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Chemical systems that can replicate cellular behaviors are gaining increasing attention and are being used to study various biological processes. Here, a protein- or amylose-based assembly at an oi...

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., Two different dithiol building blocks interconvert through reversible covalent bonds to initially form a dynamic combinatorial library of macrocycles of various size. The self‐sorting process starts by the amplification of a single library member to form self‐replicating fibers. This step is followed by enrichment of the system in the remaining building block, which forms a large macrocyclic foldamer.

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 d in=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., Highly selective chiral self‐sorting. The chiral self‐sorting behavior of large cubic [8+12] salicylimine cage compounds was investigated, revealing a high selectivity for the most symmetric cage compounds, for which an explanation is presented. The properties of the isolated enantiopure and meso cage compounds were investigated by single crystal X‐ray diffraction and gas sorption measurements showing high porosities and selectivities.

Contrary to the popular belief that multicomponent assembly systems will theoretically co-assemble under the same type of driving forces, two distinct assembly modes from a system composed of two chemically similar supramolecules were demonstrated in this work. Although with exactly the same driving forces, molecule-level self-sorting unexpectedly occurred in this two-component system made of polyhedral oligomeric silsesquioxane (POSS) core-based supramolecules with one and eight lysine derivative arms. From the experiments, it was concluded that instead of driving force types, driving force counterpoise plays a vital role here, which we called "identity card hypothesis". The hypothesis suggests that two highly similar components show high affinity for the same molecules through the differentiated "identity card"-like balance of driving forces induced by the difference in the molecular spatial shape, which has never been reported before.

The molecular components of biological systems self-sort via different mechanisms to act in a cooperative manner and to avoid interfering with each other. Herein we describe mechanistic insights and a versatile strategy for the synthesis of water-soluble, pseudopeptide molecular cages based on disulfide bonds. The use of trifunctional thiols led to a dynamic combinatorial library (DCL) of readily isolable, multi-component homo and hetero cage-like architectures showing a degree of self-sorting related to the symmetry and size of the trithiol. The work provided detailed kinetic studies and DFT molecular modeling giving original insights into the disulfide cages' properties. We also applied the selected cage system in the fluorometric detection of La3+ cations, which led to the generation of a strongly luminescent metal–organic assembly.

We report the self-sorting of a dynamic combinatorial library (DCL) of metal–organic cages composed of a rotationally isomerisable ligand. Convergence of the DCL occurs upon crystallisation and leads to low-symmetry Cu4L2L′2 cages that display differing porosities based on their overall shape and ligand configuration.

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.

We describe self-sorting supramolecular polymerization that uses chiral calix[5]arene hosts and a dumbbell-shaped fullerene guest. In a solution containing the racemic host and the guest, the (S)-host and the (R)-host preferably formed their homomeric complexes to form helical supramolecular fullerene polymers in a self-sorting manner. The self-sorting behavior has been studied using diffusion-ordered 1H NMR (DOSY) and circular dichroism (CD) studies. The present findings show that it is possible to accomplish controlled supramolecular polymerization.

Tetra- and hexanuclear coordination cages were obtained in reactions of [Pd(CH3CN)4](BF4)2 with low-symmetry dipyridyl ligands. In both cases, only one structurally defined complex was formed out of a vast pool of potential isomers.

Three tris-bis(urea) ligands with triphenylamine-based C3-symmetric spacers were synthesized, which assembled with sulfate or phosphate to form anionic A3L2 pinwheel helices (A = anion and L = ligand) and A4L4 tetrahedra, respectively. Interestingly, narcissistic self-sorting was observed in both structures from the mixture of the ligands, wherein each assembly contains only one type of ligand with no detectable mixed-ligand product as confirmed by the NMR and MS studies.

Chiral self-sorting in cage-like compounds is drawing increasing attention in recent years. It is of great importance in controlling the chirality of the formed cages and their chirality related pr...

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.

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 k 298=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., In a spin: Two three‐component nanorotors are presented where both the reversible formation and rotational dynamics decisively depend on the proper geometric fit of intra‐supramolecular hydrogen bonding. In the rate‐limiting step of the rotational exchange, two phenolic O‐H–N,N(phenanthroline) hydrogen bonds were cleaved, a process that was investigated by variable‐temperature (VT) 1H NMR spectroscopy.

Dynamic covalent component self-sorting processes have been investigated for constituents of different cyclic orders, macrocycles and macrobicyclic cages based on multiple reversible imine formatio...

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., A sea of expanding shapes: A combined experimental–computational approach enabled the synthesis of low‐symmetry imine cages from mixtures of tetraaldehyde building blocks. This “social self‐sorting” approach was applied to obtain a family of new cages containing heteroatoms, showing that pores of varying geometries and surface chemistries may be reliably accessed.

Five ligands with either nitrile or isonitrile metal binding motifs have been synthesized based on the 2,8- or 3,9-disubstituted Troger'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 Troger'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 Troger's base scaffolds seems to be especially well preorganized to ensure high-fidelity social self-sorting behavior.

The autonomous and simultaneous construction of discrete nanoobjects via the self-assembling process is a challenging issue in materials chemistry and science. Here, we report self-sorting systems ...

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.

In this work, two TPE-bridged monomers M4 and N4, and a heteroditopic monomer AE were designed and synthesized. They could self-assemble by self-sorting mode to form supramolecular cross-linked alt...

Molecular dumbbells with organic cage capping units were synthesised via a multi-component imine condensation between a tri-topic amine and di- and tetra-topic aldehydes. This is an example of self-sorting, which can be rationalised by computational modelling.

Two constitutional dynamic libraries (CDLs)—each containing two amines, two dialdehydes and two metal salts—have been found to self-sort, generating two pairs of imine-based metallosupramolecular architectures sharing no component, a [2×2] grid-like complex and a linear double helicate. These CDLs provided unique examples of a three-level self-sorting process, as only two imine-based ligand constituents, two metal complexes and two architectures were selected during their assembling out of all the possible combinations of their initial components. The metallosupramolecular architectures assembled were characterized by NMR, mass spectroscopy, and X-ray crystallography.

Imidazole-based ditopic ligands bearing two chiral alkyl groups (LRR, LSS, and LRS) were synthesized. The ligands formed Pd2L4 helicates with palladium ions (Pd2+). Self-sorting occurred between LRR and LRS to form (Pd2+)2(LRR)4 and (Pd2+)2(LRS)4 homoligand assemblies, whereas mixing of LRR and LSS with Pd2+ gave a near statistical mixture.

Microtubules play versatile roles in vital movements due to their unique structures in which the subunits α-tubulin and β-tubulin show a strictly alternating arrangement. The synthesis of artificial copolymers with an alternating arrangement has drawn much research attention. However, as far as we know, an alternating copolymer constructed from monomers with complicated self-assembled structures is still rarely reported. Herein, an alternating rhomboidal copolymer (ARC) with high fidelity was prepared by multicomponent self-assembly in one pot based on metal-coordination and host–guest interactions. The delicate structure of the copolymer benefits from the combination of orthogonal self-assembly and integrative self-sorting strategies. Orthogonal self-assembly guarantees the copolymer with a hierarchical structure that rhomboidal metallacycles maintain their structure by metal–ligand coordination and link to each other through host–guest interactions. Meanwhile, integrative self-sorting endows the copolymer with an alternating arrangement based on different host–guest sites on the two rhomboidal metallacyclic cores. This work not only leads to an alternating rhomboidal copolymer having an intricate structure but also develops a strategy to construct novel supramolecular polymers with hierarchical complexity.

Multicomponent supramolecular materials, which comprise plural supramolecular architectures that exhibit distinct self-sorting behaviors, are receiving increasing attention because they can be implemented with sophisticated functions and hierarchical structures

Synthetic polymerization and supramolecular polymerization with sequence control are far from an easy task. Herein, a narcissistic self-sorting supramolecular polymer is prepared with a sequence of...

Coordination-driven self-assembly is a powerful approach for the construction of metallosupramolecules, but designing coordination moieties that can drive the self-assembly with high selectivity and specificity remains a challenge. Here we report two ortho-modified terpyridine ligands that form head-to-tail coordination complexes with Zn(II). Both complexes show narcissistic self-sorting behaviour. In addition, starting from these ligands, we obtain two sterically congested multitopic ligands and use them to construct more complex metallo-supramolecules hexagons. Because of the non-coaxial structural restrictions in the rotation of terpyridine moieties, these hexagonal macrocycles can hierarchically self-assemble into giant cyclic nanostructures via edge-to-edge stacking, rather than face-to-face stacking. Our design of dissymmetrical coordination moieties from congested coordination pairs show remarkable self-assembly selectivity and specificity. Coordination-driven self-assembly presents a key challenge of selectively targeting desired products. Here terpy-Zn complexes assemble head-to-tail, providing selective access to metallo-macrocycles

Here we demonstrate how the hydrogen-bonding ability of a BINOL-based dialdehyde subcomponent dictated the stereochemical outcome of its subsequent self-assembly into one diastereomeric helicate form when bearing free hydroxy groups, and another in the case of its methylated congener. The presence of methyl groups also altered the self-sorting behavior when mixed with another, short linear dialdehyde subcomponent, switching the outcome of the system from narcissistic to integrative self-sorting. In all cases, the axial chirality of the BINOL building block also dictated helicate metal center handedness during stereospecific self-assembly. A new family of stereochemically pure heteroleptic helicates were thus prepared using the new knowledge gained. We also found that switching from FeII to ZnII, or the incorporation of a longer linear ligand, favored heteroleptic structure formation.

We report on the stereoselective synthesis of trefoil knots of single topological handedness in up to 90% yield (over two steps) through the formation of trimeric circular helicates from ligand strands containing either imine or, unexpectedly, amide chelating units and metal ion templates of the appropriate coordination character (zinc(II) for imines; cobalt(III) for amides). The coordination stereochemistry of the octahedral metal complexes is determined by asymmetric carbon centers in the strands, ultimately translating into trefoil knots that are a single enantiomer, both physically and in terms of their fundamental topology. Both the imine-zinc and amide-cobalt systems display self-sorting behavior, with racemic ligands forming knots that individually contain only building blocks of the same chirality. The knots and the corresponding trimeric circular helicate intermediates (Zn(II)

Self-sorting, simultaneous, and orthogonal operations during the self-assembly of complex mixtures are commonly observed for biological species but rare in artificial systems. In this study, we designed two gelators (LPF and LPFEG) containing the same chiral phenylalanine core but different achiral peripheral substituents to give hydrogels with opposite supramolecular handedness. When the two hydrogels were mixed, double-network nanofibers with opposite handedness were formed by spontaneous high-order organization and self-sorting of the two gelators. The chiroptical activity of the double-network hydrogels could be tuned by varying the molar ratio of LPF and LPFEG in the mixture, thus showing that the two gelators were highly independent of each other. Enhanced mechanical properties were observed for the interpenetrating networks when the LPF/LPFEG molar ratio was 3:7, with a more than fourfold increase in both the storage (G') and loss modulus (G'') relative to those of the individual hydrogels.

Imine condensation has been known to chemists for more than a century and is used extensively to synthesize large organic cages of defined shapes and sizes. Surprisingly, in the context of the synthetic methods for organic imine cages (OICs), a self-sorting/self-selection (molecular marriage) process has been overlooked over the years. Such processes are omnipresent in nature, from the creation of galaxies to the formation of the smallest building blocks of life (the cell). Such processes have the incredible ability to guide a system toward the formation of a specific product or products out of a collection of equally probable multiple possibilities. This Minireview sheds light on new opportunities in cage design offered by the self-sorting/self-selection protocol in OICs. Recent efforts to explore organic cages for various exciting new applications are discussed; for example, for detection of harmful small organic molecules, as templates for nucleation of metal nanoparticles (MNPs), and as proton-conducting materials.

A four component system consisting of two water-soluble calix[5]arenes (1 and 2) with differently substituted upper-rims and two α,ω-alkanediyldiammonium ions of different lengths (NC8N and NC10N) was found to assemble in a high-fidelity fashion providing exclusively the two homocalixarene capsules 1⊃NC8N⊂1 and 2⊃NC10N⊂2, irrespective of the order of guest addition. When the longer linker (NC10N) was left out from the mixture altogether, however, 1⊃NC8N⊂2 heterocapsules were formed.

New linear supramolecular polymers SP1 and SP2 were prepared by the combination of orthogonal self-assembly and competitive self-sorting assembly methods. The photoluminescence of SP1- and SP2-based films can be decreased and enhanced, respectively, by adding basic ions.

We expand on our approach combining dynamic covalent self-assembly and sulfur extrusion to synthesize new biphenyl-linked disulfide and thioether macrocycles, which are variants of the venerable phenyl-bridged paracyclophanes. We then advance this strategy further to use two different thiols in tandem to provide new, elusive unsymmetrical disulfides which can also be trapped as unsymmetrical thioether "nanohoops". This approach enables substantial amplification of two unsymmetrical trimers out of a library of at least 21 possible macrocycles of various sizes.

Two isomers of Tröger's base-linked cryptands 5a and 5b were synthesized, and both of them have two chiral N-centers, exhibiting rare diamond-like scaffolds. Particularly, when growing from the solution of rac-5a, a single enantiomer RNRN-5a was found in the crystal cell, revealing chiral self-sorting behaviour. However, when adding CF3COOH to protonate Tröger's base in the solution of rac-5a, two enantiomers were both formed in pairs in the crystal cell, exhibiting chiral self-discriminating behaviour.

A calix[5]arene monomer bearing two different ammonium sites assembles into a supramolecular polymer that self-sorts into a polypseudorotaxane upon addition of dibenzo-24-crown-8, but only in the presence of superweak counterions.

Using German establishment data, we show that the relationship between intensity of individual‐based performance pay and intensity of applicant screening depends on the nature of production. In establishments with increased multitasking, performance pay is positively associated with applicant screening. By contrast, in establishments without increased multitasking, performance pay is negatively associated with applicant screening. We do not find a similar pattern of results for group‐based performance pay or profit‐sharing. Our findings fit the hypothesis that individual‐based performance pay induces a positive self‐sorting of employees if jobs are less multifaceted. In this case, employers with a high intensity of performance pay do not need intensive applicant screening to ensure a high quality of matches between workers and jobs. However, if jobs are more multifaceted, individual‐based performance pay can entail problems of adverse self‐sorting. In order to mitigate or overcome these problems, employers making intensive use of performance pay also screen applicants more intensively.

Self-sorting, in which multiple components selectively assemble themselves by recognising self from others, is an attractive approach to produce supramolecular assemblies with controlled structures. Lock-and-key type complementary physical interactions are required for self-sorting because selective affinity is necessary to distinguish self from others. Here we show self-sorting behaviour based on a principle of geometrical complementarity by shape during our investigation of assembly of pentagonal pillar[5]arenes and hexagonal pillar[6]arenes on a surface. In the homoassembly systems, anionic pillar[5]arenes and pillar[6]arenes are adsorbed onto positively charged layers of cationic pillar[5]arenes and pillar[6]arenes, respectively, through cationic-anionic electrostatic interactions. In contrast, ionic pillar[5]arenes are adsorbed onto layers constructed from oppositely charged pillar[5]arenes, but ionic pillar[6]arenes are not. Equally, for the reverse combination, ionic pillar[6]arenes are adsorbed onto layers constructed from oppositely charged pillar[6]arenes, but ionic pillar[5]arenes are not. The geometrical complementarity by shape realises effective self-sorting even in non-directional multivalent ionic interactions. Self-sorting is an attractive approach to produce complex supramolecular systems and materials with controlled structures. Here the authors show geometrical complementarity in the self-sorting behaviour of pentagonal and hexagonal pillararenes on heterogeneous surface through layer-by-layer deposition.

International audience; Encapsulating and storing hydrophilic payloads are still challenging nowadays. Here, a simple pathway is described to generate different water-filled microcapsule dispersions. We carefully chose a unique poly(vinyl alcohol) (PVA) dispersant that is able to stabilize and cover both direct and inverse interfaces. Single hollow capsules consisting of precipitated PVA shells were first prepared in one pot. Cargo release was shown to vary from fast kinetics (pristine microcapsules) to a diffusion-controlled one (cross-linked microcapsules) after an initial burst. We then describe an extremely easy process to generate double microcapsules, the complexity of which was visualized with different fluorescent markers.

Narcissistic self-sorting in supramolecular assemblies can help to construct materials with more complex hierarchies. Whereas controlled changes in pH or temperature have been used to this extent for two-component self-sorted gels, here we show that a chemically fueled approach can provide three-component materials with high precision. The latter materials have interesting mechanical properties, such as enhanced or suppressed stiffness, and intricate multi-step gelation kinetics. In addition, we show that we can achieve supramolecular templating, where pre-existing supramolecular fibers first act as a templates for growth of a second gelator, after which they can selectively be removed.

Narcissistic self-sorting, namely that components are able to distinguish “self” from “nonself” during self-assembly, was accomplished via catenation by condensing multiple hydrazides and an aldehyde, or a hydrazide and multiple aldehydes in water. The underneath mechanism of this behavior relies on the corresponding homo [2]catenanes are thermodynamically more favored than their hetero counterparts, because the former containing two identical macrocyclic components are able to maximize the inter-component noncovalent forces. One of these catenanes contains four 4-phenylpyridinium units, which are often considered barely luminescent due to intramolecular rotations and vibrations that lead to nonradiative annihilation of their excited states. These intramolecular motions, however, are restricted upon integrating 4-phenylpyridiniums within the catenane architecture. As a consequence, compared to its non-interlocked counterparts, this catenane exhibits enhanced fluorescence, which represents a novel conceptual model for developing luminescent materials.

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.

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.

Biological systems organize multiple hierarchical structures in parallel, and create dynamic assemblies and functions by energy dissipation. In contrast, emerging artificial non-equilibrium self-assembling systems have remained relatively simplistic concerning hierarchical design, and non-equilibrium multi-component systems are uncharted territory. Here we report a modular DNA toolbox allowing to program transient non-equilibrium multicomponent systems across hierarchical length scales by introducing chemically fueled molecular recognition orchestrated by reaction networks of concurrent ATP-powered ligation and cleavage of freely programmable DNA building blocks. Going across hierarchical levels, we demonstrate transient side-chain functionalized nucleic acid polymers, and further introduce the concept of transient cooperative multivalency as a key to bridge length scales to pioneer fuel-driven encapsulation, self-assembly of colloids, and non-equilibrium transient narcissistic colloidal self-sorting on a systems level. The fully programmable and functionalizable DNA components pave the way to design chemically fueled 4D (3 space, 1 time) molecular multicomponent systems and autonomous materials., There is interest in creating life-like behaviours in synthetic multicomponent systems. Here, the authors report on a modular DNA toolbox able to create transient, dynamic structures using ATP-driven molecular recognition in which multiple systems can run in parallel and across hierarchies.

Many useful principles of self-assembly have been elucidated through studies of systems where multiple components combine to create a single structure. More complex systems, where multiple product structures self-assemble in parallel from a shared set of precursors, are also of great interest, as biological systems exhibit this behavior. The greater complexity of such systems leads to an increased likelihood that discrete species will not be formed, however. Here we show how the kinetics of self-assembly govern the formation of multiple metal-organic architectures from a mixture of five building blocks, preventing the formation of a discrete structure of intermediate size. By varying ligand symmetry, denticity, and orientation, we explore how five distinct polyhedra-a tetrahedron, an octahedron, a cube, a cuboctahedron, and a triangular prism-assemble in concert around CoII template ions. The underlying rules dictating the organization of assemblies into specific shapes are deciphered, explaining the formation of only three discrete entities when five could form in principle.

Chirality-induced recognition-promoted molecule-level self-sorting assembly in a two-component supramolecular gel system constructed by two polyhedral oligomeric silsesquioxane (POSS) core-based dendritic gelators with similar geometry and peripheral functionality, which would normally form a homogeneous co-assembled network.