Supramolecular Chemistry

Synthetic methods for the preparation of perfluorinated aromatic compounds are desirable in materials science. Here, the authors synthesize perfluorocycloparaphenylenes, fully fluorinated carbon nanorings, through a nickel-mediated one-pot method.

The preparation of heterodimeric structures via self-assembly processes is challenging. Here, the authors report the photooxidation of a donor–acceptor metalloporphyrin, which enables a self-sorting process that yields an heterodimer quantitatively.

The development of complex molecular machinery requires a detailed appreciation of the factors that control energy pathways through the nanoscale scaffold. Here, the authors demonstrate that hetero-rotaxanes can be employed to create assemblies of different redox and photo-active components that enable selective tuning of energy transfer pathways.

Typical micelles are molecular assemblies composed of amphiphiles bearing linear alkyl chains. Herein, the authors present an uncommon type of cycloalkane-based bent amphiphile and its micelle which encapsulates large metal- complexes with high uptake efficiency, selectivity, and emissivity in water.

Molecular motors and switches change conformation under the influence of an external stimulus and can be incorporated into functional systems, allowing the construction of adaptive materials and switchable catalysts. Here, the authors present two molecular motor-functionalized porphyrin macrocycles for future photo-switchable catalysis.

Vibrational circular dichroism (VCD) spectroscopy can be useful for determining the absolute configuration of chiral molecules, as long as the signal intensities are high enough. Here, the authors establish the absolute configurations of two large chiral porphyrin cages and, notably, discover that host-guest binding enhances their VCD intensities.

Heteroatom-bearing molecular loops and belts are fascinating but generally difficult to synthesize. Here, the authors demonstrate that O,S-bridged double-stranded molecular belts—cyclophenoxathiins—can be successfully constructed and employed as versatile supramolecular hosts.

Since the discovery of mechanically planar chiral rotaxanes and topologically chiral catenanes, their asymmetric synthesis has been a long-standing challenge. Here, the authors report enantioselective preparation of mechanically planar chiral rotaxanes with up to 99.9% ee in 29% yield.

Encapsulating large and contorted nanographenes inside artificial receptors remain challenging. This work reports the synthesis, characterization and binding properties of a trigonal prismatic cage compound that can serve as a receptor for contorted nanographene derivatives.

The preparation of nanocages with unprecedented architectures may lead to new functions. Here the authors report the self-assembly of organic cages featuring twin cavities; the geometry and pocket size determine the molecular packing and the proton conductivity performance.

The self-assembly of molecular knots in water is challenging. Here, authors report the self-assembly of a trefoil knot in water via imine condensation, without relying on external templates; the handedness of the trefoil knot is determined by the chirality of the bisamino precursor.

The preparation of artificial host–guest systems that display dynamic adaptation during guest binding is challenging. Here the authors report a chiral self-assembled tetrahedral cage featuring curved walls that reconfigures stereochemically to fit fullerene guests, regulates corannulene inversion, and enables the determination of co-guest enantiomeric excess by NMR spectroscopy.

Mechanical motions in hybrid sp²/sp³ -hybrid nanocarbon peapods might lead to promising materials applications, but have been insufficiently explored. Here the authors demonstrate that a diamondoid molecule trapped inside a carbonaceous cylinder undergoes solid-state rotations at terahertz frequencies.

Catenated cages are challenging synthetic targets in chemistry. Here, the authors employ a multi-component coordination strategy using a Pt(II) heteroligation to construct a cyclic bis[2]catenane metallacage, which could be reversibly transformed between the catenated structure and the bis-metallacage.

Developing simple routes for construction of multi-compartmental cages is a compelling and challenging task. Here, the authors report modular construction of multi-3D-cavity cages featuring one, two or three units of a [Pd₂L₄] entity conjoined with a [Pd₃L₆] core.

Weak interactions between functional groups are often difficult to characterize in host–guest complexes. Here, the authors report the metal-free active template synthesis of a series of rotaxanes that permit a range of kinetically stabilized, weak crown ether-axle interactions to be characterized in solution and the solid state.

Self-assembly and molecular recognition usually depend on strong, directional non-covalent interactions but also topography can play a role in the formation of supramolecular constructs which makes it nearly impossible to discern the potential of shape and motion in the creation of complexity. Here, the authors demonstrate that long-range order in supramolecular constructs can be assisted by the topography of the individual units even in the absence of highly directional interactions.

Precise assembly of heterometallic complexes is a challenge. Here, the authors design a heterometallic triangular necklace through a highly efficient threading-and-ring-closing approach driven by metal-ligand coordination, which shows strong bacterium-binding and cell wall/plasma membrane-disrupting capacity for killing bacterial cells.

Different to exploring molecular topology, the development of supramolecular topology has been limited due to a lack of reliable synthetic methods. Here, the authors describe a supramolecular strategy to access Möbius strips through bending and cyclization of twisted nanofibers self-assembled from chiral glutamate amphiphiles.

Conformational selection is one of the two dominant binding mechanisms in biology, but has rarely been studied in synthetic systems. Here, the authors report a supramolecular system that strictly follows the binding mechanism of conformational selection.

The application of photoswitches as light-responsive triggers for phase transitions of porous materials remains poorly explored. Here, the authors report a light-responsive flexible metal-organic framework which undergoes pore contraction upon combined application of light irradiation and adsorption stress via a buckling process of the framework-embedded azobenzene photoswitch.

Constructing cross-linked networks with different topologies is attractive but challenging. Here the authors present mechanically interlocked networks cross-linked by a molecular necklace whose peculiar architectural and dynamic features endow the materials with robust yet mechanically adaptive properties.

Controlling multicomponent systems is difficult due to convoluted behavior, pathway complexity, and coupled equilibria. Here the authors showed modulation of aggregate morphology in a zinc porphyrin-based supramolecular system via judicious capping with a manganese porphyrin monomer, in which the monomer’s chirality can influence the supramolecular behavior.

Molecular self-assembly in water is conventionally limited to amphiphilic molecules. This study harnesses sacrificial surface groups and a post-assembly chemical reaction to form nanostructures unachievable by spontaneous self-assembly alone.

Unlike natural supramolecular polymers, artificial counterparts do not have molecular recognition processes to preorganize the supramolecular complexes before final assembly. Here, the authors show supramolecular copolymerization driven by integrative self-sorting of two different monomers into discrete six-membered supramolecular complexes (rosettes).

Organic ferroelectrics are of potential use in state-of-the-art ferroelectric devices but mechanistic insight in generating ferroelectricity remains limited. Here, the authors demonstrate that a bowl-to-bowl inversion of a bowl shaped organic molecule generates ferroelectric dipole relaxation, extending the concept of ferroelectricity in small organic molecules.

Photothermal therapy (PTT) has recently emerged as a promising approach for cancer therapy. Here, the authors report a hyperbranched polymer vesicle with favorable photothermal stability and high photothermal efficiency for PTT through a supramolecular polymerization-enhanced self-assembly strategy.

Regulating fluorescent properties of small molecules in a controlled manner has been a fundamental research goal but realizing multi-color emission from a single fluorophore remains challenging. Here the authros demonstrate that combined pyrene fluorophore and acylhydrazone units show multi-color switchable fluorescent at different assembled states.

Host-guest solid state molecular motion is a critical but underexplored phenomenon which can be used to control molecular machines that function in the solid state. Here, the authors describe a solid state machine that shows solvent vapour- and mechanically-induced molecular motion that allows access to different crystalline and amorphous forms.

Abiotic–biotic hybrid systems are promising to trap light for fuel and chemical transformation with high efficacy and selectivity. This study reports a coenzyme-mediated supramolecular host-guest semibiological system combining supramolecular catalyst and enzymes for solar alcohol splitting.

Ionic skins are of interest for a range of electronic, sensing and interfacing applications but often have trade-offs in properties. Here, the authors report on the creation of a dual network ionic skin using a supramolecular zwitterionic competing network to produce a strain-stiffening, self-healing adhesive sensor.

Knowledge about kinetically favored intermediate states in self-assembly processes can provide information about the self-assembly process but trapping these states without changing the reaction conditions is challenging. Here, the authors report a method for trapping metastable intermediates in self-assembly processes that is based on a photopolymerization strategy.

The feasibility of molecular assemblers as a device to control chemical reactions by positioning molecules with atomic precision is a matter of debate in the literature. Here the authors describe of a rudimentary synthetic molecular assembler, supramolecular aggregate of bifunctional surfactants produced by the reaction of two phase-separated reactants that produces polymers.

Regulation of self-sorted nanofiber network patterns in double network hydrogels comprising supramolecular nanofibers is considered as key for potential applications. Here, the authors describe a selective construction of two distinct self-sorting network patterns, by controlling the kinetics of seed formation with dynamic covalent chemistry.

In biology, information is stored and processed using highly evolved molecules in bistable states. Here, the authors demonstrate bistability in a synthetic system without the need for evolved biomolecules or autocatalytic networks.

Monodisperse and well-defined self-assembled materials can be obtained by fuel-driven temporally controlled supramolecular polymerization via the buffered release of monomers. Here the authors show that a redox-responsive transient dormant state of monomer generated by redox reaction can lead to supramolecular polymers with low dispersity.

Selection in compartmentalized self-replicating systems might provide a way for life to arise from abiotic environments. Here, the authors explore selection in a system of transient autocatalytic lipids and find that autocatalytic kinetics and phase separation are the key selection factors.

The dynamic structure of supramolecular polymers is challenging to determine both in experiments and in simulations. Here the authors use coarse-grained molecular models to provide a comprehensive analysis of the molecular communication in these complex molecular systems.

Dissipative self-assembly, which requires a continuous supply of fuel to maintain the assembled states far from equilibrium, is the foundation of biological systems but it remains a challenge to introduce light as fuel into artificial dissipative self-assemblies. Here, the authors report an artificial dissipative self-assembly system that is constructed from light-induced amphiphiles.