Pseudo‐nanophase separation enabled by supramolecular‐interaction‐grafted sidechains proves a promising alternative for constructing high‐performance commercially viable membranes with quick ion transport, excellent chemical stability, and simplified membrane manufacturing. Nonetheless, the concept of pseudo‐nanophase separation is still in nuce, and determinants for controlling pseudo‐nanophase separation remain somewhat opaque. In this contribution, supramolecular sidechain topology is found critical to engineering pseudo‐nanophase separation. Three supramolecular sidechain topological (viz. linear, branched, and cyclic) structures are investigated using experimental and theoretical protocols, and the underlying mechanisms by which supramolecular sidechain topology alters the microstructure and ion‐conducting behaviors of the membranes are proposed. Consequently, the cyclic sidechain‐mediated membrane achieves the highest proton conductivity with an area resistance as low as 0.10 Ω cm 2 . The resulting membrane endows an acidic aqueous redox flow battery with an energy efficiency of up to 80.7% even at high current densities of 220 mA cm −2 , breaking the record set by the pseudo‐nanophase separation strategy constructed membranes and ranking among the highest values ever documented. This study advances the understanding of supramolecular sidechain topology for the design and preparation of high‐performance membranes via pseudo‐nanophase separation engineering for flow batteries and beyond.

A biscyclen molecular cabin, synthesized by connecting two cyclen macrocycles with four linkages, entraps a Li+H2OLi+ trimer with a water molecule clamped by two Li+ ions. This configuration results in strongly polarized water, characterized by a water proton resonance shift of up to 10.00 ppm. The arrangement facilitates unprecedented O-centered chalcogen bonds between the lone pairs of pyridinyl nitrogen atoms and polarized water oxygen, as confirmed by X-ray crystallography, NMR spectroscopy, and theoretical calculations. Further observation of O-centered chalcogen bonding in a H2O(LiCl)(2) cluster suggests its widespread presence in hydrated salt systems.

An ion pair receptor is reported that is capable of extracting LiCl and LiBr selectively from aqueous phases; the extraction efficiency is enhanced by the presence of other competitive salts.

Carcerands, special molecular constructs with enclosed interiors as a new phase of matter, have attracted immense interest because of their unique structures, physicochemical properties, and potential applications in many aspects, e.g., targeted drug delivery. However, carcerands for imprisoning, inter alia, anions of interest represent an unmet challenge. Herein, we report the design and synthesis of a superphane-based carcerand 1, featuring up to 18 anion binding sites and a fully enclosed interior space. Carcerand 1 is found capable of incarcerating H2PO4- anion, yielding an anion carceplex 5, as inferred from crystallographic analysis, 1H nuclear magnetic resonance (NMR) spectroscopy, and diffusion-ordered NMR spec-troscopy (DOSY), as well as molecular dynamics simulations. More importantly, highly toxic arsenate anion was also imprisoned within carcerand 1, offering the arsenate carceplex 6 that proved nontoxic compared with free arsenate or peripherally bound arsenate in the HEK293T cell line.

A well-defined hydrophilic/hydrophobic nanophase-separated structure is widely applied for the construction of fast ion-transport pathways in polymeric membranes for energy-related applications such as electrochemical reactors, fuel cells, and redox flow batteries (RFBs). Conventional nanophase separation is induced by covalently grafted side chains, which however complicate membrane preparation and potentially reduce the chemical stability of membranes. In this work, we report a pseudo-nanophase-separation strategy enabled by supramolecular interactions to construct fast and selective ion-transport channels in polymeric membranes. The "side chains" are "grafted" onto the polymer backbone via supramolecular interactions instead of covalent bonds, simplifying the membrane preparation process and simultaneously protecting the polymer backbone from chemical degradation, which is a critical problem usually found in membranes with molecular modifications. The pseudo-nanophase separation enables high-performance membranes for aqueous acidic RFBs, showing high efficiency and good cycling stability, which suggests its potential to design highly conductive and chemically stable membranes for various energy-related devices.

An unprecedented copper-promoted radical-mediated alkenyl C(sp 2 )–H carbonylation of alkenes with polyhaloalkanes for divergently producing α,β-unsaturated esters and aldehydes is presented.

AbstractAdsorbents widely utilized for environmental remediation, water purification, and gas storage have been usually reported to be either porous or crystalline materials. In this contribution, we report the synthesis of two covalent organic superphane cages, that are utilized as the nonporous amorphous superadsorbents for aqueous iodine adsorption with the record–breaking iodine adsorption capability and selectivity. In the static adsorption system, the cages exhibit iodine uptake capacity of up to 8.41 g g−1 in I2 aqueous solution and 9.01 g g−1 in I3− (KI/I2) aqueous solution, respectively, even in the presence of a large excess of competing anions. In the dynamic flow-through experiment, the aqueous iodine adsorption capability for I2 and I3− can reach up to 3.59 and 5.79 g g−1, respectively. Moreover, these two superphane cages are able to remove trace iodine in aqueous media from ppm level (5.0 ppm) down to ppb level concentration (as low as 11 ppb). Based on a binding–induced adsorption mechanism, such nonporous amorphous molecular materials prove superior to all existing porous adsorbents. This study can open up a new avenue for development of state–of–the–art adsorption materials for practical uses with conceptionally new nonporous amorphous superadsorbents (NAS).

Macrocycle-to-macrocycle interconversions are of interest because they can allow access to a variety of structures. However, reversible interconversion between different sized macrocycles remains challenging to control. Herein, we report a facile one-pot synthesis of a series of self-assembled macrocycles from readily prepared α,α'-linked oligopyrrolic dialdehydes and various alkyl diamines. The condensation of pyridine-bridged oligopyrrolic dialdehyde 3 and simple alkyl diamines proved independent of solvent, always yielding the [2 + 2] macrocyclic products. However, when 3 was condensed with 2,2'-oxybis(ethylamine) 14, either ([1 + 1] or [2 + 2]) products are obtained depending on the choice of solvent. Reaction of 3 and 14 in methanol, ethanol, or chloroform gave the [1 + 1] macrocycle as the sole product. In contrast, condensation of 3 and 14 in dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), or acetonitrile (MeCN) yielded the [2 + 2] macrocycle as the major product in the form of a precipitate. Reversible interconversion between the [1 + 1] and [2 + 2] macrocycles could be achieved by tuning the solvent, with the ratio driven by thermodynamic and solubility considerations.

Herein, we describe the design and synthesis of an unusual azobenzene-bearing macrocycle 1, whose trans isomer was found able to 100% transform into its cis configuration under photoirradiation, for selectively recognizing HP2O73- with reversibly photo-controllable binding and release properties.

Widespread implementation of redox flow batteries (RFBs) is restricted by inefficient ion conducting membranes. It is especially challenging for membranes to achieve high ionic conductivity, high ion selectivity, and excellent chemical stability, simultaneously. Herein, we demonstrate a versatile solution to this toughest problem via designing multi-functional sidechain topology and manipulating their arrangement in ion conducting mem-branes. A series of comb-shaped ion conducting membranes with variable sidechains, along which the number of hydrophilic sites is different, are constructed, and their structure-performance relationships are comprehensively explored. Specifically, in the case of the same number of hydrophilic sites, the membranes with densely grafted short chains (the "stone") outperform those with loosely grafted long chains in terms of proton conductivity and ion selectivity (the first two "birds"), which is attributed primarily to the interconnected and size-constrained hydrophilic channels formed in the former, as demonstrated by an integrated experimental and simulation study. Furthermore, the former arrangement improves chemical stability of the membranes (the third "bird") since the size-constrained channels hamper the offensive active species from entering. These benefits result in higher energy efficiencies (EE: 92.7-71.7% at 40-200 mA cm-2) and slower capacity decay rate (CDR: 0.09% per cycle) of vanadium RFBs compared with the membranes with loosely grafted long chains (EE: 90.8-66.7% at 40-200 mA cm-2, CDR: 0.15% per cycle). This work sheds light on the path to comprehensively outstanding ion conducting membranes via molecular engineering, for energy-related devices and beyond.

Macrocyclization proves a useful strategy for obtaining artificial supramolecular hosts via reducing the degrees of freedom of the corresponding precursors. However, synthesis of receptor containing multiple macrocycles is challenging. In this contribution, we describe the rational design and synthesis of a new class of organometallic trimacrocyclic hexasubstituted benzenes 1 and 2 via either metal–ligand coordination or dynamic covalent chemistry strategies. Such class of constructs feature a benzene core fused by three identical metallomacrocycles with high symmetry and interesting physiochemical property, as inferred from the NMR, mass spectrometry, cyclic voltammetry and DFT calculations. Trimacrocycle 2 bearing one ferrocene unit in each sub–macrocycle was found able to selectively capture bromide and iodide, as evidenced by NMR spectroscopy, DFT calculations, as well as molecular dynamics simulations. Thus, we hope this study will somewhat accelerate the development of complex functional host–guest systems for species of interest.

Notwithstanding the considerable advances in the field of biomaterials, there is still an ongoing quest for the development of new materials and strategies for anti-cancer and antimicrobial drug discovery. Herein, we detail the synthesis of two trimacrocyclic hexasubstituted benzenes (THBs, 1 and 2) via a Co-2(CO)(8)-catalyzed (2 + 2 + 2] tricyclization synthetic strategy. Compounds 1 and 2 show a great propensity for complexing guanidinium cations, as inferred from( 1)H NMR spectroscopic studies and single-crystal X-ray crystallography, as well as DFT calculations and molecular dynamics simulations. Under solid-liquid extraction conditions, 1 and 2 were able to extract guanidinium cations from the solid state into the chloroform phase. The guanidinium recognition-induced promotion of anti-cancer and antimicrobial activities was further exemplified by the MTT cell viability assays and antimicrobial studies using receptor 2 in the presence of guanidinium chloride. This study provides insight into anti-cancer and antimicrobial drug discovery in a supramolecular way.

Highly selective anion recognition and extraction is challenging and yet critical for removal of pollutants from the environment and the effective recovery of valuable chemicals from low-content (at sub-ppm or ppb level) sources. In this paper, we detail the gram-scale synthesis of a superphane 2, an anion receptor that selectively binds ReO4−. Superphane 2 can extract perrhenate from solid mixtures containing traces of ReO4− anion (as low as 200 ppb) and aqueous media with near 100% selectivity over large excesses of competing anions. Meanwhile, up to 99.99% of ReO4− can be separated from complex simulated aqueous waste streams containing ppm-level perrhenate via either liquid-liquid extraction or simple column adsorption. Importantly, after extraction or adsorption, superphane 2 can be recycled and reused by simple treatment with aqueous NaHCO3.

Superphanes, compounds in which the two benzene rings clamped parallel on top of each other by six bridges, have garnered considerable interest due to their aesthetically pleasing structures and unique chemical physical properties. However, until now progress in the research of superphane chemistry and beyond has been seriously hampered by their poor availability. Herein, we report the facile and scalable synthesis of a collection of superphanes with structural diversity and their unique photophysical properties, as well as their unusual host–guest behavior. Initially, a set of dodecaimino–containing super-phanes 7a–7e are obtained via dynamic self–assembly of a hexakis–amine and a series of readily derived aromatic dialde-hyde in one pot. The resulting superphanes are found capable of being reduced with NaBH4 to their corresponding second-ary–amine versions 3a–3e. Subsequently, superphane 3c bearing 12 amine–NHs was further subject to post–functionalization with various functional groups, e.g., ethyl, allyl, propargyl and but–2–yn–1–yl. Unprecedentedly, the sec-ondary amine–based superphanes 3a–3e were observed to exhibit genuine fluorescence both in solution and in the solid state while the imine–based superphanes 7a–7e were found to highly emissive only in solid state with fluorescent quantum yields of 3.5 ~ 17.1. Finally, fully protonated 3a was exemplified to encapsulate a 2Cl–·H2O cluster both in the solid state and in solution. With the easy and versatile synthesis, modification, as well as unique photophysical and host–guest properties, we believe that this study will break the bottleneck in superphane chemistry and open the door to a novel class of supramo-lecular hosts and advanced functional materials on the basis of superphanes.

Crystalline supramolecular architectures mediated by cations, anions, ion pairs or neutral guest species are well established. However, the robust crystallization of a well-designed receptor mediated by labile anionic solvate clusters remains unexplored. Herein, we describe the synthesis and crystalline behaviors of a trimacrocyclic hexasubstituted benzene 2 in the presence of guanidium halide salts and chloroform. Halide hexasolvate clusters, viz. [Cl(CHCl3)(6)](-), [Br(CHCl3)(6)](-), and [I(CHCl3)(6)](-), were found to be critical to the crystallization process, as suggested by the single-crystal structures, X-ray powder diffraction (XRPD), thermogravimetric analysis (TGA), scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS), and NMR spectroscopy. This study demonstrates the hitherto unexpected role that labile ionic solvate clusters can play in stabilizing supramolecular architectures.

Highly selective anion recognition and extraction are critical and challenging to deep removal of pollutants from the environment and effective recovery of valuable chemicals from low–content (at sub–ppm or ppb level) sources. Herein, we detail the gram–scale synthesis of a superphane 2, a new supramolecular host that was found capable of encapsulating ReO4– with high selectivity, as suggested by the single–crystal structures, NMR spectroscopy and theoretical calculations. Under solid–liquid extraction condidtions, 2 proved able to extract perrhenate from the solid mixture containing trace ReO4– (as low as 200 ppb) with near 100% selectivity over other 7 competing anions. Under liquid–liquid extraction conditions, using 2 as the supramolecular extractant, over 99.99% of ReO4– could be separated from the complex simulated aqueous waste streams containing ppm–level perrhenate and large excess of competing ions. Notably, after extraction, 2 could be recycled and reused by simple treatment with NaHCO3. This study opens up the door to development of superphane–based advanced materials for deep elimination of pollutants from the envirenment and purification of chemicals of interest with high efficiency and selectivity.

A new superphane, featuring an aesthetically pleasing structure, was successfully obtained via one-pot synthesis of a hexakis-amine and m-phthalaldehyde in a [2+6] manner. It proved capable of entrapping a water dimer within its cavity as inferred from the mass spectroscopy, crystallographical analysis, NMR spectroscopy, and theoretical calculations.

We report what to our knowledge is the smallest bis-calix[4]pyrrole (2). It proved capable of trapping fluoride anions exclusively relative to other anions (Cl-, Br-, SCN-, NO3-, H2PO4-, HSO4-, SO42-, and HP2O73-; tetrabutylammonium salts), as confirmed by 1H NMR spectroscopy (CDCl3), X-ray diffraction analysis, DFT calculations, and molecular dynamics simulations. The F- selectivity is ascribed to the small size of the cavity in 2.

Supramolecular extraction refers to an application of supramolecular chemistry, in particular host-guest chemistry, toward extraction. It has led to new approaches, inter alia, in so-called solvent...