Uncovering the Hidden Landscape of Tris(4?pyridyl) Ligands: Topological Complexity Derived from the Bridgehead

Supramolecular main group chemistry is a developing field which parallels the conventional domain of metallo-organic chemistry. Little explored building blocks in this area are metal-based ligands have appropriate donor symmetry to build desired molecular or extended arrangements. Tris(pyridyl) (E(py)3, E=main metal) potentially highly versatile since shifting N-donor arms from 2- 3-positions and 4-positions provides very simple way changing ligand character mononuclear/chelating multidentate/metal-bridging. Here, coordination behaviour first metal tris(4-pyridyl) ligands, E(4-py)3 (E=Sb, Bi, Ph?Sn) explored, as well their ability metal-organic frameworks (MOFs). The complicated topology these MOFs shows marked influence on counter anion switch mode, depending steric bridgehead. This structure-directing bridgehead potential strategy for future MOF design area.