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Anion templated assembly of supramolecular systems has been extensively explored in previous reports, whereas anions serve only as an auxiliary and spectator role. With the development of anion coordination chemistry in recent years, anion coordination‐driven assembly (ACDA) has emerged as a new strategy for the construction of supramolecular self‐assemblies. Anions are proved to exist as the main actors in the construction of supramolecular architectures, i. e., serve as the coordination center. This Review will focus on the recent progress in anion‐coordination‐driven assembly of discrete supramolecular architectures, such as helicates, polyhedrons and polygons, and the various applications of ‘aniono’‐systems. At the end of this Review, we highlight current challenges and opportunities for future research of anion‐coordination‐driven self‐assembly. Recent progress in anion‐coordination‐driven assembly of discrete supramolecular architectures and the corresponding applications are discussed in this Review article. Anion‐coordination‐driven self‐assembly strategy has been proved as a promising approach for construction of supramolecular architectures in parallel with the ‘metallo’‐systems.

Stimuli‐responsive systems play a crucial role in biological processes. Research on supramolecular cages formed via noncovalent interactions contributes to the development of receptors that mimic these natural systems. Recently, anion‐coordination‐driven assembly (ACDA) employing oligourea ligands and trivalent phosphate ions (PO43−) has emerged as a promising strategy for constructing responsive supramolecular architectures. These assemblies are stabilized through multiple hydrogen bonds and are capable of undergoing structural transformations in response to external stimuli, offering a conceptual framework for understanding flexibility and environmental adaptability in biological contexts. This mini‐review highlights the stimuli‐responsive properties of anionic self‐assemblies, with a focus on systems involving oligourea ligands and PO43− ion. Organized by stimulus type, it discusses multistimuli responsiveness, guest‐induced transformations, solvent sensitivity, and light‐responsive behaviors. Current challenges and identifying future opportunities in the study of ACDA‐based stimuli‐responsive systems are discussed. This mini‐review summarizes recent developments in stimuli‐responsive supramolecular assemblies based on anion‐coordination‐driven assembly using oligourea ligands and phosphate anions. The content is organized by stimulus type: multistimuli, guest/template, solvent, and light. This review highlights multistimuli adaptability and structural transformations. Remaining challenges and future directions are also outlined.

The presence of sulfate anions induces the self-assembly of anion-binding bis(cyclopeptides) in which two cyclopeptide rings are connected via a rigid linker. In this way, 2:2 complexes are formed in which two anions are sandwiched between two bis(cyclopeptide) moieties. Mixed species can be formed if two bis(cyclopeptides) containing different linkers are present and the structural mismatch between the linkers can be compensated for in the self-assembled product. Sulfate complexation seems to proceed with positive cooperativity, leading primarily to the fully formed complexes. As a consequence, these bis(cyclopeptides) represent useful building blocks for the anion-mediated formation of self-assembled products with controllable structural complexity.

Safe confinement of fission iodine isotopes for long-term radioactive waste disposal remains a formidable challenge, as conventional sorbents provide inherently weak iodine-host interactions. We report here a novel halogen bond (X-bond) directed strategy to sequester volatile iodine in hydrogen-bonded (H-bonded) frameworks with unprecedented stability. Charge-assisted H-bonded frameworks bearing open halide sites are developed, showing distinctive iodine encapsulation behaviors without compromising the crystallinity. Direct crystallographic evidence indicates the formation of X-bonds, i.e., ∣–∣⋯Cl − and ∣–∣⋯Br − , within the confined pore channels. Unusual polyhalogen anions, i.e., [I 2 Cl 2 ] 2− and [I 2 Br 2 ] 2− , sustained in H-bonded frameworks are identified for the first time. The X-bond reinforced host-guest interaction affords robust iodine trapping without leaking out even at elevated temperatures up to 180 °C. By integrating the halogen-bond chemistry with H-bonded frameworks, this study offers fresh concepts for developing effective host reservoirs to secure fission iodine isotopes from spent fuel reprocessing off-gases.

Phosphates play a crucial role in drug design, but their negative charge and high polarity make the transmembrane transport of phosphate species challenging. This leads to poor bioavailability of phosphate drugs. Combretastatin-A4 phosphate (CA4P) is such an anticancer monoester phosphate compound, but its absorption and clinical applicability are greatly limited. Therefore, developing carrier systems to effectively deliver phosphate drugs like CA4P is essential. Anion receptors have been found to facilitate the transmembrane transport of anions through hydrogen bonding. In this study, we developed a tripodal hexaurea anion receptor (L1) capable of binding anionic CA4P through hydrogen bonding, with a binding constant larger than 104 M−1 in a DMSO/water mixed solvent. L1 demonstrated superior binding ability compared to other common anions, and exhibited negligible cell cytotoxicity, making it a promising candidate for future use as a carrier for drug delivery.

Aggregation-induced emission (AIE) materials have attracted increasing research interest in recent years due to their excellent fluorescence properties in an aggregated state. Concurrently, anion coordination interactions have played a key role in the development of supramolecular assemblies and sensors. In the past decade, investigations towards fluorescent materials or sensors based on AIE and anion coordination interactions are continuously being reported. In this minireview, we briefly summarize the burgeoning progress of AIE-based materials and sensors driven by anion coordination interactions. We believe that an increasing number of achievements in anion-coordination induced emission materials will appear in the near future and will demonstrate potential applications, including bio-imaging and bio-sensors.

In this work, we report the synthesis of a new bis(tris(2-aminoethyl)amine) azacryptand L with triphenyl spacers. The binding properties of its dicopper complex for aromatic dicarboxylate anions (as TBA salts) were investigated, with the aim to obtain potential building blocks for supramolecular structures like rotaxanes and pseudo-rotaxanes. As expected, UV-Vis and emission studies of [Cu2L]4+ in water/acetonitrile mixture (pH = 7) showed a high affinity for biphenyl-4,4′-dicarboxylate (dfc2−), with a binding constant of 5.46 log units, due to the best match of the anion bite with the Cu(II)-Cu(II) distance in the cage’s cavity. Compared to other similar bistren cages, the difference of the affinity of [Cu2L]4+ for the tested anions was not so pronounced: conformational changes of L seem to promote a good interaction with both long (e.g., dfc2−) and short anions (e.g., terephthalate). The good affinity of [Cu2L]4+ for these dicarboxylates, together with hydrophobic interactions within the cage’s cavity, may promote the self-assembly of a stable 1:1 complex in water mixture. These results represent a good starting point for the application of these molecular systems as building units for the design of new supramolecular architectures based on non-covalent interactions, which could be of interest in all fields related to supramolecular devices.

Metal nanoparticles (NPs) have physicochemical properties which are distinct from both the bulk and molecular metal species, and provide opportunities in fields such as catalysis and sensing. NPs typically require protection of their surface to impede aggregation, but these coatings can also block access to the surface which would be required to take advantage of their unusual properties. Here, we show that alkyl imidazoles can stabilise Pd, Pt, Au, and Ag NPs, and delineate the limits of their synthesis. These ligands provide an intermediate level of surface protection, for which we demonstrate proof‐of‐principle in catalysis and anion binding. Protecting the surface: Imidazole ligands offer a potentially useful intermediate level of stabilisation for metal nanoparticles. We outline the parameters required for synthesis of such nanoparticles and provide two case studies for their application, in catalysis and in sensing.

Design of flexible porous materials where the diffusion of guest molecules is regulated by the dynamics of contracted pore aperture is challenging. Here, a flexible porous self‐assembly consisting of 1D channels with dynamic bottleneck gates is reported. The dynamic pendant naphthimidazolylmethyl moieties at the channel necks provide kinetic gate function, that enables unusual adsorption for light hydrocarbons. The adsorption for CO2 is mainly dominated by thermodynamics with the uptakes decreasing with increasing temperature, whereas the adsorptions for larger hydrocarbons are controlled by both thermodynamics and kinetics resulting in an uptake maximum at a temperature threshold. Such an unusual adsorption enables temperature‐dependent separation of CO2 from the corresponding hydrocarbons. A porous flexible supramolecular material that is composed of vertexes sharing octahedra is assembled from dimeric [Mn2L2Cl2]2+ bearing pendant naphthimidazolylmethyl arms. The self‐assembly is characteristic of the channels with small dynamic gates. The local dynamics of the pendant naphthimidazolylmethyl arms leads to unusual diffusion‐regulatory adsorption of light hydrocarbons, thus leading to temperature‐dependent separation of CO2 from the corresponding hydrocarbons.

Four novel ZnII coordination polymers, [(ZnCl2)2(L)2]n (1), [(ZnBr2)2(L)2]n (2), and [(ZnI2)2(L)2]n (3) and [Zn(SCN)2]1.5(L)3n (4), have been synthesized based on 4′-ferrocenyl-3,2′:6′,3′′-terpyridine with ZnII ions and different coordination anions under similar ambient conditions. Their structures have been confirmed using single crystal X-ray diffraction analysis, showing that complexes 1–3 are one-dimensional (1D) double-stranded metal ion helical polymer chains and complex 4 is of a two-dimensional (2D) network. The structural transformations of them from a 1D polymer chain to a 2D network under the influence of the coordination anions has been systematic investigated. Furthermore, the optical band gaps have been measured by optical diffuse reflectance spectroscopy, revealing that the ligand and the complexes should have semiconductor properties.