Self‐Assembly of Giant Spherical Liquid‐Crystalline Complexes and Formation of Nanostructured Dynamic Gels that Exhibit Self‐Healing Properties

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^II 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.     

Pressure‐Induced Polymerization and Electrical Conductivity of a Polyiodide

We report the high‐pressure structural characterization of an organic polyiodide salt in which a progressive addition of iodine to triiodide groups occurs. Compression leads to the initial formation of discrete heptaiodide units, followed by polymerization to a 3D anionic network. Although the structural changes appear to be continuous, the insulating salt becomes a semiconducting polymer above 10 GPa. The features of the pre‐reactive state and the polymerized state are revealed by analysis of the computed electron and energy densities. The unusually high electrical conductivity can be explained with the formation of new bonds.