Giant Expanded Porous Metallo-Hexagons.

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, H1 and H2. These hexagons feature large cavities, showcasing unique inner and outer hexagons fixed by specific connectivities for enhanced stability and high metal center density. H1 exhibits properties that can be transformed through the thermodynamic conversion of the metallopolymer formed by L1 and L2. With an edge length of 6.8 nm, H2 is 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.

Heteroleptic/Heterometallic Sierpinski Triangle with Room Temperature Fluorescence Emission and Photocatalytic Amine Oxidation Activity.

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 L1 and L2 are explained. A [Ru(bpy)3]2+ functionalized triangle S1 and a Sierpinski triangle S2 were synthesized in almost quantitative yields by the self-assembly of L1 with Zn2+ ions and by the heteroleptic self-assembly of L1 and L2 with Zn2+ ions, respectively. The Sierpinski triangle S2 contains 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 S1 and 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 S2 maintains 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.

The Marriage of Sierpinski Triangles and Platonic Polyhedra.

Fractal structures with self-similarity are of fundamental importance in the fields of aesthetic, chemistry and mathematics. Here, by taking advantage of constructs the rational geometry-directed precursor design, we report the construction of two fascinating Platonic solids, the Sierpinski tetrahedron ST-T and the Sierpinski octahedron ST-O, in which each possesses a fractal Sierpinski triangle on their independent faces. These two discrete complexes are formed in near-quantitative yield from the multi-component self-assembly of truncated Sierpinski triangular kernel L1 with tribenzotriquinacene-based hexatopic and anthracene-based tetratopic terpyridine ligands (L3 and L4 ) in the presence of metal ions, respectively. The enhanced stabilities of the 3D discrete structures were investigated by gradient tandem mass spectrometry (gMS2 ). This work provides new constructs for the imitation of complex virus assemblies and for the molecular encapsulation of giant guest molecules.