Abstract
Mimicking the superstructures and properties of spherical biological encapsulants such as viral capsids1 and ferritin2 offers viable pathways to understand their chiral assemblies and functional roles in living systems. However, stereospecific assembly of artificial polyhedra with mechanical properties and guest-binding attributes akin to biological encapsulants remains a formidable challenge. Here we report the stereospecific assembly of dynamic supramolecular snub cubes from 12 helical macrocycles, which are held together by 144 weak C–H hydrogen bonds3. The enantiomerically pure snub cubes, which have external diameters of 5.1 nm, contain 2,712 atoms and chiral cavities with volumes of 6,215 Å3. The stereospecific assembly of left- and right-handed snub cubes was achieved by means of a hierarchical chirality transfer protocol4, which was streamlined by diastereoselective crystallization. In addition to their reversible photochromic behaviour, the snub cubes exhibit photocontrollable elasticity and hardness in their crystalline states. The snub cubes can accommodate numerous small guest molecules simultaneously and encapsulate two different guest molecules separately inside the uniquely distinct compartments in their frameworks. This research expands the scope of artificial supramolecular assemblies to imitate the chiral superstructures, dynamic features and binding properties of spherical biomacromolecules and also establishes a protocol for construction of crystalline materials with photocontrollable mechanical properties.
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Data availability
All the data that support this study are available within the paper and its Supplementary Information. Crystallographic data for the left- and right-handed SSCs (assembled from enantiopure (8S)Cy-(4S)CE-TM and (8R)Cy-(4R)CE-TM or obtained by diastereoselective crystallization), (8R)Cy-(4S)CE-TM and its enantiomer, (4R)Cy-OE-Triangle, as well as the three host–guest complexes of left- or right-handed SSCs are available free of charge from https://www.ccdc.cam.ac.uk under deposition numbers 2302158–2302161, 2377477, 2302162 and 2377478–2377480, respectively. An animation demonstrating the formation of the right-handed SSC is presented in Supplementary Video 1.
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Acknowledgements
We thank Tianjin University, the University of Hong Kong and Northwestern University for supporting this research. Some data collections were carried out in the Integrated Molecular Structure Education and Research Centre (IMSERC) facility at Northwestern University, which receives support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205) and Northwestern University. The work at Northwestern University on separating chiral compounds by chiral high-performance liquid chromatography was supported partially by the Center for Bio-Inspired Energy Science (CBES), an Energy Frontier Research Center funded by the US Department of Energy (DOE) Office of Basic Energy Sciences (no. DE-SC0000989). We also thank C. Zhu at Hefei University of Technology for support relating to the high-performance liquid chromatographic separations. We thank Z. Zhang at Nankai University, X. Li and Z. Chen at Shenzhen University for technical support relating to the single-crystal X-ray diffraction investigations. H.W. and Y.W. acknowledge funding support from the Excellent Young Scientists Fund Program (Overseas) of China and the National Natural Science Foundation of China (52473192). L.Ð. acknowledges the European Union (ERC, PhotoDark, 101077698) for funding. M.Y.Y. and W.A.G. thank the funding support from NIH (R01HL155532) and NSF (CBET 2311117). W.H. acknowledges funding support from the National Key Research and Development Program (2022YFB3603800) and the National Natural Science Foundation of China (52073210 and U21A6002). Views and opinions expressed are those of the authors only and do not necessarily reflect those of the European Union or the European Research Council. Computations were performed at the Quest HPC Cluster at Northwestern University and California Institute of Technology, as well as the HPC facility of the Computational Chemistry Community of Padova (C3P).
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H.W. and Y.W. conceived the research and carried out the main experiments and analyses. L.Đ., G.W. and S.I.S. did the high-performance liquid chromatography separation. P.K., S.B. and Y.Y. carried out the nanoindentation test. D.S. contributed to the graphical design. L.Đ., W.L., M.Y.Y. and W.A.G. conducted theoretical calculations. L.Z. prepared one of the precursors. B.-T. L. and C.L.S. carried out the X-ray crystallographic analyses. H.W., Y.W. and J.F.S. wrote the manuscript. A.X.-Y.C., L.F. and B.S. were involved in discussions and contributed to manuscript preparation. Y.W., W.H. and J.F.S. directed and supervised the research. All authors discussed the experimental results and contributed to the preparation of the manuscript.
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Extended data figures and tables
Extended Data Fig. 1 Driving forces for the formation of supramolecular snub cubes.
a, Non-covalent interactions between two adjacent twisted macrocycles in the right-handed SSC, portrayed in capped sticks. The macrocycles are stabilized by one [C − H···F] (red hatched line), two [C − H···O] (green hatched lines) and three [C − H···π] (magenta hatched lines) interactions. b, Independent gradient model (IGM) analysis shows the intermolecular interaction iso-surfaces between two adjacent twisted macrocycles. c, Independent gradient model (IGM) analysis of the non-covalent interactions within a right-handed SSC, portrayed in capped sticks, illustrating the intermolecular interaction iso-surfaces. The right-handed SSC is stabilized by 144 C − H week hydrogen bonds, made up of 24 [C − H···F], 48 [C − H···O] and 72 [C − H···π] interactions. Δκ inter (ρ) = 0.003 a.u. Ιso-surfaces are coloured according to a BGR scheme over the range –0.05 < sign(λ2)ρ < +0.05 a.u.
Extended Data Fig. 2 Stacking mode of the right-handed supramolecular snub cubes in the solid state.
a, Capped-stick representation of the two adjacent SSCs, showing the packing of the two square faces in neighbouring cubes sustained by [π···π] stacking (3.4 Å) of NDI units. There is a pore with a diameter of 0.8 nm at the centres of the square faces. b, A schematic diagram illustrating the stacking of the two adjacent SSCs, showing a pair of square faces in neighbouring cubes stacked with a rotational angle of 32.6° with respect to each other. c, d, Space-filling representation and schematic diagram illustrating the stacking mode of the four neighbouring SSCs.
Extended Data Fig. 3 Hierarchical porous framework of right-handed supramolecular snub cubes.
a, A truncated octahedron (purple) located at the centre of the cubic-shaped architecture composed of eight right-handed SSCs. b, The truncated octahedron (purple) is located in the cavity of a large spherical supramolecular polyhedron with a diameter of 6.6 nm, which is assembled from 24 twisted macrocycles (8R)Cy-(4R)CE-TM portrayed with capped sticks. c, Each truncated octahedron is connected to its neighbours by six apertures with diameters of 1.7 nm. The total volume of the truncated octahedron and its six apertures is 25,797 Å3. d, Capped-stick representation of the hierarchical porous superstructure of right-handed SSCs containing two different cavities (orange and purple spheres) and two sets (e and f) of independent porous networks. e, One of the porous networks is composed of the interior cavities (orange spheres) of the right-handed SSCs, which are interconnected by six apertures with diameters of 0.8 nm. f, The other set of porous networks consists of truncated octahedra (purple), interconnected by six apertures with diameters of 1.7 nm.
Extended Data Fig. 4 Assembly of right-handed supramolecular snub cubes employing diastereoselective crystallization.
a, Synthesis of a diastereoisomeric mixture of the four [2 + 2] macrocycles starting from racemic CE and (4R)Cy-NDIDA. The mixture contains 25% (8R)Cy-(4R)CE-TM and 25% (8R)Cy-(4S)CE-TM, while the remaining 50% can be assigned to another two twisted macrocycles (8R)Cy-(2R2S)CE-TM and (8R)Cy-(2S2R)CE-TM. (8R)Cy-(4S)CE-TM is the descriptor assigned to the (RRRRRRRR)Cy-(SSSS)CE-twisted macrocycle. (8R)Cy-(2R2S)CE-TM is the descriptor assigned to the (RRRRRRRR)Cy-(RRSS)CE-twisted macrocycle. (8R)Cy-(2S2R)CE-TM is the descriptor assigned to the (RRRRRRRR)Cy-(SSRR)CE-twisted macrocycle. The starting materials and products are portrayed using graphical representations. b, The diastereoselective crystallization of the (8R)Cy-(4R)CE-TM from a diastereoisomeric mixture of (8R)Cy-(4R)CE-TM, (8R)Cy-(4S)CE-TM, (8R)Cy-(2R2S)CE-TM, and (8R)Cy-(2S2R)CE-TM, leading to the formation of right-handed SSC.
Extended Data Fig. 5 Complexation of m-carborane and cyclohexane guest molecules inside left-handed supramolecular snub cubes.
a, Capped-stick and space-filling representations of the solid-state superstructures of the (8S)Cy-(4S)CE-TM (magenta) and a m-carborane molecule (red), respectively, showing that the m-carborane molecule is located in the inner compartment of the equilateral triangular supramolecular tile. b, Capped-stick and space-filling representations of the solid-state superstructures of the (8S)Cy-(4S)CE-TM (magenta) and cyclohexane molecules (green), respectively, showing that the cyclohexane molecules are located in the outer pocks of the equilateral triangular supramolecular tile. c, Capped-stick and space-filling representations of the solid-state superstructures of the (8S)Cy-(4S)CE-TM and guest molecules, respectively, showing the guests’ relative positions. d, The solid-state superstructure shows that the disordered m-carborane molecules (red) are located in the inner cavity of the left-handed SSC portrayed in capped sticks, while the cyclohexane molecules (green) occupy the outer pockets of the left-handed SSC. e, Capped-stick and space-filling representations of the porous framework of left-handed SSC (red) complexing m-carborane (red) and cyclohexane (green) guest molecules inside its dissimilar porous compartments. The m-carborane molecules are disordered on account of the fact that they are located in special positions inside the solid-state superstructure of SSCs.
Supplementary information
Supplementary Information (download PDF )
Supplementary Figs. 1–130, Tables 1–7, Text and Notes, extensive experimental data, theoretical calculation results and detailed discussions. Crystallographic data for the left- and right-handed SSCs (assembled from enantiopure (8S)Cy-(4S)CE-TM and (8R)Cy-(4R)CE-TM or obtained by diastereoselective crystallization), (8R)Cy-(4S)CE-TM and its enantiomer, (4R)Cy-OE-Triangle, as well as the three host–guest complexes of left- and right-handed SSCs are available free of charge from https://www.ccdc.cam.ac.uk under deposition numbers 2302158–2302161, 2377477, 2302162 and 2377478–2377480, respectively.
Supplementary Video 1 (download MP4 )
Animation demonstrating the formation of the right-handed SSC.
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Wu, H., Wang, Y., Đorđević, L. et al. Dynamic supramolecular snub cubes. Nature 637, 347–353 (2025). https://doi.org/10.1038/s41586-024-08266-3
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DOI: https://doi.org/10.1038/s41586-024-08266-3
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