He LHsu H.-KLi LLin L.-TTu T.-HOng T.-GLiou G.-GYI-TSU CHAN2022-04-252022-04-25202224519308https://www.scopus.com/inward/record.uri?eid=2-s2.0-85122927817&doi=10.1016%2fj.chempr.2021.11.013&partnerID=40&md5=843f74736b73e717b1128693b40ba725https://scholars.lib.ntu.edu.tw/handle/123456789/606852Quantitative self-assembly of three-dimensional (3D) giant molecules (>10 nm in diameter) with well-defined geometry remains an outstanding synthetic challenge. Here, we report the rational construction of a 10-nm-sized cuboctahedron using dynamic heteroleptic complexation and multivalent ligand design. The obtained molecular cuboctahedron contains a double-layered multicompartment structure, reminiscent of a self-balanced cable-strut tensile architecture. Its precisely designed shape and size lead to the hierarchical self-assembly into ordered square arrays with a lattice constant of 7.9 nm. Additionally, the local structures, such as dislocations and grain boundaries of packing domains, are also recognized by cryogenic electron microscopy (cryo-EM), which interrupt the regular patterns of square lattices and then result in the oblique arrays. The observed assembly of the giant cuboctahedra into supramolecular arrays provides a foundation for the bottom-up development of uniform two-dimensional (2D) materials. ? 2021 Elsevier Inc.heteroleptic complexationmolecular cuboctahedramultivalencySDG9: Industry innovation and infrastructureself-assemblysupramolecular arraysterpyridines[SDGs]SDG3[SDGs]SDG9[SDGs]SDG11journal article10.1016/j.chempr.2021.11.0132-s2.0-85122927817