Bottom-up construction of giant structures by the self-assembly of a large number of components (n = 100) has been a daunting challenge. Here, Fujita and colleagues report the self-assembly of a spherical metal polyhedron, possessing a hitherto unreported icosidodecahedron geometry with 30 vertices and 60 edges. The authors succeeded in controlling the self-assembly by intensive tuning of the ligand flexibility. X-ray crystallographic analysis confirmed that the complex is the largest well-defined spherical molecular capsule, comparable with the size of a typical protein.

H-beta zeolite with a Si/Al ratio of 75 uniquely shows high catalytic activity for the dehydration of sorbitol, giving a 76% yield of isosorbide at 400 K over 2 h.

The self-assembly of a cuboctahedral M12 L24 complex is traced by time-dependent NMR spectroscopy and mass spectrometry. The metastable intermediate structures that exist during the self-assembly process are not a chaotic mixture of numerous species, but instead are geometrically restricted. Short-lived M8 L16 (D4d ) and relatively long-lived M9 L18 (D3h ) are fully characterized as major intermediates. Employing a ligand with a smaller bend angle (112°) allows these two species to be kinetically trapped and more clearly observed by NMR spectroscopy. X-ray crystallography shows that M9 L18 has the framework topology predicted by geometric discussion.

Supramolecular self-assembly of 24 forklike mesogenic ligands and 12 transition metal ions led to the formation of giant spherical coordination complexes that exhibit liquid-crystalline (LC) phases. Self-healing LC supramolecular gels were also obtained through the introduction of these LC nanostructured supramolecular giant spherical complexes into dynamic covalent networks formed by cross-linkers and bifunctional polymers. The giant spherical structures of the Pd complexes with 72 rodlike moieties on the periphery were characterized by NMR, diffusion-ordered NMR spectroscopy, and mass spectrometry. These complexes are stable and exhibit lyotropic LC behavior, while the mesogenic ligands show thermotropic LC properties. The self-assembled LC structures of the spherical complexes can be tuned by the length of the rodlike moieties.