their assembly. These results also exemplify the concept of “simplexity”—the fact that the output of a self‐assembling system may be simplified by increasing its initial compositional complexity—as the two complexes could self‐sort only in the presence of the third pair of organic components, those of the CuI complex. [ABSTRACT FROM AUTHOR]

Five ligands with either nitrile or isonitrile metal binding motifs have been synthesized based on the 2,8- or 3,9-disubstituted Tröger's base scaffold, respectively. These ligands self-assemble into dinuclear cyclic metallosupramolecular aggregates upon coordination to [(dppp)Pd(OTf)2] in a highly diastereoselective manner, by heterochiral self-sorting in a chiral self-discriminating manner as shown by ESI mass spectrometry, NMR spectroscopy, and single crystal XRD analysis. This observation is in contrast to earlier studies with ligands derived from Tröger's base that have larger metal binding motifs and bis (nitrile) and bis(isonitrile) ligands based on other rigid dissymmetric cores such as [2.2]paracyclophanes. Thus, the combination of these slim metal binding motifs with the rigid v-shaped 2,8- or 3,9-disubstituted Tröger's base scaffolds seems to be especially well preorganized to ensure high-fidelity social selfsorting behavior. [ABSTRACT FROM AUTHOR]

In this review, we report controlled self-assembly systems of amphiphilic random copolymers in aqueous or organic media and the solid state to produce folded micelles, related nanoaggregates, vesicles, and microphase separation materials. The key features of random copolymer self-assemblies are 1) selffolding of polymer chains, 2) precision self-assembly of side chains, and 3) dynamic self-sorting and selective recognition. Typically, random copolymers bearing hydrophilic poly(ethylene glycol) and hydrophobic alkyl groups folded into small unimer micelles (~10 nm) via the association of the hydrophobic groups in water. Importantly, those random copolymers afforded precision intermolecular self-assembly into multichain micelles; the size, aggregation number, and thermoresponsive properties can be controlled as desired by tuning their molecular weight, composition, and side chains. The binary mixture of different random copolymers further self-sorted via chain exchange in water to simultaneously form discrete micelles. Namely, amphiphilic random copolymers can dynamically recognize themselves in complex media like natural biomolecules and proteins. Amphiphilic random copolymers opened new ways to create selfassembled materials with well-defined nanostructures and compartments, dynamic recognition properties, and functions. [ABSTRACT FROM AUTHOR]