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Molecular self-assembly is a widely recognized approach for fabricating biomimetic functional nanostructures. Here, we report the synthesis of two giant hollow coronoid-like supramolecular hexagons, H1and H2. These hexagons feature large cavities, showcasing unique inner and outer hexagons fixed by specific connectivities for enhanced stability and high metal center density. H1exhibits properties that can be transformed through the thermodynamic conversion of the metallopolymer formed by L1and L2. With an edge length of 6.8 nm, H2is one of the largest hexagons reported to date. 1D and 2D NMR, TEM, ESI-MS, and TWIM-MS experiments provided conclusive evidence for the composition and structure of the assembled hexagons. This work demonstrates the feasibility of constructing giant supramolecular architectures with precise control over their size and shape, opening up new possibilities for the design and synthesis of sophisticated supramolecules and nonbiological materials.

Template-oriented multi-component synthesis method has been proven to be an exceedingly reasonable and excellent method for the synthesis of giant two-dimensional (2D) and three-dimensional (3D) supramolecules, but designing and constructing heteroleptic and controllable self-assembly without unexpected by-products remains a challenge. Here we report two discrete trefoil-shaped metallacycle S1and metallacage S2by heteroleptic self-assembly using one hexaphenylbenzene core ligand and two capping ligands. The 2D trefoil-shaped metallacycle S1could resemble the emblem of the classic ‘Mitsubishi’ motif. The use of template-oriented ligand and bent spacer ligand promotes the quantitative formation of the desired 3D trefoil-shaped metallacage S2. The formed metallacage S2possesses a molecular weight up to 36 kDa, diameter 6.6 nm and height 3.0 nm. All supramolecular coordination complexes were fully characterized by NMR spectroscopy (1H NMR, 2D COSY, 2D NOESY, 2D DOSY), high-resolution electrospray ionization mass spectrometry ESI-MS, ESI-TWIM-MS, TEM and AFM.

As a result of their optical and redox properties, bipyridyl (bpy) and terpyridyl (tpy) ruthenium complexes play vital roles in numerous domains. Herein, the design and synthesis of two bipyridyl and terpyridyl ruthenium(II) building units L1and L2are explained. A [Ru(bpy)3]2+functionalized triangle S1and a Sierpiński triangle S2were synthesized in almost quantitative yields by the self-assembly of L1with Zn2+ions and by the heteroleptic self-assembly of L1and L2with Zn2+ions, respectively. The Sierpiński triangle S2contains the coordination metals [Ru(bpy)3]2+, [Ru(tpy)2]2+, and [Zn(tpy)2]2+. According to research on the catalytic activity of amine oxidation on supramolecules S1and S2, the benzylamine substrates were nearly entirely transformed to N-benzylidenebenzylamine derivatives after 1 h under a Xe lamp. Furthermore, the observed ruthenium-containing terpyridyl supramolecule S2maintains high luminous performance at ambient temperature. This discovery opens up new possibilities for the rational molecular design of terpyridyl ruthenium fluorescent materials and catalytic functional materials.