Abstract
Hierarchical assembly is used to construct complex materials using elementary building units, mainly depending on the non-covalent interactions involving dynamic bonds. Here we present a hierarchical assembly strategy to build highly crystalline tubular frameworks. A multi-level assembly process driven by dynamic covalent bonds and coordination bonds is shown to produce a supramolecular nanotubular framework and three tubular covalent organic frameworks (COFs). These materials consist of well-ordered triangular nanotubes assembled in an oriented manner. In tubular COFs, the spacing between adjacent nanotubes can be systematically adjusted by altering the connector lengths to create mesoporous structures with adjustable pore size. Moreover, reversible transformations between tubular COFs and layered COFs were achieved by the reversible addition and removal of Zn(NO3)2. The facile demetallation–remetallation process confers tuneable structural properties to the materials and enables the layered COFs to serve as efficient ‘sponges’ for metal ions. This study represents a notable advance in hierarchical assembly; incorporating covalent bonding into this process is expected to greatly accelerate the development of new materials.
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Data availability
Crystallographic data for the structures reported in this article have been deposited at the Cambridge Crystallographic Data Centre under deposition numbers CCDC 2282802 (model compound M1), 2282805 (model compound M2) and 2282825 (the macrocycle, demetallated SNF-LIFM1). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. All data needed to evaluate the conclusions in the paper are present in the article or Supplementary Information. Source data are provided with this paper.
References
Gautieri, A., Vesentini, S., Redaelli, A. & Buehler, M. J. Hierarchical structure and nanomechanics of collagen microfibrils from the atomistic scale up. Nano Lett. 11, 757–766 (2011).
Kadler, K. E., Baldock, C., Bella, J. & Boot-Handford, R. P. Collagens at a glance. J. Cell Sci. 120, 1955–1958 (2007).
Yuan, C. et al. Hierarchically oriented organization in supramolecular peptide crystals. Nat. Rev. Chem. 3, 567–588 (2019).
Datta, S., Saha, M. L. & Stang, P. J. Hierarchical assemblies of supramolecular coordination complexes. Acc. Chem. Res. 51, 2047–2063 (2018).
Elemans, J. A. A. W., Rowan, A. E. & Nolte, R. J. M. Mastering molecular matter. Supramolecular architectures by hierarchical self-assembly. J. Mater. Chem. 13, 2661–2670 (2003).
Ikkala, O. & ten Brinke, G. Hierarchical self-assembly in polymeric complexes: towards functional materials. Chem. Commun. 2131–2137 (2004).
Rest, C., Kandanelli, R. & Fernández, G. Strategies to create hierarchical self-assembled structures via cooperative non-covalent interactions. Chem. Soc. Rev. 44, 2543–2572 (2015).
Cote, A. P. et al. Porous, crystalline, covalent organic frameworks. Science 310, 1166–1170 (2005).
Diercks, C. S. & Yaghi, O. M. The atom, the molecule, and the covalent organic framework. Science 355, eaal1585 (2017).
Ma, T. et al. Single-crystal X-ray diffraction structures of covalent organic frameworks. Science 361, 48–52 (2018).
Zhang, W. et al. Reconstructed covalent organic frameworks. Nature 604, 72–79 (2022).
Liu, Y. et al. Weaving of organic threads into a crystalline covalent organic framework. Science 351, 365–369 (2016).
Segura, J. L., Mancheño, M. J. & Zamora, F. Covalent organic frameworks based on Schiff-base chemistry: synthesis, properties and potential applications. Chem. Soc. Rev. 45, 5635–5671 (2016).
Geng, K. et al. Covalent organic frameworks: design, synthesis, and functions. Chem. Rev. 120, 8814–8933 (2020).
Veber, G. et al. Reticular growth of graphene nanoribbon 2D covalent organic frameworks. Chem 6, 1125–1133 (2020).
Iijima, S. Helical microtubules of graphitic carbon. Nature 354, 56–58 (1991).
Ghadiri, M. R., Granja, J. R., Milligan, R. A., McRee, D. E. & Khazanovich, N. Self-assembling organic nanotubes based on a cyclic peptide architecture. Nature 366, 324–327 (1993).
Chopra, N. G. et al. Boron nitride nanotubes. Science 269, 966–967 (1995).
Otsubo, K. et al. Bottom-up realization of a porous metal–organic nanotubular assembly. Nat. Mater. 10, 291–295 (2011).
Shimizu, T., Masuda, M. & Minamikawa, H. Supramolecular nanotube architectures based on amphiphilic molecules. Chem. Rev. 105, 1401–1444 (2005).
Korde, A. et al. Single-walled zeolitic nanotubes. Science 375, 62–66 (2022).
Li, G., Yu, W. & Cui, Y. A homochiral nanotubular crystalline framework of metallomacrocycles for enantioselective recognition and separation. J. Am. Chem. Soc. 130, 4582–4583 (2008).
Hummer, G., Rasaiah, J. C. & Noworyta, J. P. Water conduction through the hydrophobic channel of a carbon nanotube. Nature 414, 188–190 (2001).
Yamamoto, Y. et al. Photoconductive coaxial nanotubes of molecularly connected electron donor and acceptor layers. Science 314, 1761–1764 (2006).
Yan, Y. et al. Carbon nanotube catalysts: recent advances in synthesis, characterization and applications. Chem. Soc. Rev. 44, 3295–3346 (2015).
Picini, F. et al. Supramolecular polymerization of triarylamine-based macrocycles into electroactive nanotubes. J. Am. Chem. Soc. 143, 6498–6504 (2021).
Koner, K. et al. Porous covalent organic nanotubes and their assembly in loops and toroids. Nat. Chem. 14, 507–514 (2022).
Sun, C. et al. High aspect ratio nanotubes assembled from macrocyclic iminium salts. Proc. Natl Acad. Sci. USA 115, 8883–8888 (2018).
Strauss, M. J. et al. Lithium-conducting self-assembled organic nanotubes. J. Am. Chem. Soc. 143, 17655–17665 (2021).
Bong, D. T., Clark, T. D., Granja, J. R. & Ghadiri, M. R. Self-assembling organic nanotubes. Angew. Chem. Int. Ed. 40, 988–1011 (2001).
Gong, B. & Shao, Z. Self-assembling organic nanotubes with precisely defined, sub-nanometer pores: formation and mass transport characteristics. Acc. Chem. Res. 46, 2856–2866 (2013).
Maeda, K. et al. Construction of covalent organic nanotubes by light-induced cross-linking of diacetylene-based helical polymers. J. Am. Chem. Soc. 138, 11001–11008 (2016).
Strauss, M. J. et al. Divergent nanotube synthesis through reversible macrocycle assembly. Acc. Mater. Res. 3, 935–947 (2022).
Chaix, A. et al. Trianglamine-based supramolecular organic framework with permanent intrinsic porosity and tunable selectivity. J. Am. Chem. Soc. 140, 14571–14575 (2018).
Elbert, S. M. et al. Metal-assisted salphen organic frameworks (MaSOFs) with trinuclear metal units for synergic gas sorption. Chem. Mater. 31, 6210–6223 (2019).
Zhang, D., Ronson, T. K. & Nitschke, J. R. Functional capsules via subcomponent self-assembly. Acc. Chem. Res. 51, 2423–2436 (2018).
Browne, C., Ronson, T. K. & Nitschke, J. R. Palladium-templated subcomponent self-assembly of macrocycles, catenanes, and rotaxanes. Angew. Chem. Int. Ed. 53, 10701–10705 (2014).
Xu, H.-S. et al. Single crystal of a one-dimensional metallo-covalent organic framework. Nat. Commun. 11, 1434 (2020).
Li, K. et al. Stepwise assembly of Pd6(RuL3)8 nanoscale rhombododecahedral metal–organic cages via metalloligand strategy for guest trapping and protection. J. Am. Chem. Soc. 136, 4456–4459 (2014).
Nakamura, T., Ube, H., Shiro, M. & Shionoya, M. A self-assembled multiporphyrin cage complex through three different Zinc(II) center formation under well-balanced aqueous conditions. Angew. Chem. Int. Ed. 52, 720–723 (2013).
Yue, N. L. S., Jennings, M. C. & Puddephatt, R. J. Disilver(I) macrocycles: variation of cavity size with anion binding. Inorg. Chem. 44, 1125–1131 (2005).
Lozano-Castelló, D., Cazorla-Amorós, D. & Linares-Solano, A. Usefulness of CO2 adsorption at 273 K for the characterization of porous carbons. Carbon 42, 1233–1242 (2004).
Luo, Y. et al. High-throughput phase elucidation of polycrystalline materials using serial rotation electron diffraction. Nat. Chem. 15, 483–490 (2023).
Shen, B. et al. A single-molecule van der Waals compass. Nature 592, 541–544 (2021).
Svensson Grape, E. et al. Removal of pharmaceutical pollutants from effluent by a plant-based metal–organic framework. Nat. Water 1, 433–442 (2023).
Lazić, I., Bosch, E. G. T. & Lazar, S. Phase contrast STEM for thin samples: integrated differential phase contrast. Ultramicroscopy 160, 265–280 (2016).
Spitler, E. L. & Dichtel, W. R. Lewis acid-catalysed formation of two-dimensional phthalocyanine covalent organic frameworks. Nat. Chem. 2, 672–677 (2010).
Mu, Z. et al. Covalent organic frameworks with record pore apertures. J. Am. Chem. Soc. 144, 5145–5154 (2022).
Hussain, A., Chaniago, Y. D., Riaz, A. & Lee, M. Process design alternatives for producing ultra-high-purity electronic-grade propylene glycol monomethyl ether acetate. Ind. Eng. Chem. Res. 58, 2246–2257 (2019).
Acknowledgements
C.-Y.S. acknowledges the funding support from the NKRD Program of China (2021YFA1500401). H.-S.X. acknowledges the funding support from the National Natural Science Foundation of China (22101308), Natural Science Foundation of Guangdong Province (2022A1515011286) and Science and Technology Planning Project of Guangzhou (202201011156). C.-Y.S. acknowledges the funding support from the National Natural Science Foundation of China (21821003 and 21890380) and the LIRT Project of Guangdong PRT Program (2017BT01C161). K.P.L. acknowledges funding support from Singapore’s National Research Foundation Competitive Research Program NRF-CRP16-2015-02. T.W. and M.N. acknowledge the Swedish Research Council (VR, 2019-05465). We thank L. Jiang at Sun Yat-Sen University Instrumental Analysis and Research Center for collecting the single-crystal XRD data of demetallated SNF-LIFM1. We also thank the Inorganic and Elemental Analysis Platform at Sun Yat-Sen University Instrumental Analysis and Research Center for the support in conducting ICP analysis.
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Contributions
H.-S.X., C.-Y.S. and K.P.L. designed and led the project. H.-S.X. conceived the idea and performed the research. T.W. and M.N. conducted the STEM measurements. Y.L. carried out the 3D ED measurement. Y.L. and T.W. performed the crystal structure analysis. R.L. helped to prepare Fig. 1. W.-N.J., S.H., W.-D.Z., H.W. and T.C. helped to synthesize the building blocks and conduct the characterization. F.C., Q.G., X.L. and M.P. helped to interpret the results. H.-S.X., C.-Y.S., K.P.L. and T.W. wrote the paper.
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Supplementary information
Supplementary Information
Supplementary Text, Figs. 1–86 and Tables 1–7.
Supplementary Video 1
The demetallation and remetallation processes.
Supplementary Data 1
Crystallographic data for M1, CCDC 2282802.
Supplementary Data 2
Crystallographic data for M2, CCDC 2282805.
Supplementary Data 3
Crystallographic data for the macrocycle, CCDC 2282825.
Supplementary Data 4
Structural modelling for SNF-LIFM1.
Supplementary Data 5
Structural modelling for tubular COF-LIFM1.
Supplementary Data 6
Structural modelling for tubular COF-LIFM2.
Supplementary Data 7
Structural modelling for tubular COF-LIFM3.
Supplementary Data 8
Structural modelling for layered COF-LIFM1.
Supplementary Data 9
Structural modelling for layered COF-LIFM2.
Supplementary Data 10
Structural modelling for layered COF-LIFM3.
Source data
Source Data Fig. 2
The CO2 adsorption data at 195 K for SNF-LIFM1.
Source Data Fig. 4
The PXRD data of tubular COF-LIFM1, tubular COF-LIFM2 and tubular COF-LIFM3.
Source Data Fig. 5
The PXRD data of tubular COF-LIFM2 and layered COF-LIFM2.
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Xu, HS., Luo, Y., Li, R. et al. Hierarchical assembly of tubular frameworks driven by covalent and coordinate bonding. Nat. Synth (2024). https://doi.org/10.1038/s44160-024-00632-3
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DOI: https://doi.org/10.1038/s44160-024-00632-3
