You-Gui Huang

Viruses achieve remarkable complexity through the self-assembly of protein subunits, yet mimicking such processes synthetically has remained a grand challenge. While a 144-component metal-organic cage has been obtained, the maximum component count for known supramolecular assemblies of weak noncovalent forces is only 20. Here, we report a 62-component supramolecular cage assembled via a bioinspired strategy. By combining anion coordination with amide-π interactions, we construct a 62-component discrete dodecahedral cage structurally analogous to the dengue virus. This synthetic architecture, comprising three distinct molecular species held together via 60 H-bonds and 30 sets of amide-π interactions, demonstrates excellent stability in solution and exhibits multiple solid structural polymorphs. A reversible sol-gel transition is achieved by a mixture of the dodecahedra in acetylacetone (acac), which is driven by the host-guest–mediated higher-order assembly. These findings establish a previously unidentified paradigm for constructing multicomponent supramolecular cages, opening avenues for developing bioinspired molecular nanocontainers and providing a foundation for diverse nanotechnological applications.

Spontaneous chiral resolution was achieved in C ₃ -symmetric trinuclear silver clusters by tuning ligand steric effects and anions. Anion exchange reversibly switches homochiral and racemic polymorphs, enabling control of spontaneous resolution.

Spherical surfactant micelles, widely used as templates for synthesizing porous inorganic materials, suffer from undeterminable atomic-level structures. Developing structurally precise spherical micelle-like architectures is therefore highly beneficial for understanding template syntheses yet remains challenging. Here, we demonstrate a series of micelle-like π-stacked architectures self-assembled from tripodal synthons ([ML(SO₄)], [ML(SCN)]⁺, or [H₃L(HPO₄)]⁺, where M = Co²⁺ or Zn²⁺ and L = tris(2-benzimidazolylmethyl)amine). These structures form through anion-coordination-regulated π-π stacking. While a honeycomb architecture of oppositely aligned neutral [CoL(SO₄)] forms without the directing of anions, various cationic micelle-like π-stacked architectures of [ML(SCN)]⁺ and [H₃L(HPO₄)]⁺ are successfully constructed via anion coordination-regulated π-π stacking. Within these assemblies, the π-stacked tripodal synthons and the H-bonded anion networks mutually template each other, reminiscent of how surfactant micelles template porous inorganic materials. Remarkably, this approach yields two new Frank-Kasper (FK) C15 phases, representing the first FK C15 complexes formed by small-molecule assembly. These results establish a universal strategy leveraging the interplay between π-π stacking and anion coordination to access complex supramolecular FK structures, potentially enabling new synthetic approaches for porous inorganic materials such as zeolites and porous silicon.

Efficient deuterium separation from hydrogen isotopic mixtures poses a significant challenge due to the nearly identical physicochemical properties of D ₂ and H ₂ . Porous supramolecular assembly frameworks (SAFs) have emerged as promising candidates to address this issue, as their pore structures can be precisely tailored to achieve efficient hydrogen isotope separation. Herein, two metal‐hydroxide cluster‐based SAFs constructed from metal centers (Co ²⁺ and Cu ²⁺ ) coordinating with ligand L (HL = 1H‐benzo[f]isoindole‐1,3‐diimine) are reported. Solvothermal reaction of HL with Co(NO ₃ ) ₂ ·6H ₂ O yielded [Co ^II ₁₂ Co ^III ₈ L ₁₂ ( µ ₃ ‐OH) ₂₄ ]·12(NO ₃ ) ( 1 ) which lacks active sites. In contrast, a similar reaction using Cu(ClO ₄ ) ₂ ·6H ₂ O produced [Cu ₂₀ L ₈ ( µ ₃ ‐OH) ₂₄ (H ₂ O) ₈ ]·2(C ₂ H ₆ NH ₂ )·5(ClO ₄ )·2Cl·3(CHO ₂ ) ( 2 ), featuring both active Cu ²⁺ and = NH. Activated 2 exhibits the second‐highest D ₂ uptake of 301 cm ³ ·g ^‒1 at 77 K and 100 kPa, significantly surpassing that of activated 1 (87 cm ³ ·g ^‒1 ). Furthermore, activated 2 demonstrates exceptionally high D ₂ /H ₂ separation efficiency, with a D ₂ retention time of 52 min·g ^‒1 for a D ₂ /H ₂ /Ne mixture (2.5/2.5/95 vol.%) at a flow rate of 8 mL·min ^‒1 . Computational analyses indicate that the superior D ₂ /H ₂ uptake and separation of activated 2 can be attributed to the synergistic effect of its active Cu ²⁺ and = NH. These findings offer a novel strategy for incorporating multiple active adsorption sites into porous SAFs to optimize D ₂ /H ₂ uptake and separation.

Alkynes play a crucial role in chemical synthesis, bio-imaging, and drug design. Despite their significance, the intermolecular interactions involving alkynes have been largely unexplored. In this work, we unveil the previously overlooked alkyne-π interaction by comparing two zirconocene metal-organic cage compounds. The distinct stacking geometry in the single-crystal structures, coupling with the changes in C ≡ C vibrational signals, confirms the alkyne-π interaction as a genuine intermolecular interaction. Combining with computational studies, we reveal that alkyne-π interactions exert a substantial influence on the spectroscopic properties, despite being energetically less potent than π-π interactions. Our findings extend beyond theoretical implications. A comprehensive survey of the Cambridge Crystallographic Data Centre (CCDC) database corroborates the occurrence of alkyne-π interactions across hundreds of crystal structures, which provides a missing piece for fundamentally rationalizing their properties. Meanwhile, the changing C ≡ C vibrational signals, under alkyne-π interactions, may provide strategies for improving bio-imaging resolutions. It could also serve as a signature for desired alkyne-containing supramolecular structures. These results highlight the potential of alkyne-π interactions in designing functional materials for advanced applications in chemistry and biology.

The complete miscibility of polar N,N-dimethylformamide (DMF) with nonpolar benzene (PhH) challenges the classic "like-dissolves-like" principle, highlighting the need for a molecular-level understanding. By synergistically combining multiple research methods, we identified amide-π interactions as the pivotal driving force of this miscibility. First-principles calculations revealed a near-parallel DMF-PhH alignment resembling biological motifs. Meanwhile, the interaction energy of this amide-π stacking was intermediate between those of PhH-PhH (π-π stacking) and water-water (hydrogen bonding) systems. Energy decomposition analysis quantitatively indicated the hybrid nature of amide-π interactions arising from a combination of correlation/dispersion and electrostatics forces. We further demonstrated this interaction's structural dominance and generality through statistical analysis of the Cambridge Structural Database. This work not only resolves the DMF-PhH miscibility paradox but also establishes amide-π interactions as a universal solvation mechanism, providing theoretical guidance for the rational solvent screening in synthetic chemistry.