Desymmetrization of an Octahedral Coordination Complex Inside a Self‐Assembled Exoskeleton

摘要: The synthesis of a centrally functionalized, ribbon-shaped [6]polynorbornane ligand L that self-assembles with PdII cations into {Pd2L4} coordination cage is reported. shape-persistent contains two axial cationic centers and an array four equatorial H-bond donors pointing directly towards the center cavity. This precisely defined supramolecular environment complementary to geometry classic octahedral complexes [M(XY)6] six diatomic ligands. Very strong binding [Pt(CN)6]2− was observed, structure host–guest complex {[Pt(CN)6]@Pd2L4} supported by NMR spectroscopy, MS, X-ray data. self-assembled shell imprints its on encapsulated guest, desymmetrization platinum species influence D4h-symmetric second sphere evidenced IR spectroscopy. [Fe(CN)6]3− square-planar [Pt(CN)4]2− were strongly bound. Smaller anions such as [SiF6]2−, neutral carbonyl ([M(CO)6]; M=Cr, Mo, W) linear [Ag(CN)2]− anion only weakly bound, showing both size charge match are key factors for high-affinity binding.